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

PubMed

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

2008-09-15

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

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

PubMed

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.

ASSESSING SPECIATION AND RELEASE OF HEAVY METALS FROM COAL COMBUSTION PRODUCTS

EPA Science Inventory

In this study, the speciation of heavy metals such as arsenic, selenium, lead, zinc and mercury in coal combustion products (CCPs) was evaluated using sequential extraction procedures. Coal fly ash, bottom ash and flue gas desulphurization (FGD) sludge samples were used in the ex...

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

PubMed

Zhong, Huan; Wang, Wen-Xiong

2008-01-01

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

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

PubMed

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.

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA 1

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

Evaluation of arsenic speciation in rainbow trout and fathead minnows from dietary exposure

EPA Science Inventory

The concentration of total arsenic and various arsenic species were measured in food and fish tissue samples from two dietary arsenic exposures to juvenile fish. For arsenic speciation, samples were extracted with 10% MeOH and analyzed by HPLC/ICPMS. Total arsenic concentration...

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

USDA-ARS?s Scientific Manuscript database

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

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA - JOURNAL

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

Determination of the distribution and speciation of selenium in an argillaceous sample using chemical extractions and post-extractions analyses: application to the hydrogeological experimental site of Poitiers.

PubMed

Bassil, Joseph; Naveau, Aude; Bueno, Maïté; Di Tullo, Pamela; Grasset, Laurent; Kazpard, Véronique; Razack, Moumtaz

2016-05-01

To better understand selenium's dynamics in environmental systems, the present study aims to investigate selenium speciation and distribution in black argillaceous sediments, partially fulfilling karstic cavities into the Hydrogeological Experimental Site of Poitiers. These sediments are suspected to be responsible for selenium concentrations exceeding the European Framework Directive's drinking water limit value (10 μg L(-1)) in some specific wells. A combination of a sequential extractions scheme and single parallel extractions was thus applied on a representative argillaceous sample. Impacts of the extractions on mineral dissolution and organic matter mobilization were followed by quantifying major cations and total organic carbon (TOC) in the aqueous extracts. The nature of the released organic matter was characterized using thermochemolysis coupled with gas chromatography-mass spectrometry (GC-MS). About 10 % of selenium from the black argillaceous studied matrix could be defined as 'easily mobilizable' when the majority (around 70 %) revealed associated with the aliphatic and alkaline-soluble organic matter's fraction (about 20 %). In these fractions, selenium speciation was moreover dominated by oxidized species including a mixture of Se(VI) (20-30 %) and Se(IV) (70-80 %) in the 'easily mobilizable' fraction, while only Se(IV) was detected in alkaline-soluble organic matter fraction.

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

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

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

Bioleaching of vanadium from barren stone coal and its effect on the transition of vanadium speciation and mineral phase

NASA Astrophysics Data System (ADS)

Wang, Xin; Lin, Hai; Dong, Ying-bo; Li, Gan-yu

2018-03-01

This study determined the optimal conditions required to obtain maximum vanadium extraction and examined the transition of mineral phases and vanadium speciation during the bioleaching process. Parameters including the initial pH value, initial Fe2+ concentration, solid load, and inoculum quantity were examined. The results revealed that 48.92wt% of the vanadium was extracted through bioleaching under optimal conditions. Comparatively, the chemical leaching yield (H2SO4, pH 2.0) showed a slower and milder increase in vanadium yield. The vanadium bioleaching yield was 35.11wt% greater than the chemical leaching yield. The Community Bureau of Reference (BCR) sequential extraction results revealed that 88.62wt% of vanadium existed in the residual fraction. The bacteria substantially changed the distribution of the vanadium speciation during the leaching process, and the residual fraction decreased to 48.44wt%. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) results provided evidence that the crystal lattice structure of muscovite was destroyed by the bacteria.

THE LIBERATION OF ARSENOSUGARS FROM MATRIX COMPONENTS IN DIFFICULT TO EXTRACT SEAFOOD SAMPLES UTILIZING TMAOH/ACETIC ACID SEQUENTIALLY IN A TWO-STAGE EXTRACTION PROCESS

EPA Science Inventory

Sample extraction is one of the most important steps in arsenic speciation analysis of solid dietary samples. One of the problem areas in this analysis is the partial extraction of arsenicals from seafood samples. The partial extraction allows the toxicity of the extracted arse...

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

PubMed Central

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

Concentrations and speciation of arsenic in New England seaweed species harvested for food and agriculture.

PubMed

Taylor, Vivien F; Jackson, Brian P

2016-11-01

A survey of arsenic (As) concentrations and speciation was conducted on 10 species of seaweed from commercial harvesters and from collection at two sites in New England. Concentrations of As ranged from 4 to 106 mg/kg, mostly in the form of arsenosugars, with the distribution of arsenosugar analogs varying between taxa. In brown algae, As levels were correlated with phosphate concentrations, and arsenosugar speciation reflected differences in sulfur and phosphate concentrations between taxa. Several samples of the brown algae species Laminaria digitata contained significant levels of inorganic As (2.8-20 mg/kg), the most toxic form of As. A weak acid extraction with microwave heating was compared with a weaker methanol: water extraction method, and found to give slightly higher extraction efficiency with comparable relative concentrations of inorganic As, supporting the use of this faster and simpler extraction method for monitoring. Seaweed is a niche dietary item in the U.S. but its popularity is increasing; it is also used in agriculture and livestock farming which provide potential indirect routes for human exposure. The presence of occasional high concentrations of iAs, as well as the lack of toxicity studies on organic As species, suggest that monitoring of these high As foods is warranted. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sulfur Speciation and Extraction in Jet A (Briefing Charts)

DTIC Science & Technology

2015-08-16

Extraction fluid: denatured ethanol from Fisher Scientific and deionized water – Jet A fuel , approximately 500-800 ppm sulfur by weight – Data...Outline • Background • Experimental Setup – Extraction of sulfur compounds from fuel to alcohol/water extraction fluid – Each rinse is...Hydrophobic / Oleophillic Membrane Oleophobic / Hydrophillic Membrane Emulsion Phase Fuel Phase Water (Extraction Fluid) Phase DISTRIBUTION A

Speciation of AsIII and AsV in fruit juices by dispersive liquid–liquid microextraction and hydride generation-atomic fluorescence spectrometry

USDA-ARS?s Scientific Manuscript database

A new procedure was developed to speciate and quantify As(III) and As(V) in fruit juices. At pH 3.0, As(III) and ammonium pyrrolidine dithiocarbamate (APDC) formed a complex, which was extracted into carbon tetrachloride by dispersive liquid–liquid microextraction (DLLME) and subsequently quantified...

EFFECTS OF PH AND COMPETING ANIONS ON THE SPECIATION OF ARSENIC IN FIXED IONIC STRENGTH SOLUTIONS BY SOLID PHASE EXTRACTION CARTRIDGES

EPA Science Inventory

Anion-exchange resins (AERs) separate As(V) and As(lIl) in solution by retaining As(V) and allowing As(lIl) to pass through. AERs offer several advantages including portability, ease of use, and affordability (relative to other As speciation methods). The use of AERs for the inst...

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

EPA Science Inventory

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

Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection.

PubMed

Ponce de León, Claudia A; DeNicola, Katie; Montes Bayón, Maria; Caruso, Joseph A

2003-06-01

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.

The variations of aluminium species in mountainous forest soils and its implications to soil acidification.

PubMed

Bradová, Monika; Tejnecký, Václav; Borůvka, Luboš; Němeček, Karel; Ash, Christopher; Šebek, Ondřej; Svoboda, Miroslav; Zenáhlíková, Jitka; Drábek, Ondřej

2015-11-01

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008-2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al(3+) compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al(3+) and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al(3+) were determined in the summer, and the lowest in spring.

Iodine speciation in coastal and inland bathing waters and seaweeds extracts using a sequential injection standard addition flow-batch method.

PubMed

Santos, Inês C; Mesquita, Raquel B R; Bordalo, Adriano A; Rangel, António O S S

2015-02-01

The present work describes the development of a sequential injection standard addition method for iodine speciation in bathing waters and seaweeds extracts without prior sample treatment. Iodine speciation was obtained by assessing the iodide and iodate content, the two inorganic forms of iodine in waters. For the determination of iodide, an iodide ion selective electrode (ISE) was used. The indirect determination of iodate was based on the spectrophotometric determination of nitrite (Griess reaction). For the iodate measurement, a mixing chamber was employed (flow batch approach) to explore the inherent efficient mixing, essential for the indirect determination of iodate. The application of the standard addition method enabled detection limits of 0.14 µM for iodide and 0.02 µM for iodate, together with the direct introduction of the target water samples, coastal and inland bathing waters. The results obtained were in agreement with those obtained by ICP-MS and a colorimetric reference procedure. Recovery tests also confirmed the accuracy of the developed method which was effectively applied to bathing waters and seaweed extracts. Copyright © 2014 Elsevier B.V. All rights reserved.

Optimizing Standard Sequential Extraction Protocol With Lake And Ocean Sediments

EPA Science Inventory

The environmental mobility/availability behavior of radionuclides in soils and sediments depends on their speciation. Experiments have been carried out to develop a simple but robust radionuclide sequential extraction method for identification of radionuclide partitioning in sed...

Inorganic selenium speciation analysis in Allium and Brassica vegetables by ionic liquid assisted liquid-liquid microextraction with multivariate optimization.

PubMed

Castro Grijalba, Alexander; Martinis, Estefanía M; Wuilloud, Rodolfo G

2017-03-15

A highly sensitive vortex assisted liquid-liquid microextraction (VA-LLME) method was developed for inorganic Se [Se(IV) and Se(VI)] speciation analysis in Allium and Brassica vegetables. Trihexyl(tetradecyl)phosphonium decanoate phosphonium ionic liquid (IL) was applied for the extraction of Se(IV)-ammonium pyrrolidine dithiocarbamate (APDC) complex followed by Se determination with electrothermal atomic absorption spectrometry. A complete optimization of the graphite furnace temperature program was developed for accurate determination of Se in the IL-enriched extracts and multivariate statistical optimization was performed to define the conditions for the highest extraction efficiency. Significant factors of IL-VA-LLME method were sample volume, extraction pH, extraction time and APDC concentration. High extraction efficiency (90%), a 100-fold preconcentration factor and a detection limit of 5.0ng/L were achieved. The high sensitivity obtained with preconcentration and the non-chromatographic separation of inorganic Se species in complex matrix samples such as garlic, onion, leek, broccoli and cauliflower, are the main advantages of IL-VA-LLME. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantitative analysis of arsenic speciation in guano and ornithogenic sediments using microwave-assisted extraction followed by high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry.

PubMed

Lou, Chuangneng; Liu, Wenqi; Liu, Xiaodong

2014-10-15

Seabird guano is one of the main sources of nutrient fertilizers in remote coastal island areas, but guano-derived contaminants such as arsenic may cause serious threats to local ecosystems and public health issues. In this study, a new method was developed to analyze arsenic speciation in guano and ornithogenic sediments. Good extraction efficiencies of As(III) (arsenite), DMA (dimethylarsinate), MMA (monomethylarsonate) and As(V) (arsenate) were obtained by using 1.0molL(-1) orthophosphoric acid and 0.1molL(-1) ascorbic acid, followed by microwave-assisted extraction and high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS) detection. Under the optimized conditions, the extraction efficiencies of four arsenic species were over 80%. The relative standard deviations (RSDs) were 9.60, 6.15, 6.34 and 2.93% (n=7), and the detection limits (μgL(-1)) were 0.82, 2.38, 1.45 and 2.31 for As(III), DMA, MMA and As(V), respectively. This method was successfully used to determine arsenic speciation in the guano samples collected from the Xisha Islands of the South China Sea, and the results indicated that As(III) and As(V) were the dominant arsenic species in modern and ancient guano, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Speciation of vanadium in Chinese cabbage (Brassica rapa L.) and soils in response to different levels of vanadium in soils and cabbage growth.

PubMed

Tian, Liyan; Yang, Jinyan; Alewell, Christine; Huang, Jen-How

2014-09-01

This study highlights the accumulation and speciation of vanadium in Chinese cabbage (Brassica rapa L.) in relation to the speciation of soil vanadium with pot experiments at 122-622mgVkg(-1) by spiking NH4VO3. Cabbage planting decreased the bioavailable and residual vanadium based on sequential extraction, leading to enrichment of oxalate-extractable vanadium in soils. The biomass production increased with increasing concentrations of soil vanadium from 122 to 372mgVkg(-1), probably due to the increasing nitrogen availability and low vanadium availability in our soils with a consequent low vanadium toxicity. Although the concentrations of root vanadium (14.4-24.9mgVkg(-1)) related positively with soil vanadium, the bio-dilution alleviated the increase of leaf vanadium (2.1-2.7mgVkg(-1)). The predominance of vanadium(IV) in leaves (∼60-80% of total vanadium) indicates bio-reduction of vanadium in Chinese cabbage, since the mobile vanadium in oxic soils was usually pentavalent. Approximately 15-20% of the leaf vanadium was associated with recalcitrant leaf tissues. The majority of leaf vanadium was water and ethanol extractable, which is considered mobile and may cause more toxic effects on Chinese cabbage. Copyright © 2014 Elsevier Ltd. All rights reserved.

Changes in heavy metal bioavailability and speciation from a Pb-Zn mining soil amended with biochars from co-pyrolysis of rice straw and swine manure.

PubMed

Meng, Jun; Tao, Mengming; Wang, Lili; Liu, Xingmei; Xu, Jianming

2018-08-15

Biochar has been utilized as a good amendment to immobilize heavy metals in contaminated soils. However, the effectiveness of biochar in metal immobilization depends on biochar properties and metal species. In this study, the biochars produced from co-pyrolysis of rice straw with swine manure at 400°C were investigated to evaluate their effects on bioavailability and chemical speciation of four heavy metals (Cd, Cu, Pb and Zn) in a Pb-Zn contaminated soil through incubation experiment. Results showed that co-pyrolysis process significantly change the yield, ash content, pH, and electrical conductivity (EC) of the blended biochars compared with the single straw/manure biochar. The addition of these biochars significantly increased the soil pH, EC, and dissolved organic carbon (DOC) concentrations. The addition of biochars at a rate of 3% significantly reduced the CaCl 2 -extractable metal concentrations in the order of Pb>Cu>Zn>Cd. The exchangeable heavy metals decreased in all the biochar-amended soils whereas the carbonate-bound metal speciation increased. The increase in soil pH and the decrease in the CaCl 2 extractable metals indicated that these amendments can directly transform the highly availability metal speciation to the stable speciation in soils. In conclusion, biochar derived from co-pyrolysis of rice straw with swine manure at a mass ratio of 3:1 could most effectively immobilize the heavy metals in the soil. Copyright © 2018 Elsevier B.V. All rights reserved.

Magnetic solid-phase extraction combined with graphite furnace atomic absorption spectrometry for speciation of Cr(III) and Cr(VI) in environmental waters.

PubMed

Jiang, Hong-mei; Yang, Ting; Wang, Yan-hong; Lian, Hong-zhen; Hu, Xin

2013-11-15

A new approach of magnetic solid phase extraction (MSPE) coupled with graphite furnace atomic absorption spectrometry (GFAAS) has been developed for the speciation of Cr(III) and Cr(VI) using zincon-immobilized silica-coated magnetic Fe3O4 nanoparticles (Zincon-Si-MNPs) as the MSPE absorbent. Cr(III) was quantitatively reserved on the absorbent at pH 9.1 while total Cr was reserved at pH 6.5. The absorbed Cr species were eluted by using 2 mol/L HCl and detected by GFAAS. The concentration of Cr(VI) could be calculated by subtracting Cr(III) from total Cr. All the parameters affecting the separation and extraction efficiency of Cr species such as pH, extraction time, concentration and volume of eluent, sample volume and influence of co-existing ions were systematically examined and the optimized conditions were established accordingly. The detection limit (LOD) of the method was 0.016 and 0.011 ng mL(-1) for Cr(III) and Cr(VI), respectively, with the enrichment factor of 100 and 150. The precisions of this method (Relative standard deviation, RSD, n=7) for Cr(III) and Cr(VI) at 0.1 ng mL(-1) were 6.0% and 6.2%, respectively. In order to validate the proposed method, a certified reference material of environmental water was analyzed, and the result of Cr speciation was in good agreement with the certified value. This MSPE-GFAAS method has been successfully applied for the speciation of Cr(III) and Cr(VI) in lake and tap waters with the recoveries of 88-109% for the spiked samples. Moreover, the MSPE separation mechanism of Cr(III) and Cr(VI) based on their adsorption-desorption on Zincon-Si-MNPs has been explained through various spectroscopic characterization. © 2013 Elsevier B.V. All rights reserved.

Speciation of antimony in airborne particulate matter using ultrasound probe fast extraction and analysis by HPLC-HG-AFS.

PubMed

Bellido-Martín, A; Gómez-Ariza, J L; Smichowsky, P; Sánchez-Rodas, D

2009-09-07

A fast extraction procedure has been developed for Sb(III) and Sb(V) oxoanions speciation in airborne particulate matter samples. Different extraction media (diammonium tartrate, hidroxilammonium clorhidrate, citric acid+ascorbic acid, phosphoric acid and citrate solutions) were tried, with assistance of an ultrasonic probe. The operation power and time of extraction were also optimized. The higher extraction recoveries were obtained with a 100 mmol L(-1) hidroxilammonium clorhidrate aqueous solution assisted by the ultrasound probe operated at 50 W during 3 min. The extracts were analyzed by HPLC-HG-AFS. The chromatographic separation of Sb(III) and Sb(V) was also optimized using diammonium tartrate and phthalic acid as mobile phases. The separation of both Sb species was performed in less than 3 min under isocratic conditions, using a 200 mmol L(-1) diammonium tartrate solution. The proposed extraction procedure and the HPLC-HG-AFS instrumental coupling have been successfully applied to airborne particulate matter samples, with high Sb content, collected in heavy traffic streets from Buenos Aires (Argentina). The results showed the presence of both Sb species at similar concentrations in the ng m(-3) level. The extraction yield was higher than 90% for all the analyzed samples.

[Remediation efficiency of lead-contaminated soil at an industrial site by ultrasonic-assisted chemical extraction].

PubMed

Wang, Xin-jie; Huang, Jin-lou; Liu, Zhi-qiang; Yue, Xi

2013-09-01

This research chose five lead-contaminated sites of a lead-acid battery factory to analyze the speciation distribution and concentration of lead. Under the same conditions (0.1 mol x L(-1) EDTA,30 min, 25 degrees C), the removal effect of heavy metal was compared between ultrasonic-assisted chemical extraction (UCE) and conventional chemical extraction ( CCE), and the variation of lead speciation was further explored. The results showed that the lead removal efficiency of UCE was significantly better than CCE. The lead removal efficiency of WS, A, B, C and BZ was 10.06%, 48.29%, 48.69%, 53.28% and 36.26% under CCE. While the removal efficiency of the UCE was 22.42%, 69.31%, 71.00%, 74.49% and 71.58%, with the average efficiency higher by 22%. By comparing the speciation distribution of the two washing methods, it was found that the acid extractable content maintained or decreased after UCE, whereas it showed an increasing trend after CCE. The reduction effect of the reducible was as high as 98% by UCE. UCE also showed a more efficient reduction effect of the organic matter-sulfite bounded form and the residual form. Hence, it is feasible to improve the washing efficiency of heavy metal contained in soil by conducting the cleaning process with the help of ultrasonic wave, which is a simple and fast mean to remove lead from contaminated sites.

Dispersion, Speciation, and Pollution Assessment of Heavy Metals Pb and Zn in Surface Sediment from Disturbed Ecosystem of Jeneberang Waters

NASA Astrophysics Data System (ADS)

Najamuddin; Surahman

2017-10-01

Surface sediments were collected from seventeen stations in Jeneberang waters (riverine, estuarine, and marine). Lead (Pb) and zinc (Zn) concentrations were determined by atomic absorption spectrometry, and the speciation of metals was obtained by a sequential extraction procedure. Dispersion of Pb and Zn were found higher in the riverine and marine samples than the estuarine samples. Following speciation, the metals were found similar composition of fraction in the riverine and estuarine samples but any different in the marine samples. The results indicated that there is a change of dispersion pattern and speciation composition of metals due to the presence of the dam that lies at the boundary between the estuary and the river. The toxicity unit was indicated low toxicity level; pollution level was in weakly to moderately polluted while the aquatic environment risk attributed were no risky to light risk.

DETECTION OF ARSENOSUGARS FROM KELP EXTRACTS VIA IC-ELECTROSPRAY IONIZATION-MS-MS AND IC MEMBRANE HYDRIDE GENERATION ICP-MS

EPA Science Inventory

The selectivity and the ability to obtain structural information from detection schemes used in arsenic speciation research are growing analytical requirements driven by the growing number of arsenicalS extracted from natural products and the need to minimize misidentification in...

Determination of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Matos Reyes, M. N.; Cervera, M. L.; Campos, R. C.; de la Guardia, M.

2007-09-01

A fast, sensitive and simple non-chromatographic analytical method was developed for the speciation analysis of toxic arsenic species in cereal samples, namely rice and wheat semolina. An ultrasound-assisted extraction of the toxic arsenic species was performed with 1 mol L - 1 H 3PO 4 and 0.1% (m/v) Triton XT-114. After extraction, As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) concentrations were determined by hydride generation atomic fluorescence spectrometry using a series of proportional equations corresponding to four different experimental reduction conditions. The detection limits of the method were 1.3, 0.9, 1.5 and 0.6 ng g - 1 for As(III), As(V), DMA and MMA, respectively, expressed in terms of sample dry weight. Recoveries were always greater than 90%, and no species interconversion occurred. The speciation analysis of a rice flour reference material certified for total arsenic led to coherent results, which were also in agreement with other speciation studies made on the same certified reference material.

[Analysis of primary elemental speciation distribution in mungbean during enzymatic hydrolization].

PubMed

Li, Ji-Hua; Huang, Mao-Fang; Zhu, De-Ming; Zheng, Wei-Wan; Zhong, Ye-Jun

2009-03-01

In the present paper, trace elements contents of cuprum, zincum, manganese and ferrum in mungbean and their primary speciation distribution during enzymatic hydrolization were investigated with ICP-AES OPTIMA 5300DV plasma emission spectroscopy. The trace elements were separated into two forms, i.e. dissolvable form and particulate form, by cellulose membrane with 0.45 microm of pore diameter. All the samples were digested by strong acid (perchloric acid and nitric acid with 1 : 4 ratio ). The parameters of primary speciations of the four elements were calculated and discussed. The results showed: (1) Contents of cuprum, zincum, manganese and ferrum in mungbean were 12.77, 31.26, 18.14 and 69.38 microg x g(-1) (of dry matter), respectively. Different treatment resulted in different elemental formulation in product, indicating that more attention should be paid to the trace elements pattern when producing mungbean beverage with different processes. (2) Extraction rates of cuprum, zincum, manganese and ferrum in extract were 68.84%, 51.84%, 63.97% and 30.40% with enzymatic treatments and 36.22%, 17.58%, 7.85% and 22.99% with boil treatment, respectively. Both boil and enzymatic treatments led to poor elemental extraction rates, which proved that it was necessary to take deep enzymatic hydrolysis treatment in mungbean beverage process as the trace element utilization rate was concerned. (3) Amylase, protease and cellulose showed different extraction effectiveness of the four trace elements. Generally, protease exhibited highest efficiency for the four elements extraction. All of the four trace elements were mostly in dissolvable form in all hydrolysates and soup. (4) Relative standard deviations and recovery yields are within 0.12%-0.90% (n = 11) and 98.6%-101.4%, respectively. The analysis method in this paper proved to be accurate.

Ultrasensitive Speciation Analysis of Mercury in Rice by Headspace Solid Phase Microextraction Using Porous Carbons and Gas Chromatography-Dielectric Barrier Discharge Optical Emission Spectrometry.

PubMed

Lin, Yao; Yang, Yuan; Li, Yuxuan; Yang, Lu; Hou, Xiandeng; Feng, Xinbin; Zheng, Chengbin

2016-03-01

Rice consumption is a primary pathway for human methylmercury (MeHg) exposure in inland mercury mining areas of Asia. In addition, the use of iodomethane, a common fumigant that significantly accelerates the methylation of mercury in soil under sunlight, could increase the MeHg exposure from rice. Conventional hyphenated techniques used for mercury speciation analysis are usually too costly for most developing countries. Consequently, there is an increased interest in the development of sensitive and inexpensive methods for the speciation of mercury in rice. In this work, gas chromatography (GC) coupled to dielectric barrier discharge optical emission spectrometry (DBD-OES) was developed for the speciation analysis of mercury in rice. Prior to GC-DBD-OES analysis, mercury species were derivatized to their volatile species with NaBPh4 and preconcentrated by headspace solid phase microextraction using porous carbons. Limits of detection of 0.5 μg kg(-1) (0.16 ng), 0.75 μg kg(-1) (0.24 ng), and 1.0 μg kg(-1) (0.34 ng) were obtained for Hg(2+), CH3Hg(+), and CH3CH2Hg(+), respectively, with relative standard deviations (RSDs) better than 5.2% and 6.8% for one fiber or fiber-to-fiber mode, respectively. Recoveries of 90-105% were obtained for the rice samples, demonstrating the applicability of the proposed technique. Owing to the small size, low power, and low gas consumption of DBD-OES as well as efficient extraction of mercury species by porous carbons headspace solid phase micro-extraction, the proposed technique provides several advantages including compactness, cost-effectiveness, and potential to couple with miniature GC to accomplish the field speciation of mercury in rice compared to conventional hyphenated techniques.

Organotin speciation in environmental matrices by automated on-line hydride generation-programmed temperature vaporization-capillary gas chromatography-mass spectrometry detection.

PubMed

Serra, H; Nogueira, J M F

2005-11-11

In the present contribution, a new automated on-line hydride generation methodology was developed for dibutyltin and tributyltin speciation at the trace level, using a programmable temperature-vaporizing inlet followed by capillary gas chromatography coupled to mass spectrometry in the selected ion-monitoring mode acquisition (PTV-GC/MS(SIM)). The methodology involves a sequence defined by two running methods, the first one configured for hydride generation with sodium tetrahydroborate as derivatising agent and the second configured for speciation purposes, using a conventional autosampler and data acquisition controlled by the instrument's software. From the method-development experiments, it had been established that injector configuration has a great effect on the speciation of the actual methodology, particularly, the initial inlet temperature (-20 degrees C; He: 150 ml/min), injection volume (2 microl) and solvent characteristics using the solvent venting mode. Under optimized conditions, a remarkable instrumental performance including very good precision (RSD < 4%), excellent linear dynamic range (up to 50 microg/ml) and limits of detection of 0.12 microg/ml and 9 ng/ml, were obtained for dibutyltin and tributyltin, respectively. The feasibility of the present methodology was validated through assays upon in-house spiked water (2 ng/ml) and a certified reference sediment matrix (Community Bureau of Reference, CRM 462, Nr. 330 dibutyltin: 68+/-12 ng/g; tributyltin: 54+/-15 ng/g on dry mass basis), using liquid-liquid extraction (LLE) and solid-phase extraction (SPE) sample enrichment and multiple injections (2 x 5 microl) for sensitivity enhancement. The methodology evidenced high reproducibility, is easy to work-up, sensitive and showed to be a suitable alternative to replace the currently dedicated analytical systems for organotin speciation in environmental matrices at the trace level.

INVESTIGATION OF ARSENIC SPECIATION ON DRINKING WATER TREATMENT MEDIA UTILIZING AUTOMATED SEQUENTIAL CONTINUOUS FLOW EXTRACTION WITH IC-ICP-MS DETECTION

EPA Science Inventory

Three treatment media, used for the removal of arsenic from drinking water, were sequentially extracted using 10mM MgCl2 (pH 8), 10mM NaH2PO4 (pH 7) followed by 10mM (NH4)2C2O4 (pH 3). The media were extracted using an on-line automated continuous extraction system which allowed...

Chemical fractionation of heavy metals in urban soils of Guangzhou, China.

PubMed

Lu, Ying; Zhu, Feng; Chen, Jie; Gan, Haihua; Guo, Yanbiao

2007-11-01

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominantly located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron-Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.

Development of an analytical method for antimony speciation in vegetables by HPLC-hydride generation-atomic fluorescence spectrometry.

PubMed

Olivares, David; Bravo, Manuel; Feldmann, Jorg; Raab, Andrea; Neaman, Alexander; Quiroz, Waldo

2012-01-01

A new method for antimony speciation in terrestrial edible vegetables (spinach, onions, and carrots) was developed using HPLC with hydride generation-atomic fluorescence spectrometry. Mechanical agitation and ultrasound were tested as extraction techniques. Different extraction reagents were evaluated and optimal conditions were determined using experimental design methodology, where EDTA (10 mmol/L, pH 2.5) was selected because this chelate solution produced the highest extraction yield and exhibited the best compatibility with the mobile phase. The results demonstrated that EDTA prevents oxidation of Sb(III) to Sb(V) and maintains the stability of antimony species during the entire analytical process. The LOD and precision (RSD values obtained) for Sb(V), Sb(III), and trimethyl Sb(V) were 0.08, 0.07, and 0.9 microg/L and 5.0, 5.2, and 4.7%, respectively, for a 100 microL sample volume. The application of this method to real samples allowed extraction of 50% of total antimony content from spinach, while antimony extracted from carrots and onion samples ranged between 50 and 60 and 54 and 70%, respectively. Only Sb(V) was detected in three roots (onion and spinach) that represented 60-70% of the total antimony in the extracts.

Occurrence of inorganic arsenic in edible Shiitake (Lentinula edodes) products.

PubMed

Llorente-Mirandes, Toni; Barbero, Mercedes; Rubio, Roser; López-Sánchez, José Fermín

2014-09-01

The present study reports arsenic speciation analysis in edible Shiitake (Lentinula edodes) products. The study focused on the extraction, and accurate quantification of inorganic arsenic (iAs), the most toxic form of arsenic, which was selectively separated and determined using anion exchange LC-ICPMS. A wide variety of edible Shiitake products (fresh mushrooms, food supplements, canned and dehydrated) were purchased and analysed. A cultivated Shiitake grown under controlled conditions was also analysed. The extraction method showed satisfactory extraction efficiencies (>90%) and column recoveries (>85%) for all samples. Arsenic speciation revealed that iAs was the major As compound up to 1.38 mg As kg(-1) dm (with a mean percentage of 84% of the total arsenic) and other organoarsenicals were found as minor species. Shiitake products had high proportions of iAs and therefore should not be ignored as potential contributors to dietary iAs exposure in populations with a high intake of Shiitake products. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

Iwai, Takahiro; Chiba, Koichi; Narukawa, Tomohiro

2016-01-01

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

Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction.

PubMed

Minkina, Tatiana; Nevidomskaya, Dina; Bauer, Tatiana; Shuvaeva, Victoria; Soldatov, Alexander; Mandzhieva, Saglara; Zubavichus, Yan; Trigub, Alexander

2018-09-01

For a correct assessment of risk of polluted soil, it is crucial to establish the speciation and mobility of the contaminants. The aim of this study was to investigate the speciation and transformation of Zn in strongly technogenically transformed contaminated Spolic Technosols for a long time in territory of sludge collectors by combining analytical techniques and synchrotron techniques. Sequential fractionation of Zn compounds in studied soils revealed increasing metal mobility. Phyllosilicates and Fe and Mn hydroxides were the main stabilizers of Zn mobility. A high degree of transformation was identified for the composition of the mineral phase in Spolic Technosols by X-ray powder diffraction. Technogenic phases (Zn-containing authigenic minerals) were revealed in Spolic Technosols samples through the analysis of their Zn K-edge EXAFS and XANES spectra. In one of the samples Zn local environment was formed by predominantly oxygen atoms, and in the other one mixed ZnS and ZnO bonding was found. Zn speciation in the studied technogenically transformed soils was due to the composition of pollutants contaminating the floodplain landscapes for a long time, and, second, this is the combination of physicochemical properties controlling the buffer properties of investigated soils. X-ray spectroscopic and X-ray powder diffraction analyses combined with sequential extraction assays is an effective tool to check the affinity of the soil components for heavy metal cations. Copyright © 2018 Elsevier B.V. All rights reserved.

Polonium-210 and selenium in tissues and tissue extracts of the mussel Mytilus galloprovincialis (Gulf of Trieste).

PubMed

Kristan, Urška; Planinšek, Petra; Benedik, Ljudmila; Falnoga, Ingrid; Stibilj, Vekoslava

2015-01-01

Marine organisms such as mussels and fish take up polonium (Po) and selenium (Se), and distribute them into different cellular components and compartments. Due to its high radiotoxicity and possible biomagnification across the marine food chain Po-210 is potentially hazardous, while selenium is an essential trace element for humans and animals. The aim of this study was to investigate and compare the presence and extractability of the elements in the mussels Mytilus galloprovincialis collected in the Gulf of Trieste. The levels of Po-210 in the samples ranged from 220 to 400 Bq kg(-1) and of Se from 2.6 to 8.2 mg kg(-1), both on a dry matter basis. Using various extraction types and conditions in water, buffer or enzymatic media, the best extractability was obtained with enzymatic extraction (Protease XIV, 1h shaking at 40 °C) and the worst by water extraction (24 h shaking at 37 °C). 90% of Po-210 and 70% of Se was extractable in the first case versus less than 10% of Po-210 and less than 40% of Se in the second. Such evident differences in extractability between the investigated elements point to different metabolic pathways of the two elements. In enzymatic extracts Se speciation revealed three Se compounds (SeCys2, SeMet, one undefined), while Po-210 levels were too low to allow any conclusions about speciation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Speciation evolution of zinc and copper during pyrolysis and hydrothermal carbonization treatments of sewage sludges

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

Huang, Rixiang; Zhang, Bei; Saad, Emily M.

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)more » 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.« less

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

PubMed

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

2013-03-22

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

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

PubMed

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

2015-02-01

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

Dispersive micro-solid phase extraction combined with dispersive liquid-liquid microextraction for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chen, Shizhong; Zhu, Shengping; Lu, Dengbo

2018-01-01

A method was developed for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after preconcentration/separation using dispersive micro-solid phase extraction (DMSPE) and dispersive liquid-liquid micro-extraction (DLLME). In DMSPE, titanium dioxide nanofibers were used for preconcentration and separation of analytes. The upper aqueous phase and elution solution from DMSPE were used for further preconcentration and separation of Sb(III) and Sb(V) by DLLME without any pre-oxidation or pre-reduction operation, respectively. The extracts from DLLME were used for ETV-ICP-MS determination with APDC as a chemical modifier. Under optimal conditions, the detection limits of this method were 0.019 and 0.025 pg mL- 1 with relative standard deviations of 5.7% and 6.9% for Sb(III) and Sb(V) (c = 1.0 ng mL- 1, n = 9), respectively. This method was applied for speciation analysis of Sb and its distribution in the tea leaves and the tea infusion, including total, suspended, soluble, organic and inorganic Sb as well as Sb(III) and Sb(V). The results showed that the contents of Sb are 62.7, 12.9 and 47.3 ng g- 1 in the tea leaves, tea residue and tea soup, respectively; those of soluble, organic, inorganic, Sb(III) and Sb(V) are 0.41, 0.11, 0.29, 0.21 and 0.07 ng mL- 1 in the tea soup, respectively. A certified reference material of tea leaves (GBW 07605) was analyzed by this method with satisfactory results.

Evaluation of microwave and ultrasound extraction procedures for arsenic speciation in bivalve mollusks by liquid chromatography-inductively coupled plasma-mass spectrometry

NASA Astrophysics Data System (ADS)

Santos, Clarissa M. M.; Nunes, Matheus A. G.; Barbosa, Isa S.; Santos, Gabriel L.; Peso-Aguiar, Marlene C.; Korn, Maria G. A.; Flores, Erico M. M.; Dressler, Valderi L.

2013-08-01

Liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS) was used for arsenic speciation analysis in tissues of bivalve mollusks (Anomalocardia brasiliana sp. and Macoma constricta sp.). Microwave and ultrasound radiation, combined with different extraction conditions (solvent, sample amount, time, and temperature), were evaluated for As-species extraction from the mollusks' tissues. Accuracy, extraction efficiency, and the stability of As species were evaluated by analyzing certified reference materials (DORM-2, dogfish muscle; BCR-627, tuna fish tissue; and SRM 1566b, oyster tissue) and analyte recovery tests. The best conditions were found to be microwave-assisted extraction using 200 mg of samples and water at 80 °C for 6 min. The agreement of As-species concentration in samples ranged from 97% to 102%. Arsenobetaine (AsB) was the main species present in bivalve mollusk tissues, while monomethylarsonic acid (MMA) and arsenate (As(V)) were below the limit of quantification (0.001 and 0.003 μg g- 1, respectively). Two unidentified As species also were detected and quantified. The sum of the As-species concentration was in agreement (90 to 104%), with the total As content determined by ICP-MS after sample digestion.

Speciation analysis of antimony in extracts of size-classified volcanic ash by HPLC-ICP-MS.

PubMed

Miravet, R; López-Sánchez, J F; Rubio, R; Smichowski, P; Polla, G

2007-03-01

Although there is concern about the presence of toxic elements and their species in environmental matrices, for example water, sediment, and soil, speciation analysis of volcanic ash has received little attention. Antimony, in particular, an emerging element of environmental concern, has been less studied than other potentially toxic trace elements. In this context, a study was undertaken to assess the presence of inorganic Sb species in ash emitted from the Copahue volcano (Argentina). Antimony species were extracted from size-classified volcanic ash (<36 microm, 35-45 microm, 45-150 microm, and 150-300 microm) by use of 1 mol L(-1) citrate buffer at pH 5. Antimony(III) and (V) in the extracts were separated and quantified by high-performance liquid chromatography combined on-line with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Antimony species concentrations (microg g(-1)) in the four fractions varied from 0.14 to 0.67 for Sb(III) and from 0.02 to 0.03 for Sb(V). The results reveal, for the first time, the occurrence of both inorganic Sb species in the extractable portion of volcanic ash. Sb(III) was always the predominant species.

Multifactorial genetic divergence processes drive the onset of speciation in an Amazonian fish

PubMed Central

Torrente-Vilara, Gislene; Quilodran, Claudio; Rodrigues da Costa Doria, Carolina; Montoya-Burgos, Juan I.

2017-01-01

Understanding the processes that drive population genetic divergence in the Amazon is challenging because of the vast scale, the environmental richness and the outstanding biodiversity of the region. We addressed this issue by determining the genetic structure of the widespread Amazonian common sardine fish Triportheus albus (Characidae). We then examined the influence, on this species, of all previously proposed population-structuring factors, including isolation-by-distance, isolation-by-barrier (the Teotônio Falls) and isolation-by-environment using variables that describe floodplain and water characteristics. The population genetics analyses revealed an unusually strong structure with three geographical groups: Negro/Tapajós rivers, Lower Madeira/Central Amazon, and Upper Madeira. Distance-based redundancy analyses showed that the optimal model for explaining the extreme genetic structure contains all proposed structuring factors and accounts for up to 70% of the genetic structure. We further quantified the contribution of each factor via a variance-partitioning analysis. Our results demonstrate that multiple factors, often proposed as individual drivers of population divergence, have acted in conjunction to divide T. albus into three genetic lineages. Because the conjunction of multiple long-standing population-structuring processes may lead to population reproductive isolation, that is, the onset of speciation, we suggest that the multifactorial population-structuring processes highlighted in this study could account for the high speciation rate characterising the Amazon Basin. PMID:29261722

A synthesis of the theories and concepts of early human evolution.

PubMed

Maslin, Mark A; Shultz, Susanne; Trauth, Martin H

2015-03-05

Current evidence suggests that many of the major events in hominin evolution occurred in East Africa. Hence, over the past two decades, there has been intensive work undertaken to understand African palaeoclimate and tectonics in order to put together a coherent picture of how the environment of Africa has varied over the past 10 Myr. A new consensus is emerging that suggests the unusual geology and climate of East Africa created a complex, environmentally very variable setting. This new understanding of East African climate has led to the pulsed climate variability hypothesis that suggests the long-term drying trend in East Africa was punctuated by episodes of short alternating periods of extreme humidity and aridity which may have driven hominin speciation, encephalization and dispersals out of Africa. This hypothesis is unique as it provides a conceptual framework within which other evolutionary theories can be examined: first, at macro-scale comparing phylogenetic gradualism and punctuated equilibrium; second, at a more focused level of human evolution comparing allopatric speciation, aridity hypothesis, turnover pulse hypothesis, variability selection hypothesis, Red Queen hypothesis and sympatric speciation based on sexual selection. It is proposed that each one of these mechanisms may have been acting on hominins during these short periods of climate variability, which then produce a range of different traits that led to the emergence of new species. In the case of Homo erectus (sensu lato), it is not just brain size that changes but life history (shortened inter-birth intervals, delayed development), body size and dimorphism, shoulder morphology to allow thrown projectiles, adaptation to long-distance running, ecological flexibility and social behaviour. The future of evolutionary research should be to create evidence-based meta-narratives, which encompass multiple mechanisms that select for different traits leading ultimately to speciation.

A synthesis of the theories and concepts of early human evolution

PubMed Central

Maslin, Mark A.; Shultz, Susanne; Trauth, Martin H.

2015-01-01

Current evidence suggests that many of the major events in hominin evolution occurred in East Africa. Hence, over the past two decades, there has been intensive work undertaken to understand African palaeoclimate and tectonics in order to put together a coherent picture of how the environment of Africa has varied over the past 10 Myr. A new consensus is emerging that suggests the unusual geology and climate of East Africa created a complex, environmentally very variable setting. This new understanding of East African climate has led to the pulsed climate variability hypothesis that suggests the long-term drying trend in East Africa was punctuated by episodes of short alternating periods of extreme humidity and aridity which may have driven hominin speciation, encephalization and dispersals out of Africa. This hypothesis is unique as it provides a conceptual framework within which other evolutionary theories can be examined: first, at macro-scale comparing phylogenetic gradualism and punctuated equilibrium; second, at a more focused level of human evolution comparing allopatric speciation, aridity hypothesis, turnover pulse hypothesis, variability selection hypothesis, Red Queen hypothesis and sympatric speciation based on sexual selection. It is proposed that each one of these mechanisms may have been acting on hominins during these short periods of climate variability, which then produce a range of different traits that led to the emergence of new species. In the case of Homo erectus (sensu lato), it is not just brain size that changes but life history (shortened inter-birth intervals, delayed development), body size and dimorphism, shoulder morphology to allow thrown projectiles, adaptation to long-distance running, ecological flexibility and social behaviour. The future of evolutionary research should be to create evidence-based meta-narratives, which encompass multiple mechanisms that select for different traits leading ultimately to speciation. PMID:25602068

Fate of metals before and after chemical extraction of incinerated sewage sludge ash.

PubMed

Li, Jiang-Shan; Tsang, Daniel C W; Wang, Qi-Ming; Fang, Le; Xue, Qiang; Poon, Chi Sun

2017-11-01

Chemical extraction of incinerated sewage sludge ash (ISSA) can effectively recycle P, but it may change the speciation and mobility of the remaining metals. This study investigated the changes of the leaching potential and distribution of metals in the chemically extracted ISSA. Batch extraction experiments with different extractants, including inorganic acids, organic acids, and chelating agents, were conducted on the ISSA collected from a local sewage sludge incinerator. The extraction of Zn, Cu, Pb, Ni, Cd, Ba, Cr and As from the ISSA and the corresponding changes of the mobility and speciation were examined. The results showed that the metals in ISSA were naturally stable because large portions of metals were associated with the residual fraction. The inorganic (HNO 3 and H 2 SO 4 ) and organic acids (citric acid and oxalic acid) significantly co-dissolved the metals through acid dissolution, but the reduction in the total concentrations did not tally the leaching potential of the residual metals. The increase in the exchangeable fraction due to destabilization by the extractants significantly enhanced the mobility and leachability of the metals in the residual ISSA. Chelating agents (EDTA and EDTMP) only extracted a small quantity of metals and had a marginal effect on the fate of the residual metals, but they significantly reduced the Fe/Mn oxide-bound fraction. In comparison, the bioaccessibility of residual metals were reduced to varying extent. Therefore, the disposal or reuse of chemically extracted ISSA should be carefully evaluated in view of possible increase in mobility of residual metals in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

Selenium speciation and extractability in Dutch agricultural soils.

PubMed

Supriatin, Supriatin; Weng, Liping; Comans, Rob N J

2015-11-01

The study aimed to understand selenium (Se) speciation and extractability in Dutch agricultural soils. Top soil samples were taken from 42 grassland fields and 41 arable land fields in the Netherlands. Total Se contents measured in aqua regia were between 0.12 and 1.97 mg kg(-1) (on average 0.58 mg kg(-1)). Organic Se after NaOCl oxidation-extraction accounted for on average 82% of total Se, whereas inorganic selenite (selenate was not measurable) measured in ammonium oxalate extraction using HPLC-ICP-MS accounted for on average 5% of total Se. The predominance of organic Se in the soils is supported by the positive correlations between total Se (aqua regia) and total soil organic matter content, and Se and organic C content in all the other extractions performed in this study. The amount of Se extracted followed the order of aqua regia > 1 M NaOCl (pH8) > 0.1 M NaOH>ammonium oxalate (pH3) > hot water>0.43 M HNO3 > 0.01 M CaCl2. None of these extractions selectively extracts only inorganic Se, and relative to other extractions 0.43 M HNO3 extraction contains the lowest fraction of organic Se, followed by ammonium oxalate extraction. In the 0.1M NaOH extraction, the hydrophobic neutral (HON) fraction of soil organic matter is richer in Se than in the hydrophilic (Hy) and humic acid (HA) fractions. The organic matter extracted in 0.01 M CaCl2 and hot water is in general richer in Se compared to the organic matter extracted in 0.1M NaOH, and other extractions (HNO3, ammonium oxalate, NaOCl, and aqua regia). Although the extractability of Se follows to a large extent the extractability of soil organic carbon, there is several time variations in the Se to organic C ratios, reflecting the changes in composition of organic matter extracted. Copyright © 2015 Elsevier B.V. All rights reserved.

Speciation and transformation of heavy metals during vermicomposting of animal manure.

PubMed

Lv, Baoyi; Xing, Meiyan; Yang, Jian

2016-06-01

This work was conducted to evaluate the effects of vermicomposting on the speciation and mobility of heavy metals (Zn, Pb, Cr, and Cu) in cattle dung (CD) and pig manure (PM) using tessier sequential extraction method. Results showed that the pH, total organic carbon and C/N ratio were reduced, while the electric conductivity and humic acid increased after 90days vermicomposting. Moreover, the addition of earthworm could accelerate organic stabilization in vermicomposting. The total heavy metals in final vermicompost from CD and PM were higher than the initial values and the control without worms. Sequential extraction indicated that vermicomposting decreased the migration and availability of heavy metals, and the earthworm could reduce the mobile fraction, while increase the stable fraction of heavy metals. Furthermore, these results indicated that vermicomposting played a positive role in stabilizing heavy metals in the treatment of animal manure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multicomutation flow system for manganese speciation by solid phase extraction and flame atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Tobiasz, Anna; Sołtys, Monika; Kurys, Ewa; Domagała, Karolina; Dudek-Adamska, Danuta; Walas, Stanisław

2017-08-01

In the paper an application of solid phase extraction technique for speciation analysis of manganese in water samples with the use of flame atomic absorption spectrometry is presented. Two types of sorbents, activated silica gel and Dowex 1 × 4, were used respectively for simultaneously Mn2 + and MnO42 - retention and preconcentration. The whole procedure was realized in multicomutation flow system. Different conditions like: type and concentration of eluent, sample pH and loading time were tested during the study. Under appropriate conditions, it was possible to obtained enrichment factors of 20 and 16 for Mn(II) and Mn(VII), respectively. Precision of the procedure was close to 4% (measured as relative standard deviation), whereas the detection limit (3σ) was 1.4 μg·L- 1 for Mn(II) and 4.8 μg·L- 1 for Mn(VII).

Speciation of chromium (VI) and total chromium determination in welding dust samples by flow-injection analysis coupled to atomic absorption spectrometry.

PubMed

Girard, L; Hubert, J

1996-11-01

We have studied the speciation of chromium (VI) in stainless-steel welding dusts. The approach used for the analysis of Cr(VI) and total Cr relies on a flow-injection analyzer (FIA) equipped with two different sequential detectors. The system measures Cr(VI). by colorimetry (with 1,5-diphenyl carbohydrazide) and total chromium content by flame atomic absorption spectroscopy (AAS). The extraction of the samples of welding-fume dusts is achieved in a buffer solution (acetic acid and sodium acetate at pH 4). This extraction procedure gives a 96% recovery of chromium (VI). The FIA-AAS system that has been described is also more sensitive, has a lower detection limit (0.005 mug ml(-1)) and gives a better precision (< 1%) than other equivalent systems that have been previously described.

Microbiology: A microbial arsenic cycle in a salt-saturated, extreme environment

USGS Publications Warehouse

Oremland, R.S.; Kulp, T.R.; Blum, J.S.; Hoeft, S.E.; Baesman, S.; Miller, L.G.; Stolz, J.F.

2005-01-01

Searles Lake is a salt-saturated, alkaline brine unusually rich in the toxic element arsenic. Arsenic speciation changed from arsenate [As(V)] to arsenite [As(III)] with sediment depth. Incubated anoxic sediment slurries displayed dissimilatory As(V)-reductase activity that was markedly stimulated by H2 or sulfide, whereas aerobic slurries had rapid As(III)-oxidase activity. An anaerobic, extremely haloalkaliphilic bacterium was isolated from the sediment that grew via As(V) respiration, using either lactate or sulfide as its electron donor. Hence, a full biogeochemical cycle of arsenic occurs in Searles Lake, driven in part by inorganic electron donors.

An expert system for chemical speciation of individual particles using low-Z particle electron probe X-ray microanalysis data.

PubMed

Ro, Chul-Un; Kim, HyeKyeong; Van Grieken, René

2004-03-01

An electron probe X-ray microanalysis (EPMA) technique, using an energy-dispersive X-ray detector with an ultrathin window, designated a low-Z particle EPMA, has been developed. The low-Z particle EPMA allows the quantitative determination of concentrations of low-Z elements, such as C, N, and O, as well as chemical elements that can be analyzed by conventional energy-dispersive EPMA, in individual particles. Since a data set is usually composed of data for several thousands of particles in order to make environmentally meaningful observations of real atmospheric aerosol samples, the development of a method that fully extracts chemical information contained in the low-Z particle EPMA data is important. An expert system that can rapidly and reliably perform chemical speciation from the low-Z particle EPMA data is presented. This expert system tries to mimic the logic used by experts and is implemented by applying macroprogramming available in MS Excel software. Its feasibility is confirmed by applying the expert system to data for various types of standard particles and a real atmospheric aerosol sample. By applying the expert system, the time necessary for chemical speciation becomes shortened very much and detailed information on particle data can be saved and extracted later if more information is needed for further analysis.

Uncertainty analysis of the nonideal competitive adsorption-donnan model: effects of dissolved organic matter variability on predicted metal speciation in soil solution.

PubMed

Groenenberg, Jan E; Koopmans, Gerwin F; Comans, Rob N J

2010-02-15

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Pressurised solvent extraction for organotin speciation in vegetable matrices.

PubMed

Marcic, Christophe; Lespes, Gaëtane; Potin-Gautier, Martine

2005-08-01

Because organotin compounds (OTC) are widely used in many fields of activity, they have become an ubiquitous environmental presence. The presence of organotins in the environment impacts upon food safety, making it important to monitor the levels of organotin pesticides in fruits and vegetables. Nevertheless, only a few studies have been published on organotin speciation in plants. The objective of the present study was to evaluate and optimise a specific procedure based on pressurised solvent extraction (PSE) that is suitable for monitoring organotin content in vegetables. In ASE, solvents are used at elevated temperatures and pressures to increase the rate and efficiency of the extraction process. The results from this procedure were compared to those from the technique usually employed, solid/liquid extraction (SLE) performed in an acidic solvent by mechanical shaking. Three extracting solutions were tested-methanol, ethyl acetate and a mixture of methanol and ethyl acetate-and the mixture was found to give the most quantitative results while preserving the speciation. French bean and lettuce leaves as well as potato tubers were used as the plant materials. These vegetables were considered because they are the vegetables consumed in the most quantities in Europe. The study focuses on trisubstituted OTCs, which are the most toxic tin species. The samples were spiked with four trisubstituted organotins: tributyltin (TBT), triphenyltin (TPhT), tricyclohexyltin (TcHexT) and trioctyltin (TOcT). The influence of the pressure and the temperature of the PSE on the quantitativity of the process and on species preservation was evaluated using the experimental design methodology. The optimised PSE allowed detection limits down to 1-2 ng (Sn) g(-1) to be reached. These are higher than those obtained by SLE (0.1-1 ng (Sn) g(-1)). Although the repeatability is similar for both PSE and SLE (2-12% for triorganotin compounds), this appears to be highly time-dependent in the case of SLE. Comparison with SLE confirms that PSE is an interesting tool for vegetable analysis considering the satisfactory OTC preservation and repeatability obtained for a relatively short extraction duration (only 15 min against 2-12 h for SLE).

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

PubMed

Zuo, Xiaojun; Fu, Dafang; Li, He

2012-11-01

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

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

PubMed

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

2018-06-17

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

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

PubMed

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

2016-02-01

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

Speciation of Se and DOC in soil solution and their relation to Se bioavailability.

PubMed

Weng, Liping; Vega, Flora Alonso; Supriatin, Supriatin; Bussink, Wim; Van Riemsdijk, Willem H

2011-01-01

A 0.01 M CaCl(2) extraction is often used to asses the bioavailability of plant nutrients in soils. However, almost no correlation was found between selenium (Se) in the soil extraction and Se content in grass. The recently developed anion Donnan membrane technique was used to analyze chemical speciation of Se in the 0.01 M CaCl(2) extractions of grassland soils and fractionation of DOC (dissolved organic carbon). The results show that most of Se (67-86%) in the extractions (15 samples) are colloidal-sized Se. Only 13-34% of extractable Se are selenate, selenite and small organic Se (<1 nm). Colloidal Se is, most likely, Se bound to or incorporated in colloidal-sized organic matter. The dominant form of small Se compounds (selenate, selenite/small organic compounds) depends on soil. A total of 47-85% of DOC is colloidal-sized and 15-53% are small organic molecules (<1 nm). In combination with soluble S (sulfur) and/or P (phosphor), concentration of small DOC can explain most of the variability of Se content in grass. The results indicate that mineralization of organic Se is the most important factor that controls Se availability in soils. Competition with sulfate and phosphate needs to be taken into account. Further research is needed to verify if concentration of small DOC is a good indicator of mineralization of soil organic matter.

Speciation analysis of Mn(II)/Mn(VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES.

PubMed

Chen, Songqing; Qin, Xingxiu; Gu, Weixi; Zhu, Xiashi

2016-12-01

Ionic liquids-β-cyclodextrin polymer (ILs-β-CDCP) was attached on Fe 3 O 4 nanoparticles to prepare magnetic solid phase extraction agent (Fe 3 O 4 @ILs-β-CDCP). The properties and morphology of Fe 3 O 4 @ILs-β-CDCP were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction(XRD), size distribution and magnetic analysis. A new method of magnetic solid phase extraction (MSPE) coupled to ICP-OES for the speciation of Mn(II)/Mn(VII) in water samples was established. The results showed that Mn(VII) and total manganese [Mn(II)+Mn(VII)] were quantitatively extracted after adjusting aqueous sample solution to pH 6.0 and 10.0, respectively. Mn(II) was calculated by subtraction of Mn(VII) from total manganese. Fe 3 O 4 @ILs-β-CDCP showed a higher adsorption capacity toward Mn(II) and Mn(VII). Several factors, such as the pH value, extraction temperature and sample volume, were optimized to achieve the best extraction efficiency. Moreover, the adsorption ability of Fe 3 O 4 @ILs-β-CDCP would not be significantly lower after reusing of 10 times. The accuracy of the developed method was confirmed by analyzing certified reference materials (GSB 07-1189-2000), and by spiking spring water, city water and lake water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2011-01-01

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

[Determination of cadmium by HG-aFS in soil of virescent zone in Chengdu city].

PubMed

Chen, Yuan; Zeng, Ying; Wu, Hong-ji; Wang, Qin-er

2008-12-01

The different speciations of cadmium in soil samples from Chengdu greenbelt were extracted by Tessier sequential extraction method. The contents of total cadmium and different speciation cadmium were determined using HG-AFS. Under optimization condition of HG-AFS and using 2% HCl as medium, and 30 g x L(-1) KBH4 as reductive reagent, 1 mg x L(-1) Co2+ acting together with 10 g x L(-1) CH4N2S can advance the generating efficiency of cadmium compound. The effects of the coexisting elements in soil on the determination of cadmium can be reduced if certain amount of Na4P2O7, K2SO4 and BaCl2 are added. The linear range is 0-10 mg x L(-1) with r=0.9991 and the detection limit is 0.016 mg x L(-1). The recovery is 97.80%-100.2% with RSD of 1.93%. The analytical method is very sensitive and accurate. The distribution of average percentage of five speciations of cadmium in experimental soil samples is: residual fraction (62.1%) > exchangeable fraction (11.7%) > Fe-Mn oxide-bound (9.71%) > carbonate-bound (4.17%) > organic-bound (3.47%). Although residual fraction is the main speciation of cadmium in soil, the content of exchangeable fraction is relatively high. Thus the bioactivity of cadmium in the research area should be recognized. The concentration of cadmium exceeds the country standard in 19 soil sample, accounting for 86. 4% of all soil samples. The soil from Chengdu greenbelt located in 1st ring road, 2nd ring road and 3rd ring road was polluted to different degree. The relative pollution magnitude of them is: 2nd ring road > 1st ring road > 3rd ring road.

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

PubMed

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

2011-09-01

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

Fate of heavy metals during municipal solid waste incineration.

PubMed

Abanades, S; Flamant, G; Gagnepain, B; Gauthier, D

2002-02-01

A thermodynamic analysis was performed to determine whether it is suitable to predict the heavy metal (HM) speciation during the Municipal Solid Waste Incineration process. The fate of several selected metals (Cd, Pb, Zn, Cr, Hg, As, Cu, Co, Ni) during incineration was theoretically investigated. The equilibrium analysis predicted the metal partitioning during incineration and determined the impact of operating conditions (temperature and gas composition) on their speciation. The study of the gas composition influence was based on the effects of the contents of oxygen (reducing or oxidising conditions) and chlorine on the HM partitioning. The theoretical HM speciation which was calculated in a complex system representing a burning sample of Municipal Solid Waste can explain the real partitioning (obtained from literature results) of all metals among the various ashes except for Pb. Then, the results of the thermodynamic study were compared with those of characterisation of real incinerator residues, using complementary techniques (chemical extraction series and X-ray micro-analyses). These analysis were performed to determine experimentally the speciation of the three representative metals Cr, Pb, and Zn. The agreement is good for Cr and Zn but not for Pb again, which mainly shows unleachable chemical speciations in the residues. Pb tends to remain in the bottom ash whereas thermodynamics often predicts its complete volatilisation under chlorides, and thus its presence exclusively in fly ash.

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

NASA Astrophysics Data System (ADS)

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

2010-11-01

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

Interpreting the genomic landscape of speciation: a road map for finding barriers to gene flow.

PubMed

Ravinet, M; Faria, R; Butlin, R K; Galindo, J; Bierne, N; Rafajlović, M; Noor, M A F; Mehlig, B; Westram, A M

2017-08-01

Speciation, the evolution of reproductive isolation among populations, is continuous, complex, and involves multiple, interacting barriers. Until it is complete, the effects of this process vary along the genome and can lead to a heterogeneous genomic landscape with peaks and troughs of differentiation and divergence. When gene flow occurs during speciation, barriers restricting gene flow locally in the genome lead to patterns of heterogeneity. However, genomic heterogeneity can also be produced or modified by variation in factors such as background selection and selective sweeps, recombination and mutation rate variation, and heterogeneous gene density. Extracting the effects of gene flow, divergent selection and reproductive isolation from such modifying factors presents a major challenge to speciation genomics. We argue one of the principal aims of the field is to identify the barrier loci involved in limiting gene flow. We first summarize the expected signatures of selection at barrier loci, at the genomic regions linked to them and across the entire genome. We then discuss the modifying factors that complicate the interpretation of the observed genomic landscape. Finally, we end with a road map for future speciation research: a proposal for how to account for these modifying factors and to progress towards understanding the nature of barrier loci. Despite the difficulties of interpreting empirical data, we argue that the availability of promising technical and analytical methods will shed further light on the important roles that gene flow and divergent selection have in shaping the genomic landscape of speciation. © 2017 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2017 European Society For Evolutionary Biology.

Ecological speciation by temporal isolation in a population of the stonefly Leuctra hippopus (Plecoptera, Leuctridae).

PubMed

Boumans, Louis; Hogner, Silje; Brittain, John; Johnsen, Arild

2017-03-01

Stream dwelling invertebrates are ideal candidates for the study of ecological speciation as they are often adapted to particular environmental conditions within a stream and inhabit only certain reaches of a drainage basin, separated by unsuitable habitat. We studied an atypical population of the stonefly Leuctra hippopus at a site in central Norway, the Isterfoss rapids, in relation to three nearby and two remote conspecific populations. Adults of this population emerge about a month earlier than those of nearby populations, live on large boulders emerging from the rapids, and are short-lived. This population also has distinct morphological features and was studied earlier during the period 1975-1990. We reassessed morphological distinctness with new measurements and added several analyses of genetic distinctness based on mitochondrial and nuclear sequence markers, as well as AFLP fingerprinting and SNPs mined from RAD sequences. The Isterfoss population is shown to be most closely related to its geographical neighbors, yet clearly morphologically and genetically distinct and homogeneous. We conclude that this population is in the process of sympatric speciation, with temporal isolation being the most important direct barrier to gene flow. The shift in reproductive season results from the particular temperature and water level regime in the Isterfoss rapids. The distinct adult body shape and loss of flight are hypothesized to be an adaptation to the unusual habitat. Ecological diversification on small spatial and temporal scales is one of the likely causes of the high diversity of aquatic insects.

Trait-based diversification shifts reflect differential extinction among fossil taxa.

PubMed

Wagner, Peter J; Estabrook, George F

2014-11-18

Evolution provides many cases of apparent shifts in diversification associated with particular anatomical traits. Three general models connect these patterns to anatomical evolution: (i) elevated net extinction of taxa bearing particular traits, (ii) elevated net speciation of taxa bearing particular traits, and (iii) elevated evolvability expanding the range of anatomies available to some species. Trait-based diversification shifts predict elevated hierarchical stratigraphic compatibility (i.e., primitive→derived→highly derived sequences) among pairs of anatomical characters. The three specific models further predict (i) early loss of diversity for taxa retaining primitive conditions (elevated net extinction), (ii) increased diversification among later members of a clade (elevated net speciation), and (iii) increased disparity among later members in a clade (elevated evolvability). Analyses of 319 anatomical and stratigraphic datasets for fossil species and genera show that hierarchical stratigraphic compatibility exceeds the expectations of trait-independent diversification in the vast majority of cases, which was expected if trait-dependent diversification shifts are common. Excess hierarchical stratigraphic compatibility correlates with early loss of diversity for groups retaining primitive conditions rather than delayed bursts of diversity or disparity across entire clades. Cambrian clades (predominantly trilobites) alone fit null expectations well. However, it is not clear whether evolution was unusual among Cambrian taxa or only early trilobites. At least among post-Cambrian taxa, these results implicate models, such as competition and extinction selectivity/resistance, as major drivers of trait-based diversification shifts at the species and genus levels while contradicting the predictions of elevated net speciation and elevated evolvability models.

Arsenic Speciation of Terrestrial Invertebrates

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

Moriarty, M.M.; Koch, I.; Gordon, R.A.

2009-07-01

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

METAL SPECIATION IN SOIL, SEDIMENT, AND WATER SYSTEMS VIA SYNCHROTRON RADIATION RESEARCH

EPA Science Inventory

Metal contaminated environmental systems (soils, sediments, and water) have challenged researchers for many years. Traditional methods of analysis have employed extraction methods to determine total metal content and define risk based on the premise that as metal concentration in...

Validation of an updated fractionation and indirect speciation procedure for inorganic arsenic in oxic and suboxic soils and sediments.

PubMed

Lock, Alan; Wallschläger, Dirk; McMurdo, Colin; Tyler, Laura; Belzile, Nelson; Spiers, Graeme

2016-12-01

A sequential extraction procedure (SEP) for the speciation analysis of As(III) and As(V) in oxic and suboxic soils and sediments was validated using a natural lake sediment and three certified reference materials, as well as spike recoveries of As(III) and As(V). Many of the extraction steps have been previously validated making the procedure useful for comparisons to similar previous SEP studies. The novel aspect of this research is the validation for the SEP to maintain As(III) and As(V) species. The proposed five step extraction procedure includes the extraction agents (NH 4 ) 2 SO 4 , NH 4 H 2 PO 4 , H 3 PO 4  + NH 2 OH·HCl, oxalate + ascorbic acid (heated), and HNO 3  + HCl + HF, targeting operationally defined easily exchangeable, strongly sorbed, amorphous Fe oxide bound, crystalline Fe oxide bound, and residual As fractions, respectively. The third extraction step, H 3 PO 4  + NH 2 OH·HCl, has not been previously validated for fraction selectivity. We present evidence for this extraction step to target As complexed with amorphous Fe oxides when used in the SEP proposed here. All solutions were analyzed on ICP-MS. The greatest concentrations of As were extracted from the amorphous Fe oxide fraction and the dominant species was As(V). Lake sediment materials were found to have higher As(III) concentrations than the soil materials. Because different soils/sediments have different chemical characteristics, maintenance of As species during extractions must be validated for specific soil/sediment types using spiking experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Assessment of total arsenic and arsenic species stability in alga samples and their aqueous extracts.

PubMed

García Salgado, S; Quijano Nieto, M A; Bonilla Simón, M M

2008-05-30

In order to achieve reliable information on speciation analysis, it is necessary to assess previously the species stability in the sample to analyse. Furthermore, in those cases where the sample treatment for species extraction is time-consuming, an assessment of the species integrity in the extracts is of paramount importance. Thus, the present paper reports total arsenic and arsenic species stability in alga samples (Sargassum fulvellum and Hizikia fusiformis), as well as in their aqueous extracts, which were stored in amber glass and polystyrene containers at different temperatures. Total arsenic determination was carried out by inductively coupled plasma atomic emission spectroscopy (ICP-AES), after sample acid digestion in a microwave oven, while arsenic speciation was conducted by anion exchange high performance liquid chromatography on-line coupled to ICP-AES, with and without sample introduction by hydride generation (HPLC-ICP-AES and HPLC-HG-ICP-AES), after aqueous microwave-assisted extraction. The results obtained for solid alga samples showed that total arsenic (for Hijiki alga) and arsenic species present (As(V) for Hijiki and NIES No. 9 Sargasso) are stable for at least 12 months when samples are stored in polystyrene containers at +20 degrees C. On the other hand, a different behaviour was observed in the stability of total arsenic and As(V) species in aqueous extracts for both samples, being the best storage conditions for Sargasso extracts a temperature of -18 degrees C and polystyrene containers, under which they are stable for at least 15 days, while Hijiki extracts must be stored in polystyrene containers at +4 degrees C in order to ensure the stability for 10 days.

Speciation of heavy metals Cu, Ni and Zn by modified BCR sequential extraction procedure in sediments from Banten Bay, Banten Province, Indonesia

NASA Astrophysics Data System (ADS)

Lestari; Budiyanto, F.; Hindarti, D.

2018-02-01

Banten Bay is categorized as a marine area that is busy with marine tourism activities, settlements and also industries. One potential impact of the condition is the occurrence of pollution from both industrial and domestic sources, erosion and sedimentation in the coastal environment. Samples were collected from 25 representative stations in April 2016. Chemical speciation of three heavy metals (Cu, Ni, and Zn) was studied using a modified sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR). The aims of this study are to determine geochemical speciation of 4 bounds of metal: acid-soluble, reducible, oxidizable and residual, and to assess their impacts in the sediments of Banten Bay, Indonesia. The result shows that the percentage of Copper (45.90-83.75%), Nickel (18.28-65.66%), and Zinc (30.45-79.51%) were mostly accumulated in residual fraction of the total concentrations. The Risk Assessment Code (RAC) reveals that about 0-7.07% of Copper and 1.11-24.35 % of Zinc at sites exist in exchangeable fraction and therefore, they are in low risk category. While 7.34-34.90 of Ni at sites exists in exchangeable fraction and therefore, it is in medium risk category to aquatic environment.

Spatial and Temporal Variability in Sediment P Distribution and Speciation in Coastal Louisiana

NASA Astrophysics Data System (ADS)

Bowes, K.; White, J. R.; Maiti, K.

2017-12-01

Excess loading of phosphorus (P) and nitrogen (N) into aquatic systems leads to degradation of water quality and diminished important ecosystem services. In the Northern Gulf of Mexico (NGOM), excess P and N loading has led to a seasonally present hypoxic area with less than 2 mg/L O2 in bottom waters, approximating 26,000 km2 in 2017. A sequential extraction (SEDEX) method was performed on surficial sediments from five different coastal and shelf sites as a function of distance from the Mississippi River mouth in the NGOM. To better quantify temporal variability in P distribution and speciation, samples were collected during both low (August) and high (May) river flow regimes. Sequential extraction techniques have been successful in separating pools of P into exchangeable or loosely sorbed P, Fe-P, Authigenic-P, Detrital-P, and Organic-P. Preliminary results suggest Authigenic-P is approximately 3-6 times more concentrated in NGOM sediments than all other P pools. Fractionation results did not show a consistent trend with sediment depth. Sediment samples had an average moisture content of 58.72% ± 12.06% and an average bulk density of 0.582 ± 0.275 g/cm3. Continued analysis of P speciation and cycling in NGOM sediments is critical in understanding the driving force behind coastal eutrophication and informing effective nutrient management strategies.

[Analysis of washing efficiency and change in lead speciation in lead-contaminated soil of a battery factory].

PubMed

Ren, Bei; Huang, Jin-lou; Miao, Ming-sheng

2013-09-01

Lead-contaminated soil with different pollution load in a lead battery factory in the southwest of China was chosen as the research object, the lead content and speciation were analyzed, and different washing agents were screened. The lead washing efficiency and lead speciation were analyzed under different pH conditions, and the soil of different particle size was washed using different duration to determine the best washing time. The results showed that the soil of sites A and B in the factory was severely contaminated, the lead concentration reaching 15,703.22 mg x kg(-1) and 1747.78 mg x kg(-1), respectively, and the proportion of the active-state lead was relatively high, while the residue state accounted for only 17.32%, 11.64%, 14.6% and 10.2%. EDTA and hydrochloric acid showed the best extraction effect in the 5 washing agents tested, which included EDTA, hydrochloric acid, citric acid, rhamnolipid and SDS. Cleaning under acidic conditions could not only effectively extract the total amount of lead but also effectively reduce the environmental risk of active-state lead. pH 4-7 was suggested as the most appropriate condition. The cleaning effect of coarse sand and fine sand was good, while for washing powder clay, it is better to improve the process, with the optimal washing time determined as 240 min.

Arsenic bioaccessibility and speciation in the soils amended with organoarsenicals and drinking-water treatment residuals based on a long-term greenhouse study

NASA Astrophysics Data System (ADS)

Nagar, Rachana; Sarkar, Dibyendu; Makris, Konstantinos C.; Datta, Rupali

2014-10-01

SummaryAlthough organoarsenical pesticides are no longer applied to agricultural fields in the US, their widespread use until recently, toxicity, and potential transformation to inorganic arsenic has raised serious concern. Drinking-water treatment residuals (WTRs) have been proposed as a low-cost amendment for remediation of organoarsenical pesticide contaminated soils. A long-term greenhouse study was initiated to evaluate the effect WTR application on bioaccessibility, geochemical partitioning, and speciation of the Dimethylarsinic acid (DMA). Two soils (Immokalee and Orelia series) were spiked with DMA (1500 mg As kg-1) and amended with an Al- and Fe-based WTR at two rates (5% and 10% by wt.). Soil sampling was done immediately after spiking (time zero) and after 0.25, 0.5, 1, and 3 (time final) years of equilibration and subjected to bioaccessibility test and sequential extraction. Results showed that compared to the unamended (no WTR) control, As bioaccessibility in the WTR-amended soils significantly (p < 0.001) decreased by 40-70% in 3 years. The Fe-WTR was more effective than Al-WTR in decreasing soil As bioaccessibility. The in vitro and water-extracted samples were subjected to As speciation at time zero and time final. Results showed transformation of DMA into inorganic As, irrespective of WTR amendments. The Orelia soil showed significantly (p < 0.001) higher transformation than the Immokalee soil.

Speciation Analysis of Trace Mercury in Sea Cucumber Species of Apostichopus japonicus Using High-Performance Liquid Chromatography Conjunction With Inductively Coupled Plasma Mass Spectrometry.

PubMed

Liu, Hao; Luo, Jiaoyang; Ding, Tong; Gu, Shanyong; Yang, Shihai; Yang, Meihua

2018-03-25

In this paper, a simple and cost-effective method using high-performance liquid chromatography in conjunction with inductively coupled plasma mass spectrometry with a rapid ultrasound-assisted extraction was used for analysis speciation of trace mercury in sea cucumber species of Apostichopus japonicus. The effective separation of inorganic mercury, methylmercury, and ethylmercury was achieved within 10 min using Agilent ZORBAX SB-C 18 analytical and guard columns with an isocratic mobile phase consisting of 8% methanol and 92% H 2 O containing 0.12% L-cysteine (m/v) and 0.01 mol/L ammonium acetate. Mercury species were extracted from A. japonicus samples using a solution containing 2-mercaptoethanol, L-cysteine, and hydrochloric acid and sonicating for 0.5 h. The limits of detection of inorganic mercury, methylmercury, and ethylmercury were 0.12, 0.08, and 0.20 μg/L, and the minimum detectable concentrations (measured at 0.500 g sample volume in 10.00 mL) were 2.4, 1.6, and 4.0 μg/kg, respectively. Analysis of a scallop certified reference material (GBW 10024) revealed accordance between the experimental and certified values. This study provides a reference for the evaluation of mercury speciation in sea cucumber and other seafood.

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

PubMed

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

2013-01-01

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

Influence of chemical speciation and biofilm composition on mercury accumulation by freshwater biofilms.

PubMed

Dranguet, P; Le Faucheur, S; Cosio, C; Slaveykova, V I

2017-01-25

Mercury (Hg) is a pollutant of high concern for aquatic systems due to the biomagnification of its methylated form along the food chain. However, in contrast to other metals, gaining knowledge of its bioavailable forms for aquatic microorganisms remains challenging, making Hg risk assessment difficult. Ubiquitous and sessile freshwater biofilms are well known to accumulate and to transform Hg present in their ambient environment. The present study thus aims to evaluate whether non-extractable (proxy of intracellular) Hg accumulated by biofilms could be a good indicator of Hg bioavailability for microorganisms in freshwater. To that end, the link between Hg concentration and speciation, as well as biofilm composition (percentage of abiotic, biotic, chlorophyll and phycocyanin-fractions and abundance of dsrA, gcs, merA and hgcA bacterial genes) and biofilm Hg accumulation was examined. The studied biofilms were grown on artificial substrata in four reservoirs along the Olt River (Romania), which was contaminated by Hg coming from chlor-alkali plant effluents. The 0.45 μm-filterable Hg concentrations in ambient waters were measured and inorganic IHg speciation was modelled. Biofilms were analyzed for their non-extractable IHg and methylmercury (MeHg) contents as well as for their composition. The non-extractable IHg content was related, but not significantly, to the concentration of total IHg (r 2 = 0.88, p = 0.061) whereas a significant correlation was found with the predicted IHg concentration that is not bound to dissolved organic matter (r 2 = 0.95, p = 0.027), despite its extremely low concentrations (10 -25 M), showing a limitation of the thermodynamic Hg modelling to predict Hg bioavailability. The studied biofilms were different in biomass and composition and a principal component analysis showed that the non-extractable IHg content correlated with the abundance of the merA and hgcA genes, while MeHg accumulation was only linked with the abundance of the rRNA 16S gene. The present study suggests that non-extractable IHg concentrations in biofilms are a useful proxy of IHg bioavailable forms in waters whereas the hgcA and merA genes are good biomarkers of both biofilm IHg exposure and bioavailability.

Lead forms in urban turfgrass and forest soils as related to organic matter content and pH

Treesearch

Ian D. Yesilonis; Bruce R. James; Richard V. Pouyat; Bahram Momen

2008-01-01

Soil pH may influence speciation and extractability of Pb, depending on type of vegetation in urban soil environments. We investigated the relationship between soil pH and Pb extractability at forest and turf grass sites in Baltimore, Maryland. Our two hypotheses were: (1) due to lower pH values in forest soils, more Pb will be in exchangeable forms in forested than in...

Gas chromatography--inductively coupled plasma--time-of-flight mass spectrometry for the speciation analysis of organolead compounds in environmental water samples.

PubMed

Heisterkamp, M; Adams, F C

2001-07-01

The application of inductively coupled plasma--time-of-flight mass spectrometry for the speciation analysis of organolead compounds in environmental waters is described. Construction of the transfer line was achieved by means of a relatively simple and rapid coupling procedure. Derivatization of the ionic lead species was achieved by in-situ propylation with sodium tetrapropylborate; simultaneous extraction of the derivatized compounds in hexane was followed by separation and detection by capillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight mass spectrometry. Detection limits for the different organolead species ranged from 10 to 15 fg (as Pb), corresponding to procedural detection limits between 50 and 75 ng L(-1), on the basis of a 50 mL snow sample, extraction with 200 microL hexane, and subsequent injection of 1 microL of the organic extract on to the column. The accuracy of the system was confirmed by additional analysis of the water samples by capillary gas chromatography coupled with microwave-induced plasma-atomic-emission spectrometry and the analysis of a standard reference material CRM 605 (road dust) with a certified content of trimethyllead.

Speciation of arsenic in biological samples.

PubMed

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.

Selective and sensitive speciation analysis of Cr(VI) and Cr(III), at sub-μgL-1 levels in water samples by electrothermal atomic absorption spectrometry after electromembrane extraction.

PubMed

Tahmasebi, Zeinab; Davarani, Saied Saeed Hosseiny

2016-12-01

In this work, electromembrane extraction in combination with electrothermal atomic absorption spectrometry (ET-AAS) was investigated for speciation, preconcentration and quantification of Cr(VI) and Cr(III) in water samples through the selective complexation of Cr(VI) with 1,5-diphenylcarbazide (DPC) as a complexing agent. DPC reduces Cr(VI) to Cr(III) ions and then Cr(III) species are extracted based on electrokinetic migration of their cationic complex (Cr(III)-DPC) toward the negative electrode placed in the hollow fiber. Also, once oxidized to Cr(VI), Cr(III) ions in initial sample were determined by this procedure. The influence of extraction parameters such as pH, type of organic solvent, chelating agent concentration, stirring rate, extraction time and applied voltage were evaluated following a one-at-a-time optimization approach. Under optimized conditions, the extracted analyte was quantified by ETAAS, with an acceptable linearity in the range of 0.05-5ngmL -1 (R 2 value=0.996), and a repeatability (%RSD) between 3.7% and 12.2% (n=4) for 5.0 and 1.0ngmL -1 of Cr(VI), respectively. Also, we obtained an enrichment factor of 110 that corresponded to the recovery of 66%. The detection limit (S/N ratio of 3:1) was 0.02ngmL -1 . Finally, this new method was successfully employed to determine Cr(III) and Cr(VI) species in real water samples. Copyright © 2016. Published by Elsevier B.V.

Speciation and distribution of cadmium and lead in salinized horizons of antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.; Astefanei, D.

2009-04-01

The utilization of intensive technologies for the vegetable cultivation in glass houses by the administration of high doses of organic fertilizes, the supra-dimensional irrigation and the maintaining of soil at high humidity state, in special in case of vicious drainage have as result the rapid degradation of morphological, chemical and physical characteristics of soils, concretized by: (i) decrease of structural aggregates stability; (ii) more dense packing of soil; (iii) accumulation of easy soluble salts (in special at superior horizons level); (iv) limitation of organic compounds and micro-elements biodisponibility. All these determined a significant reduction of productivity and of exploitation duration of soils from glass houses. These phenomena modified continuously the dynamic of speciation processes and inter-phases distribution, of heavy metals in soils from glass houses, and can determined a non-controlled accumulation of heavy metals, in special as mobile forms with high biodisponibility. Ours studied have been performed using soil profiles drawing from Copou-glass house, Iasi (Romania). Has been followed the modification of distribution for speciation forms of cadmium and lead (two heavy metals with high toxicity degree), between hortic antrosol horizons, and between chemical-mineralogical components of this, with the progressive salinization of superior horizons, in 2007-2008 period. The separation, differentiation and determination of cadmium and lead speciation forms was done by combined solid-liquid sequential extraction (SPE) and extraction in aqueous polymer-inorganic salt two-phase systems (ABS) procedure, presented in some of ours previous studies. After extraction, the total contents of the two heavy metals and fractions from these differential bonded by mineral and organic components of hortic antrosol have been determined by atomic absorption spectrometry. The specific interaction mechanisms of Cd and Pb with organic-mineral components of soils have been estimated on the basis of Raman and FT-IR spectra, recorded for fractions obtained after each extraction step. These data were correlated with those obtained by chemical analysis and UV-VIS spectrometry, and were used for to establish the type and weight of Cd and Pb speciation forms in studied antrosol. Our studies have been show that in medium and inferior horizons of hortic antrosols, the heavy metals have a general accumulation tendency, preferential by binding on organic matter and organic-mineral complexes, components with higher abundance in such type of soils. The selectivity and complexation mechanisms are controlled by speciation forms of the two metals. This phenomenon has two important consequences, the strong fixation of heavy metals in hortic antrosol and significant modification of structure and conformation of organic macromolecules. A specific phenomenon of hortic antrosols is that the accumulation rate of heavy metals is higher than levigation rate, and the mobile forms of these have a higher biodisponibility, being relative easy assimilated by plants. The progressive salinization of superior horizons of soils from glass houses, determined a sever perturbation of equilibrium between Cd and Pb speciation forms. In consequence these will have an accentuated migration tendency in superior horizons, as complexes with inorganic ligands, with a high mobility and biodsiponibility. The accumulation of soluble salts in superior horizons, and the formation of frangipane horizon (horizon of geochemical segregation of hortic antrosols) modified the ionic strength from soil solution and the thermodynamic activity of cadmium and lead species. Under these conditions, the levigation rate of cadmium and lead is higher than the accumulation rate, which means that the migration of these metals in soil solution occurs fast and in high concentrations. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 an Project PNCDI 2-D5 no. 52141 / 08).

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

PubMed

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

2016-03-01

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

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

PubMed

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

2005-09-01

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

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

PubMed

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

2014-09-02

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

CHARACTERIZATION OF ARSENOSUGARS AND ASSOCIATED DEGRADATION PRODUCTS FOLLOWING AN AGGRESSIVE ACID/BASE EXTRACTION PROCEDURE

EPA Science Inventory

The speciation of arsenic in seafood products is important for the determination of an improved toxicity based relative source (water vs. diet) contribution estimate. The two major sources of arsenic are drinking water and seafood ingestion. Drinking water contains predominatel...

ARSENIC SPECIATION IN CARROT EXTRACTS WITH AN EMPHASIS ON THE DETECTION OF MMA(III) AND MMTA

EPA Science Inventory

The two predominant routes of arsenic exposure are dietary ingestion and drinking water consumption. Dietary arsenic, unlike drinking water arsenic, contains a variety of arsenicals with dramatically different toxicities. The list of arsenicals detected in dietary samples conti...

Ultra-sensitive speciation analysis of mercury by CE-ICP-MS together with field-amplified sample stacking injection and dispersive solid-phase extraction.

PubMed

Chen, YiQuan; Cheng, Xian; Mo, Fan; Huang, LiMei; Wu, Zujian; Wu, Yongning; Xu, LiangJun; Fu, FengFu

2016-04-01

A simple dispersive solid-phase extraction (DSPE) used to extract and preconcentrate ultra-trace MeHg, EtHg and Hg(2+) from water sample, and a sensitive method for the simultaneous analysis of MeHg, EtHg and Hg(2+) by using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) with field-amplified sample stacking injection (FASI) were first reported in this study. The DSPE used thiol cotton particles as adsorbent, and is simple and effective. It can be used to extract and preconcentrate ultra-trace mercury compounds in water samples within 30 min with a satisfied recovery and no mercury species alteration during the process. The FASI enhanced the sensitivity of CE-ICP-MS with 25-fold, 29-fold and 27-fold for MeHg, EtHg and Hg(2+) , respectively. Using FASI-CE-ICP-MS together with DSPE, we have successfully determined ultra-trace MeHg, EtHg and Hg(2+) in tap water with a limits of quantification (LOQs) of 0.26-0.45 pg/mL, an RSD (n = 3) < 6% and a recovery of 92-108%. Ultra-high sensitivity, as well as much less sample and reagent consumption and low operating cost, make our method a valuable technique to the speciation analysis of ultra-trace mercury. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Speciation of arsenic in different types of nuts by ion chromatography-inductively coupled plasma mass spectrometry.

PubMed

Kannamkumarath, Sasi S; Wróbel, Kazimierz; Wróbel, Katarzyna; Caruso, Joseph A

2004-03-24

In this work the quantitative determination and analytical speciation of arsenic were undertaken in different types of nuts, randomly purchased from local markets. The hardness of the whole nuts and high lipid content made the preparation of this material difficult for analysis. The lack of sample homogeneity caused irreproducible results. To improve the precision of analysis, arsenic was determined separately in nut oil and in the defatted sample. The lipids were extracted from the ground sample with the two portions of a mixture of chloroform and methanol (2:1). The defatted material was dried and ground again, yielding a fine powder. The nut oil was obtained by combining the two organic extracts and by evaporating the solvents. The two nut fractions were microwave digested, and total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for oils from different types of nuts showed element concentration in the range 2.9-16.9 ng g(-)(1). Lower levels of arsenic were found in defatted material (<0.1 ng g(-)(1) with the exception of Brazil nuts purchased with and without shells, 3.0 and 2.8 ng g(-)(1) respectively). For speciation analysis of arsenic in nut oils, elemental species were extracted from 2 g of oil with 12 mL of chloroform/methanol (2:1) and 8 mL of deionized water. The aqueous layer, containing polar arsenic species, was evaporated and the residue dissolved and analyzed by ion chromatography-ICP-MS. The anion exchange chromatography enabled separation of As(III), dimethylarsinic acid (DMAs(V)), monomethylarsonic acid (MMAs(V)), and As(V) within 8 min. Several types of nuts were analyzed, including walnuts, Brazil nuts, almonds, cashews, pine nuts, peanuts, pistachio nuts, and sunflower seeds. The recovery for the speciation procedure was in the range 72.7-90.6%. The primary species found in the oil extracts were As(III) and As(V). The arsenic concentration levels in these two species were 0.7-12.7 and 0.5-4.3 ng g(-)(1), respectively. The contribution of As in DMAs(V) ranged from 0.1 +/- 0.1 ng g(-)(1) in walnuts to 1.3 +/- 0.3 ng g(-)(1) in pine nuts. MMAs(V) was not detected in almonds, peanuts, pine nuts, sunflower seeds, or walnuts, and the highest concentration was found in pistachio nuts (0.5 +/- 0.2 ng g(-)(1)).

Cryptic speciation reversal in the Etheostoma zonale (Teleostei: Percidae) species group, with an examination of the effect of recombination and introgression on species tree inference.

PubMed

Halas, Dominik; Simons, Andrew M

2014-01-01

Mitochondrial and nuclear introgression among closely related taxa can greatly complicate the process of determining their phylogenetic relationships. In the Central Highlands of North America, many fish taxa have undergone introgression; in this study, we demonstrate the existence of an unusual introgression event in the Etheostoma zonale species group. We used one mitochondrial and seven nuclear loci to determine the relationships of the taxa within the E. zonale group, and their degree of differentiation. We found evidence of multiple divergent populations within each species; much of the divergence within species has taken place during the Pleistocene. We also found evidence of a previously unknown cryptic species in the Upper Tennessee River which diverged from the remainder of the group during the Pliocene, and has undergone mitochondrial and nuclear introgression with E. zonale, in an apparent process of speciation reversal. We examined the effects that using varying types of recombination tests to eliminate the signal of recombination from nuclear loci would have on the phylogenetic placement of this introgressed lineage in our species tree analyses. Copyright © 2013 Elsevier Inc. All rights reserved.

Next-generation sequencing detects repetitive elements expansion in giant genomes of annual killifish genus Austrolebias (Cyprinodontiformes, Rivulidae).

PubMed

García, G; Ríos, N; Gutiérrez, V

2015-06-01

Among Neotropical fish fauna, the South American killifish genus Austrolebias (Cyprinodontiformes: Rivulidae) constitutes an excellent model to study the genomic evolutionary processes underlying speciation events. Recently, unusually large genome size has been described in 16 species of this genus, with an average DNA content of about 5.95 ± 0.45 pg per diploid cell (mean C-value of about 2.98 pg). In the present paper we explore the possible origin of this unparallel genomic increase by means of comparative analysis of the repetitive components using NGS (454-Roche) technology in the lowest and highest Rivulidae genomes. Here, we provide the first annotated Rivulidae-repeated sequences composition and their relative repetitive fraction in both genomes. Remarkably, the genomic proportion of the moderately repetitive DNA in Austrolebias charrua genome represents approximately twice (45%) of the repetitive components of the highly related rivulinae taxon Cynopoecilus melanotaenia (25%). Present work provides evidence about the impact of the repeat families that could be distinctly proliferated among sublineages within Rivulidae fish group, explaining the great genome size differences encompassing the differentiation and speciation events in this family.

Trait-based diversification shifts reflect differential extinction among fossil taxa

PubMed Central

Wagner, Peter J.; Estabrook, George F.

2014-01-01

Evolution provides many cases of apparent shifts in diversification associated with particular anatomical traits. Three general models connect these patterns to anatomical evolution: (i) elevated net extinction of taxa bearing particular traits, (ii) elevated net speciation of taxa bearing particular traits, and (iii) elevated evolvability expanding the range of anatomies available to some species. Trait-based diversification shifts predict elevated hierarchical stratigraphic compatibility (i.e., primitive→derived→highly derived sequences) among pairs of anatomical characters. The three specific models further predict (i) early loss of diversity for taxa retaining primitive conditions (elevated net extinction), (ii) increased diversification among later members of a clade (elevated net speciation), and (iii) increased disparity among later members in a clade (elevated evolvability). Analyses of 319 anatomical and stratigraphic datasets for fossil species and genera show that hierarchical stratigraphic compatibility exceeds the expectations of trait-independent diversification in the vast majority of cases, which was expected if trait-dependent diversification shifts are common. Excess hierarchical stratigraphic compatibility correlates with early loss of diversity for groups retaining primitive conditions rather than delayed bursts of diversity or disparity across entire clades. Cambrian clades (predominantly trilobites) alone fit null expectations well. However, it is not clear whether evolution was unusual among Cambrian taxa or only early trilobites. At least among post-Cambrian taxa, these results implicate models, such as competition and extinction selectivity/resistance, as major drivers of trait-based diversification shifts at the species and genus levels while contradicting the predictions of elevated net speciation and elevated evolvability models. PMID:25331898

Genomic signatures of geographic isolation and natural selection in coral reef fishes.

PubMed

Gaither, Michelle R; Bernal, Moisés A; Coleman, Richard R; Bowen, Brian W; Jones, Shelley A; Simison, W Brian; Rocha, Luiz A

2015-04-01

The drivers of speciation remain among the most controversial topics in evolutionary biology. Initially, Darwin emphasized natural selection as a primary mechanism of speciation, but the architects of the modern synthesis largely abandoned that view in favour of divergence by geographic isolation. The balance between selection and isolation is still at the forefront of the evolutionary debate, especially for the world's tropical oceans where biodiversity is high, but isolating barriers are few. Here, we identify the drivers of speciation in Pacific reef fishes of the genus Acanthurus by comparative genome scans of two peripheral populations that split from a large Central-West Pacific lineage at roughly the same time. Mitochondrial sequences indicate that populations in the Hawaiian Archipelago and the Marquesas Islands became isolated approximately 0.5 Ma. The Hawaiian lineage is morphologically indistinguishable from the widespread Pacific form, but the Marquesan form is recognized as a distinct species that occupies an unusual tropical ecosystem characterized by upwelling, turbidity, temperature fluctuations, algal blooms and little coral cover. An analysis of 3737 SNPs reveals a strong signal of selection at the Marquesas, with 59 loci under disruptive selection including an opsin Rh2 locus. While both the Hawaiian and Marquesan populations indicate signals of drift, the former shows a weak signal of selection that is comparable with populations in the Central-West Pacific. This contrast between closely related lineages reveals one population diverging due primarily to geographic isolation and genetic drift, and the other achieving taxonomic species status under the influence of selection. © 2015 The Authors. Molecular Ecology Published by John Wiley & Sons Ltd.

EXTRACTION AND SPECIATION OF ARSENIC CONTAINING DRINKING WATER TREATMENT SOLIDS BY IC-ICP-MS

EPA Science Inventory

In 2001, the U.S. Environmental Protection Agency (EPA) passed the Arsenic Rule, which established a maximum contaminant level of 105g/L. Compliance with this regulation has caused a number of drinking water utilities to investigate potential treatment options. The adsorption o...

EVALUATION OF EXTRACTION AND SPECTROSCOPIC METHODS FOR PB SPECIATION IN AN AMENDED SOIL

EPA Science Inventory

Immobilization of pyromorphite (Pbs(PO4hCI) via P amendments to Pb contaminated soils is proving to be a viable method of remediation. However, the issue of ascertaining the amount of soil Pb converted to pyromorphite is difficult in heterogeneous soil systems. Previous attempts ...

SPECIATION OF SUBSURFACE CONTAMINANTS BY CONE PENETROMETRY GAS CHROMATOGRAPHY/MASS SPECTROMETRY. (R826184)

EPA Science Inventory

A thermal extraction cone penetrometry gas chroma tography/mass spectrometry system (TECP GC/MS) has been developed to detect subsurface contaminants in situ. The TECP can collect soil-bound organics up to depths of 30 m. In contrast to traditional cone penetrometer sample collec...

IN-SITU REMEDIATION OF CHROMIUM-CONTAMINATED SOILS AND SEDIMENTS USING SODIUM DITHIONITE

EPA Science Inventory

Soil cores were collected from beneath an old chrome plating shop at the USCG Support Center near Elizabeth City, NC in order to determine the extent of chromium contamination in the soils and ground water. Selective extractions were used to assess the chemical speciation and di...

EPA STUDIES OF ARSENIC SPECIATION IN SEAFOOD MATRICES WITH AN EMPHASIS ON EXTRACTABILITY AND ARSENOSUGAR INTEGRITY

EPA Science Inventory

The anthropogenic and geological occurrence of arsenic (As) results in human exposure to a potentially carcinogenic element. The two predominant pathways to As exposure are drinking water (DW) and dietary ingestion (DI). DW exposures are almost exclusively toxic inorganic As. ...

Arsenic speciation and fucoxanthin analysis from seaweed dietary supplements using LC-MS

USDA-ARS?s Scientific Manuscript database

Inorganic species are considered more toxic to humans than organic arsenic and total arsenic. Analysis of total arsenic in metallic form, organic and inorganic arsenic species from seaweeds and dietary supplements using LC-ICP-MS was developed. Solvent extraction with sonication and microwave extr...

Chemical speciation and bioavailability of rare earth elements (REEs) in the ecosystem: a review.

PubMed

Khan, Aysha Masood; Bakar, Nor Kartini Abu; Bakar, Ahmad Farid Abu; Ashraf, Muhammad Aqeel

2017-10-01

Rare earths (RE), chemically uniform group of elements due to similar physicochemical behavior, are termed as lanthanides. Natural occurrence depends on the geological circumstances and has been of long interest for geologist as tools for further scientific research into the region of ores, rocks, and oceanic water. The review paper mainly focuses to provide scientific literature about rare earth elements (REEs) with potential environmental and health effects in understanding the research. This is the initial review of RE speciation and bioavailability with current initiative toward development needs and research perceptive. In this paper, we have also discussed mineralogy, extraction, geochemistry, analytical methods of rare earth elements. In this study, REEs with their transformation and vertical distribution in different environments such as fresh and seawater, sediments, soil, weathering, transport, and solubility have been reported with most recent literature along key methods of findings. Speciation and bioavailability have been discussed in detail with special emphasis on soil, plant, and aquatic ecosystems and their impacts on the environment. This review shows that REE gained more importance in last few years due to their detrimental effects on living organisms, so their speciation, bioavailability, and composition are much more important to evaluate their health risks and are discussed thoroughly as well.

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

AN UNUSUAL PATTERN OF GENE FLOW BETWEEN THE TWO SOCIAL FORMS OF THE FIRE ANT SOLENOPSIS INVICTA.

PubMed

Ross, Kenneth G; Shoemaker, D DeWayne

1993-10-01

Uncertainty over the role of shifts in social behavior in the process of speciation in social insects has stimulated interest in determining the extent of gene flow between conspecific populations differing in colony social organization. Allele and genotype frequencies at 12 neutral polymorphic protein markers, as well as the numbers of alleles at the sex-determining locus (loci), are shown here to be consistent with significant ongoing gene flow between two geographically adjacent populations of Solenopsis invicta that differ in colony queen number. Data from a thirteenth protein marker that is under strong differential selection in the two social forms confirm that such gene flow occurs. Data from this selected locus, combined with knowledge of the reproductive biology of the two social forms, further suggest that interform gene flow is largely unidirectional and mediated through males only. This unusual pattern of gene flow results from the influence of the unique social enviroments of the two forms on the behavior of workers and on the reproductive physiology of sexuals. © 1993 The Society for the Study of Evolution.

Fast arsenic speciation in water by on-site solid phase extraction and high-resolution continuum source graphite furnace atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Mihucz, Victor G.; Bencs, László; Koncz, Kornél; Tatár, Enikő; Weiszburg, Tamás; Záray, Gyula

2017-02-01

A method of high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS-GFAAS), combined with on-site separation/solid phase extraction (SPE) has been developed for the speciation of inorganic As (iAs) in geothermal and drinking water samples. The HR-CS-GFAAS calibration curves were linear up to 200 μg/L As, but using second order polynomial fitting, accurate calibration could be performed up to 500 μg/L. It has been demonstrated that sample pH should not be higher than 8 for an accurate speciation of As(V) with a recovery of ≈ 95%. Geothermal water had fairly high salt content (≈ 2200 mg/L) due to the presence of chlorides and sulfates at mg/L levels. Therefore, a two-fold dilution of these types of samples before SPE is recommended, especially, for total As determinations, when the As concentration is as high as 400 μg/L. For drinking water, sampled from public wells with records of As concentrations higher than the 10 μg/L in the past, the reduction of As contamination below the WHO's health limit value could be observed. However, the electrical conductivity was close to 2500 μS/cm, i.e., the guideline limit for drinking water, which was due to their higher chloride content. The proposed fit-for-purpose SPE-HR-CS-GFAAS method could be a candidate for screening drinking water quality.

Evaluation of comprehensive two-dimensional gas chromatography with flame photometric detection: potential application for sulfur speciation in shale oil.

PubMed

Mitrevski, Blagoj; Amer, Mohammad W; Chaffee, Alan L; Marriott, Philip J

2013-11-25

Flame photometric detection in the sulfur channel has been evaluated for sulfur speciation and quantification in comprehensive two-dimensional gas chromatography [GC × GC-FPD(S)] for S-compound speciation in shale extracts. Signal non-linearity and potential quenching effects were reportedly major limitations of this detector for analysis of sulfur in complex matrices. However, reliable linear relationships with correlation coefficient >0.99 can be obtained if the sum of the square root of each modulation slice in GC × GC is plotted vs. sulfur concentration. Furthermore, the quenching effects are reduced due to essentially complete separation of S-containing components from the hydrocarbon matrix. An increase of S/N of up to 150 times has been recorded for benzothiophene and dibenzothiophene in GC × GC-FPD when compared to GC-FPD due to the modulation process. As a consequence, 10 times lower detection limits were observed in the former mode. The applicability of the method was demonstrated using shale oil sample extracts. Three sulfur classes were completely separated and the target class (thiophenes) was successfully quantified after the rest of the sample was diverted to the second detector by using a heart-cut strategy. Based on the proposed method, 70% of the sulfur in the shale oil was assigned to the thiophenes, 24% to benzothiophenes, and 5% to dibenzothiophene compounds. Copyright © 2013 Elsevier B.V. All rights reserved.

Speciation of inorganic arsenic in drinking water by wavelength-dispersive X-ray fluorescence spectrometry after in situ preconcentration with miniature solid-phase extraction disks.

PubMed

Hagiwara, Kenta; Inui, Tetsuo; Koike, Yuya; Aizawa, Mamoru; Nakamura, Toshihiro

2015-03-01

A rapid and simple method using wavelength-dispersive X-ray fluorescence (WDXRF) spectrometry after in situ solid-phase extraction (SPE) was developed for the speciation and evaluation of the concentration of inorganic arsenic (As) in drinking water. The method involves the simultaneous collection of As(III) and As(V) using 13 mm ϕ SPE miniature disks. The removal of Pb(2+) from the sample water was first conducted to avoid the overlapping PbLα and AsKα spectra on the XRF spectrum. To this end, a 50 mL aqueous sample (pH 5-9) was passed through an iminodiacetate chelating disk. The filtrate was adjusted to pH 2-3 with HCl, and then ammonium pyrrolidine dithiocarbamate solution was added. The solution was passed through a hydrophilic polytetrafluoroethylene filter placed on a Zr and Ca loaded cation-exchange disk at a flow rate of 12.5 mL min(-1) to separate As(III)-pyrrolidine dithiocarbamate complex and As(V). Each SPE disk was affixed to an acrylic plate using adhesive cellophane tape, and then examined by WDXRF spectrometry. The detection limits of As(III) and As(V) were 0.8 and 0.6 μg L(-1), respectively. The proposed method was successfully applied to screening for As speciation and concentration evaluation in spring water and well water. Copyright © 2014 Elsevier B.V. All rights reserved.

Speciation of mercury in sludge solids: washed sludge

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

Bannochie, C. J.; Lourie, A. P.

2017-10-24

The objective of this applied research task was to study the type and concentration of mercury compounds found within the contaminated Savannah River Site Liquid Waste System (SRS LWS). A method of selective sequential extraction (SSE), developed by Eurofins Frontier Global Sciences1,2 and adapted by SRNL, utilizes an extraction procedure divided into seven separate tests for different species of mercury. In the SRNL’s modified procedure four of these tests were applied to a washed sample of high level radioactive waste sludge.

Extraction and speciation of arsenic in lacustrine sediments

USGS Publications Warehouse

Ficklin, W.H.

1990-01-01

Arsenic was partially extracted with 4.OM hydrochloric acid, from samples collected at 25-cm intervals in a 350-cm column of sediment at Milltown Reservoir, Montana and from a 60-cm core of sediment collected at the Cheyenne River Embayment of Lake Oahe, South Dakota. The sediment in both reservoirs is highly contaminated with arsenic. The extracted arsenic was separated into As(III) and As(V) on acetate form Dowex 1-X8 ion-exchange resin with 0.12M HCl eluent. Residual arsenic was sequentially extracted with KClO3 and HCl. Arsenic was determined by graphite-furnace atomic-absorption spectrometry. The analytical results define oxidized and reduced zones in the sediment columns. ?? 1990.

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

PubMed

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

2018-07-15

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

The long-term environmental impacts of the Mount Polley mine tailings spill, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Byrne, Patrick; Hudson-Edwards, Karen; Macklin, Mark; Brewer, Paul; Bird, Graham; Williams, Richard

2015-04-01

On the 4th August 2014 a tailings impoundment failure at the Mount Polley gold and copper mine in British Columbia, Canada, released approximately 25 million m3 of solid and liquid waste into Hazeltine Creek, Quesnel Lake and Polley Lake. The sheer volume of the tailings released caused Haseltine Creek channel to expand from 2m to over 25m in width and Polley Lake water level to rise by 1.7m. The spill also removed trees in a 900 km2 corridor either side of Hazeltine Creek. Local residents and government officials have expressed serious concerns regarding the potential long-term effects on regional biodiversity, water security and to the livelihoods of First Nation communities. Among impoundment failures, the Mount Polley disaster is unique in that the solid tailings contain an unusual mixture of metal contaminants (arsenic, copper, gold, manganese, nickel, lead, vanadium). As particulate matter is the principal carrier of metal contaminants, the spilled tailings may reside in the regional soils and sediments for 1000s of years serving as a secondary source of pollution. The environmental risk posed by the spilled tailings is compounded by the location of the spill in a mountainous forested catchment, affected by severe winters with prominent spring snow melts that have the potential to remobilise very large quantities of spilled tailings. No data currently exist on the short- to long-term behaviour of these tailings in soils and sediments and the effects of the clean-up operations on their behaviour in this type of river environment. In this study, we adopt a multidisciplinary approach to determine the environmental and geomorphological impacts of the tailings spill. We have two specific objectives. (1) The physicochemical speciation and geochemical stability of spilled tailings will be characterised in surface and hyporheic sediments using bulk chemistry, mineralogical (XRD and SEM) and speciation methods (sequential extractions, electron microprobe analysis, XAS). (2) Pre- and post-remediation geomorphological assessments will use unmanned aerial vehicle (UAV) photographic surveys and ground-based topographic surveys to (i) establish the efficacy of remediation efforts in stabilising Hazeltine Creek channel and (ii) quantify the physical remobilisation of tailings during the spring snowmelt.

Unpacking paleoenvironmental change across OAE2 using paired d34S records of pyrite and organic matter

NASA Astrophysics Data System (ADS)

Raven, M. R.; Gomes, M.; Fike, D. A.

2017-12-01

Pyrite sulfur isotopes have proven to be a powerful tool for reconstructing major changes in global redox state and the emergence of microbial metabolisms. Still, pyrite can be a challenging archive, as its formation depends on the availability of reactive iron species and can occur over multiple generations of sedimentary processes. Accordingly, pyrite δ34S records commonly have large point-to-point variability reflecting local processes. By pairing pyrite δ34S records with those of coexisting organic matter (OM), including both kerogens and extractable bitumens, we can begin to parse the various potential causes of this variability and gain greater insights into changes in the sedimentary paleoenvironment. Here, we present the first collection of records of OM δ34S for the Cretaceous, focusing on sections spanning Ocean Anoxic Event 2 (OAE2, 94 Mya), a period of globally widespread marine anoxia and carbon cycle disruption. In carbonates and shales from OAE2 in Pont d'Issole, France, pyrite and OM δ34S values vary in parallel throughout most of the section, consistent with their shared sulfide source. There are also distinct exceptions: In one interval, an excursion in pyrite δ34S is entirely absent from the organic sulfur record but associated with unusual organic sulfur redox speciation (by XAS), potentially reflecting later exposure to oxic porewaters. Across the core interval of shale deposition during OAE2, the offset between pyrite and OM δ34S values declines smoothly from +17.4 to -7.9‰, which we interpret in terms of changes in the speciation of detrital iron minerals that may have regional implications. We then compare these results with data for other well-characterized OAE2 sections, including Cismon (Italy), Tarfaya (Morocco), and the Demerara Rise (offshore Brazil), which represent environments with a variety of apparent redox states. These paired pyrite - OM δ34S profiles yield new information about how the local and global forcings associated with OAE2 impacted environmental redox states, which in turn drove major changes in microbial energy cycling and sulfur and carbon burial fluxes during this critical period of Earth history.

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

PubMed

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

2018-03-01

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

Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

USGS Publications Warehouse

Bolin, Trudy B.; Birdwell, Justin E.; Lewan, Michael; Hill, Ronald J.; Grayson, Michael B.; Mitra-Kirtley, Sudipa; Bake, Kyle D.; Craddock, Paul R.; Abdallah, Wael; Pomerantz, Andrew E.

2016-01-01

The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

Solid-phase extraction-gas chromatography-mass spectrometry using a fullerene sorbent for the determination of inorganic mercury(II), methylmercury(I) and ethylmercury(I) in surface waters at sub-ng/ml levels.

PubMed

Muñoz, J; Gallego, M; Valcárcel, M

2004-11-05

A novel, straightforward solid-phase extraction system for the determination of inorganic mercury and organomercury compounds in water is proposed. The analytes, in a buffer medium at pH 4.5, are sorbed as diethyldithiocarbamate complexes on a C60 fullerene column an subsequently eluted and derivatized with sodium tetra-n-propylborate in ethyl acetate. Following elution, 1 microl of extract is injected into a gas chromatograph-mass spectrometer system. The proposed gas chromatography-mass spectrometry speciation method exhibits a linear range of 4-1 ng/ml, and a detection limit of 1.5 ng/l (sample volume, 50 ml). Its repeatibility, as relative standard deviation (RSD) (from 11 standards containing 50 ng/l for each analyte), is ca. 7%. No interferences from metals ions, such as Zn2+, Fe3+, Sb3+, As3+, Pb2+, Ni2+, Cu2+, Sn2+, Co2+, Mn2+ and Cd2+ were encountered at concentrations 1000 times higher than those of the mercury compounds. The method was used for the speciation of inorganic mercury, methylmercury and ethylmercury in various types of water including sea and waste water.

Simultaneous quantitation and identification of organic and inorganic selenium in diet supplements by liquid chromatography with tandem mass spectrometry.

PubMed

Zembrzuska, Joanna; Matusiewicz, Henryk; Polkowska-Motrenko, Halina; Chajduk, Ewelina

2014-01-01

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for selenium speciation in dietary supplements. Chromatographic separation was performed on a TSK-Gel ODS-100V column using a mixture of 5mM ammonium acetate water solution and methanol as a mobile phase. Conditions chosen for this process allowed to separate all investigated chemical compounds of selenium: seleno-l-methionine, methyl-seleno-l-cysteine, l-selenocystine, methaneseleninic acid, selenite and selenate. A tandem mass spectrometer with an ion trap operating in negative or positive ion mode according to the selenium form being determined was used as a detector. Three extraction procedures: water extraction, enzymatic hydrolysis and sequential extraction were used for preparation of samples for the determination of the actual forms of selenium in diet supplements. The developed method was used for analysis of six dietary supplements containing selenium bought in a pharmacy and supermarket. Apart from speciation analysis of selenium content in supplements total selenium content was determined using instrumental neutron activation analysis (INAA). All expected forms of selenium except for selenite were determined using LC-MS/MS technique. It should be stressed that amounts of selenate were smaller than expected. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Sentence-Composition Effect: Processing of Complex Sentences Depends on the Configuration of Common Noun Phrases versus Unusual Noun Phrases

ERIC Educational Resources Information Center

Johnson, Marcus L.; Lowder, Matthew W.; Gordon, Peter C.

2011-01-01

In 2 experiments, the authors used an eye tracking while reading methodology to examine how different configurations of common noun phrases versus unusual noun phrases (NPs) influenced the difference in processing difficulty between sentences containing object- and subject-extracted relative clauses. Results showed that processing difficulty was…

Impact of the uranium (VI) speciation in mineralised urines on its extraction by calix[6]arene bearing hydroxamic groups used in chromatography columns.

PubMed

Baghdadi, S; Bouvier-Capely, C; Ritt, A; Peroux, A; Fevrier, L; Rebiere, F; Agarande, M; Cote, G

2015-11-01

Actinides determination in urine samples is part of the analyses performed to monitor internal contamination in case of an accident or a terrorist attack involving nuclear matter. Mineralisation is the first step of any of these analyses. It aims at reducing the sample volume and at destroying all organic compounds present. The mineralisation protocol is usually based on a wet ashing step, followed by actinides co-precipitation and a furnace ashing step, before redissolution and the quantification of the actinides by the appropriate techniques. Amongst the existing methods to perform the actinides co-precipitation, alkali-earth (typically calcium) precipitation is widely used. In the present work, the extraction of uranium(VI), plutonium(IV) and americium(III) from the redissolution solutions (called "mineralised urines") on calix[6]arene columns bearing hydroxamic groups was investigated as such an extraction is a necessary step before their determination by ICP-MS or alpha spectrometry. Difficulties were encountered in the transfer of uranium(VI) from raw to mineralised urines, with yield of transfer ranging between 0% and 85%, compared to about 90% for Pu and Am, depending on the starting raw urines. To understand the origin of such a difficulty, the speciation of uranium (VI) in mineralised urines was investigated by computer simulation using the MEDUSA software and the associated HYDRA database, compiled with recently published data. These calculations showed that the presence of phosphates in the "mineralised urines" leads to the formation of strong uranyl-phosphate complexes (such as UO2HPO4) which compete with the uranium (VI) extraction by the calix[6]arene bearing hydroxamic groups. The extraction constant of uranium (VI) by calix[6]arene bearing hydroxamic groups was determined in a 0.04 mol L(-1) sodium nitrate solution (logK=4.86±0.03) and implemented in an extraction model taking into account the speciation in the aqueous phase. This model allowed to simulate satisfactorily the experimental uranium extraction data and to support the preliminary conclusions about the role of the phosphates present in mineralised urines. These calculations also showed that the phosphate/calcium ratio is a key parameter as far as the efficiency of the uranium (VI) extraction by the calix[6]arene columns is concerned. It predicted that the addition of CaCl2 in mineralised urines would release uranium (VI) from phosphates by forming calcium (II)-phosphate complexes and thus facilitate the uranium (VI) extraction on calix[6]arene columns. These predictions were confirmed experimentally as the addition of 0.1 mol L(-1) CaCl2 to a mineralised urine containing naturally a high concentration of phosphate (typically 0.04 mol L(-1)) significantly increased the percentage of uranium (VI) extraction on the calix[6]arene columns. Copyright © 2015 Elsevier B.V. All rights reserved.

Soil properties controlling Zn speciation and fractionation in contaminated soils

NASA Astrophysics Data System (ADS)

Jacquat, Olivier; Voegelin, Andreas; Kretzschmar, Ruben

2009-09-01

We determined the speciation of Zn in 49 field soils differing widely in pH (4.1-7.7) and total Zn content (251-30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content.

PubMed

Voegelin, Andreas; Tokpa, Gerome; Jacquat, Olivier; Barmettler, Kurt; Kretzschmar, Ruben

2008-01-01

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.

Liquid chromatography-mass spectrometry (LC-MS): a powerful combination for selenium speciation in garlic (Allium sativum).

PubMed

Dumont, Emmie; Ogra, Yasumitsu; Vanhaecke, Frank; Suzuki, Kazuo T; Cornelis, Rita

2006-03-01

Liquid chromatography (LC) hyphenated with both elemental and molecular mass spectrometry has been used for Se speciation in Se-enriched garlic. Different species were separated by ion-pair liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) after hot-water extraction. They were identified by on-line reversed-phase liquid chromatography-electrospray ionization tandem mass spectrometry (RPLC-ESI-MS-MS). Se-methionine and Se-methylselenocysteine were determined by monitoring their product ions. Another compound, gamma-glutamyl-Se-methylselenocysteine, shown to be the most abundant form of Se in the garlic, was determined without any additional sample pre-treatment after extraction and without the need for a synthesized standard. Product ions for this dipeptide were detected by LC-ESI-MS-MS for three isotopes of Se-78 Se, 80Se: and 82Se. The method was extended to the species extracted during in-vitro gastrointestinal digestion. Because both Se-methylselenocysteine and gamma-glutamyl-Se-methylselenocysteine have anticarcinogenic properties, their extractability and stability during human digestion are very important. Garlic was also treated with saliva, to enable detection and analysis of species extracted during mastication. Detailed information on the extractability of selenium species by both simulated gastric and intestinal fluid are given, and variation of the distribution of Se among the different species with time is discussed. Although the main species in garlic is the dipeptide gamma-glutamyl-Se-methylselenocysteine, Se-methylselenocysteine is the main compound present in the extracts after treatment with gastrointestinal fluids. Two more, so far unknown compounds were observed in the chromatogram. The extracted species and their transformations were analysed by combining LC-ICP-MS and LC-ESI-MS-MS. In both the simulated gastric and intestinal digests, Se-methionine, Se-methylselenocysteine, and gamma-glutamyl-Se-methylselenocysteine could be determined by LC-ESI-MS-MS by measuring their typical product ions.

Matrix Dissolution Techniques Applied to Extract and Quantify Precipitates from a Microalloyed Steel

NASA Astrophysics Data System (ADS)

Lu, Junfang; Wiskel, J. Barry; Omotoso, Oladipo; Henein, Hani; Ivey, Douglas G.

2011-07-01

Microalloyed steels possess good strength and toughness, as well as excellent weldability; these attributes are necessary for oil and gas pipelines in northern climates. These properties are attributed in part to the presence of nanosized carbide and carbonitride precipitates. To understand the strengthening mechanisms and to optimize the strengthening effects, it is necessary to quantify the size distribution, volume fraction, and chemical speciation of these precipitates. However, characterization techniques suitable for quantifying fine precipitates are limited because of their fine sizes, wide particle size distributions, and low volume fractions. In this article, two matrix dissolution techniques have been developed to extract precipitates from a Grade100 (yield strength of 690 MPa) microalloyed steel. Relatively large volumes of material can be analyzed, and statistically significant quantities of precipitates of different sizes are collected. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) are combined to analyze the chemical speciation of these precipitates. Rietveld refinement of XRD patterns is used to quantify fully the relative amounts of the precipitates. The size distribution of the nanosized precipitates is quantified using dark-field imaging in the TEM.

Mercury speciation by differential photochemical vapor generation at UV-B vs. UV-C wavelength

NASA Astrophysics Data System (ADS)

Chen, Guoying; Lai, Bunhong; Mei, Ni; Liu, Jixin; Mao, Xuefei

2017-11-01

Photochemical vapor generation (PVG) is an effective sample introduction scheme for volatile mercury (Hg). Speciation of Hg++ and MeHg+ was fulfilled for the first time by differential PVG under UV-B vs. UV-C wavelength and applied to fish oil supplements. After liquid-liquid extraction, the aqueous extract was mixed with 0.4% anthranilic acid (AA)-20% formic acid (FA) in a quartz coil, and exposed sequentially to 311 nm or 254 nm UV light. The resulting Hg0 vapor was detected by atomic fluorescence spectrometry (AFS). At each wavelength, the AFS intensity was a linear function of Hg++ and MeHg+ concentrations, which were solvable from a set of two equations. This method achieved ultrahigh sensitivity with 0.50 and 0.63 ng mL- 1 limits of detection for Hg++ and MeHg+, respectively, and 73% recovery for MeHg+ at 10 ng mL- 1. Validation was performed by ICP-MS on total Hg. Obviation of chemical or chromatographic separation rendered this method rapid, green, and cost-effective.

Non-chromatographic speciation of chromium at sub-ppb levels using cloud point extraction in the presence of unmodified silver nanoparticles.

PubMed

López-García, Ignacio; Vicente-Martínez, Yesica; Hernández-Córdoba, Manuel

2015-01-01

The cloud point extraction (CPE) of silver nanoparticles (AgNPs) by Triton X-114 allows chromium (III) ions to be transferred to the surfactant-rich phase, where they can be measured by electrothermal atomic absorption spectrometry. Using 20 mL sample and 50 μL Triton X-114 (30% w/v), the enrichment factor was 1150, and calibration graphs were obtained in the 5-100 ng L(-1) chromium range in the presence of 5 µg L(-1) AgNPs. Speciation of trivalent and hexavalent chromium was achieved by carrying out two CPE experiments, one of them in the presence of ethylenediaminetetraacetate. While in the first experiment, in absence of the complexing agent, the concentration of total chromium was obtained, the analytical signal measured in the presence of this chemical allowed the chromium (VI) concentration to be measured, being that of chromium (III) calculated by difference. The reliability of the procedure was verified by using three standard reference materials before applying to water, beer and wine samples. Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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

2014-05-01

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

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

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

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE PAGES

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh; ...

2018-04-09

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

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

PubMed

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

2011-01-01

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

Investigation of Pu(IV)-acetohydroxamic acid complex by solvent extraction with di(2-ethylhexyl) phosphoric acid

NASA Astrophysics Data System (ADS)

Brown, M. Alex; Paulenova, Alena; Tkac, Peter

2010-03-01

The stability constant of the Pu(IV)-acetohydroxamic acid complex Pu(AHA)3+ at 1 M ionic strength (pH = 0) has been investigated by method of solvent extraction. Di(2-ethylhexyl) phosphoric acid (HDEHP) was used to extract Pu(IV) from perchloric and nitric acid media at various AHA concentrations. Distribution ratios over a range of ligand concentrations were used in conjunction with graphical methods to obtain logβ1 = 14.3 ± 0.03 in perchloric acid. The stability constant determined from solutions in nitric acid was excluded because of the uncertainty in plutonium speciation.

Utilization of modified corn silk as a biosorbent for solid-phase extraction of Cr(III) and chromium speciation.

PubMed

Yu, Hongmei; Pang, Jing; Wu, Mei; Wu, Qiaoli; Huo, Cuixiu

2014-01-01

The ues of corn silk modified with diluted nitric acid (HNO3-MCS) as a novel biosorbent has been established for solid-phase extraction of Cr(III) and chromium speciation in water samples. The functional groups of the HNO3-MCS surface are favorable for the adsorption of Cr(III). Effective extraction conditions were optimized in both batch and column methods. At pH 3.0 - 6.0, a discrimination of Cr(III) and Cr(VI) is achieved on the HNO3-MCS surface. Cr(III) ions are retained onto the HNO3-MCS surface, however, the adsorption of Cr(VI) is negligible under the same conditions. The adsorption isotherm of HNO3-MCS for Cr(III) has been demonstrated in accordance with a linear form of the Langmuir equation, and the maximum adsorption capacity is 35.21 mg g(-1). The well fitted linear regression of the pseudo-second order model showed the indication of a chemisorption mechanism for the entire concentration range. Thermodynamic studies have shown that the adsorption process is spontaneous and endothermic. The adsorbed Cr(III) was quantitatively eluted by a nitric acid solution with detection by flame atomic absorption spectrometry (FAAS). With a sample volume of 30 mL, a detection limit (3σ) of 0.85 μg L(-1) and a precision of 2.0% RSD at the 40 μg L(-1) level were achieved. The concentration of Cr(III) could be accurately quantified within a linear range of 3 - 200 μg L(-1). After Cr(VI) has been reduced to Cr(III) with hydroxylamine hydrochloride, the total amount of chromium was obtained, and the content of Cr(VI) was given by subtraction. The procedure was validated by analyzing chromium in a certified reference material (GBW (E) 080039). It was also successfully applied for the speciation of chromium in wastewater samples.

Total arsenic determination and speciation in infant food products by ion chromatography-inductively coupled plasma-mass spectrometry.

PubMed

Vela, Nohora P; Heitkemper, Douglas T

2004-01-01

Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mixed rice/formula cereals, milk-based infant formula, applesauce and puree of peaches, pears, carrots, sweet potatoes, green beans, and squash were evaluated for total and speciated arsenic content. Arsenic concentrations found in rice-based cereals (63-320 ng/g dry weight) were similar to those reported for raw rice. Results for the analysis of powdered infant formula by inductively coupled plasma-mass spectrometry (ICP-MS) indicated a narrow and low arsenic concentration range (12 to 17 ng/g). Arsenic content in puree infant food products, including rice cereals, fruits, and vegetables, varies from <1 to 24 ng/g wet weight. Sample treatment with trifluoroacetic acid at 100 degrees C were an efficient and mild method for extraction of arsenic species present in different food matrixes as compared to alternative methods that included sonication and accelerated solvent extraction. Extraction recoveries from 94 to 128% were obtained when the summation of species was compared to total arsenic. The ion chromatography (IC)-ICP-MS method selected for arsenic speciation allowed for the quantitative determination of inorganic arsenic [As(III) + As(V)], dimethylarsinic acid (DMA), and methylarsonic acid (MMA). Inorganic arsenic and DMA are the main species found in rice-based and mixed rice/formula cereals, although traces of MMA were also detected. Inorganic arsenic was present in freeze-dried sweet potatoes, carrots, green beans, and peaches. MMA and DMA were not detected in these samples. Arsenic species in squash, pears, and applesauce were not detected above the method detection limit [5 ng/g dry weight for As(III), MMA, and DMA and 10 ng/g dry weight for As(V)].

Speciation analysis of inorganic antimony in soil using HPLC-ID-ICP-MS.

PubMed

Amereih, Sameer; Meisel, Thomas; Kahr, Elisabeth; Wegscheider, Wolfhard

2005-12-01

Speciation analysis of Sb(III) and Sb(V) in a soil sample was performed through extraction and on-line isotope dilution concentration determination after a chromatographic separation. The total Sb concentration found in a through traffic contaminated soil sample was (4.17 microg g(-1), 0.3 microg g(-1) SD, n=6). It was determined using ICP-MS after soil digestion using the sodium peroxide sintering method. The optimized extraction procedure for speciation analysis was carried out using 100 mmol L(-1) citric acid at pH 2.08 by applying an ultrasonic bath for 45 min at room temperature. The effects of citric acid concentration (0-500 mmol L(-1)), pH (1-6), and temperature (30-60 degrees C) on inorganic antimony species distribution in the examined sample were studied and optimized. The separation of Sb(III) and Sb(V) was achieved using an anion exchange column (PRP-X100) and 10 mmol L(-1) EDTA and 1 mmol L(-1) phthalic acid at pH 4.5 as a mobile phase. The eluent from the HPLC was mixed with an enriched (94.2%) (123)Sb spike solution that was pumped by a peristaltic pump with a constant flow rate (0.5 mL min(-1)) in a three-way valve. The blend passed directly to the Conikal nebulizer of the ICP-MS. By using the above extraction procedure and methodology, 43.2% Sb(V) (2.9% RSD, n=3) and 6.0% Sb(III) (1.3% RSD, n=3) of total Sb found in the sample could be detected. The detection limits achieved by the proposed method were 20 ng L(-1) and 65 ng L(-1) for Sb(V) and Sb(III), respectively. The precision, evaluated by using RSD with 100 ng L(-1) calibration solutions, was 2.7% and 3.2% (n=6) for Sb(V) and Sb(III), respectively, in aqueous solutions.

The Development of Molybdenum Speciation as a Paleoredox Tool

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

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

Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction combined with graphite furnace atomic absorption spectrometric for selenium speciation in foods and beverages.

PubMed

Tuzen, Mustafa; Pekiner, Ozlem Zeynep

2015-12-01

A rapid and environmentally friendly ultrasound assisted ionic liquid dispersive liquid liquid microextraction (USA-IL-DLLME) was developed for the speciation of inorganic selenium in beverages and total selenium in food samples by using graphite furnace atomic absorption spectrometry. Some analytical parameters including pH, amount of complexing agent, extraction time, volume of ionic liquid, sample volume, etc. were optimized. Matrix effects were also investigated. Enhancement factor (EF) and limit of detection (LOD) for Se(IV) were found to be 150 and 12 ng L(-1), respectively. The relative standard deviation (RSD) was found 4.2%. The accuracy of the method was confirmed with analysis of LGC 6010 Hard drinking water and NIST SRM 1573a Tomato leaves standard reference materials. Optimized method was applied to ice tea, soda and mineral water for the speciation of Se(IV) and Se(VI) and some food samples including beer, cow's milk, red wine, mixed fruit juice, date, apple, orange, grapefruit, egg and honey for the determination of total selenium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques.

PubMed

Terzano, Roberto; Santoro, Anna; Spagnuolo, Matteo; Vekemans, Bart; Medici, Luca; Janssens, Koen; Göttlicher, Jörg; Denecke, Melissa A; Mangold, Stefan; Ruggiero, Pacifico

2010-08-01

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg(-1). Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as mu-XRF, mu-XRD and mu-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 microm. The main Hg-species found in the soil samples were metacinnabar (beta-HgS), cinnabar (alpha-HgS), corderoite (Hg(3)S(2)Cl(2)), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 microm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution. Copyright 2010 Elsevier Ltd. All rights reserved.

Mercury(II) and methyl mercury determinations in water and fish samples by using solid phase extraction and cold vapour atomic absorption spectrometry combination.

PubMed

Tuzen, Mustafa; Karaman, Isa; Citak, Demirhan; Soylak, Mustafa

2009-07-01

A method has been developed for mercury(II) and methyl mercury speciation on Staphylococcus aureus loaded Dowex Optipore V-493 micro-column in the presented work, by using cold vapour atomic absorption spectrometry. Selective and sequential elution with 0.1 molL(-1) HCl for methyl mercury and 2 molL(-1) HCl for mercury(II) were performed at the pH range of 2-6. Optimal analytical conditions including pH, amounts of biosorbent, sample volumes were investigated. The detection limits of the analytes were 2.5 ngL(-1) for Hg(II) and 1.7 ngL(-1) for methyl mercury. The capacity of biosorbent for mercury(II) and methyl mercury was 6.5 and 5.4 mgg(-1), respectively. The validation of the presented procedure is performed by the analysis of standard reference material. The speciation procedure established was successfully applied to the speciation of mercury(II) and methyl mercury in natural water and microwave digested fish samples.

Equilibrium of molybdenum in selected extraction systems

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

Tkac, Peter; Paulenova, Alena

2007-07-01

The concentration of molybdenum(VI) in dissolved irradiated nuclear fuel is comparable with the concentrations of Tc, Am and Np. Therefore it is of big interest to understand its behavior under conditions related to the UREX/TRUEX process. The effect of the poly-speciation of molybdenum in aqueous solution on its extraction by neutral solvents TBP and CMPO/TBP was studied. Extraction yields of molybdenum decreased significantly when AHA was added to aqueous phase. Our investigation confirmed a strong ability of the aceto-hydroxamic acid to form complexes with Mo in high acidic solutions. Spectroscopic data (UV-Vis) confirmed that a fraction of the Mo(VI)-AHA complexmore » is present in the organic phase after extraction. (authors)« less

Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO2 photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry.

PubMed

Liang, Jing; Wang, Qiuquan; Huang, Benli

2005-01-01

An online UV photolysis and UV/TiO2 photocatalysis reduction device (UV-UV/TiO2 PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 microL dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV-UV/TiO2 PCRD-KBH4-acid interface. The detection limits obtained for seleno-DL: -cystine (SeCys), selenite (Se(IV)), seleno-DL: -methionine (SeMet), and selenate (Se(VI)) were 2.1, 2.9, 4.3, and 3.5 ng mL(-1), respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV-UV/TiO2 PCRD-ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH4.

Comparing WHAM 6 and MINEQL+ 4.5 for the chemical speciation of Cu2+ in the rhizosphere of forest soils.

PubMed

Cloutier-Hurteau, Benoît; Sauvé, Sébastien; Courchesne, François

2007-12-01

Metal speciation data calculated by modeling could give useful information regarding the fate of metals in the rhizospheric environment. However, no comparative study has evaluated the relative accuracy of speciation models in this microenvironment. Consequently, the present study evaluates the reliability of free Cu ion (Cu2+) activity modeled by WHAM 6 and MINEQL+ 4.5 for 18 bulk and 18 rhizospheric soil samples collected in two Canadian forested areas located near industrial facilities. The modeling of Cu speciation was performed on water extracts using pH, dissolved organic carbon (DOC), major ions, and total dissolved Al, Ca, Cu, Mg, and Zn concentrations as input data. Four scenarios representing the composition of dissolved organic substances using fulvic, humic, and acetic acids were derived from the literature and used in the modeling exercise. Different scenarios were used to contrast soil components (rhizosphere vs bulk) and soil pH levels (acidic vs neutral to alkaline). Reference Cu2+ activity values measured by an ion-selective electrode varied between 0.39 and 41 nM. The model MINEQL+ 4.5 provided good predictions of Cu2+ activities [root-mean-square residual (RMSR)= 0.37], while predictions from WHAM 6 were poor (RMSR = 1.74) because they overestimated Cu complexation with DOC. Modeling with WHAM 6 could be improved by adjusting the proportion of inert DOC and the composition of DOC (RMSR = 0.94), but it remained weaker than predictions with MINEQL+ 4.5. These results suggested that the discrepancies between speciation models were attributed to differences in the binding capacity of humic substances with Cu, where WHAM 6 appeared to be too aggressive. Therefore, we concluded that chemical interactions occurring between Cu and DOC were key factors for an accurate simulation of Cu speciation, especially in rhizospheric forest soils, where high variation of the DOC concentration and composition are observed.

Adding to the Mercury Speciation Toolbox

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Levels and speciation of arsenic in the atmosphere in Beijing, China.

PubMed

Yang, Guosheng; Ma, Lingling; Xu, Diandou; Li, Jie; He, Tingting; Liu, Liyan; Jia, Hongliang; Zhang, Yongbao; Chen, Yang; Chai, Zhifang

2012-05-01

Arsenic levels and speciation in the total suspended particles (TSPs) were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry in Beijing, China from February 2009 to March 2011. The high TSP levels fluctuated between 0.07 and 0.79 mg m(-3), with a mean level of 0.32 ± 0.17 mg m(-3). The total arsenic concentrations ranged from 0.03 to 0.31 μg m(-3) (mean: 0.13 ± 0.06 μg m(-3)) in Beijing's air. The concentrations of As(III) and As(V) ranged from 0.73 to 20 ng m(-3) (mean: 4.7 ± 3.6 ng m(-3)) and from 14 to 2.5 × 10(2) ng m(-3) (mean: 67 ± 35 ng m(-3)), respectively. As levels and speciation demonstrated relative higher levels in spring and autumn and lower values in summer and winter. As(V) accounted for 81-99% of the extractable species in the TSP samples which showed that As(V) was the major fraction of the extractable As. Organoarsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA) were not found in all samples. Higher values of enrichment factors demonstrated that arsenic in TSP mainly come from anthropogenic sources. High As and its species levels in air and respiratory exposure (0.30-0.84 μg d(-1)) attributed to higher excess cancer risk ((4.2 ± 2.0) × 10(-4)) for people in Beijing. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

USGS Publications Warehouse

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

1993-01-01

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

Chemical speciation and recovery of gold(I, III) from wastewater and silver by liquid-liquid extraction with the ion-pair reagent amiloride mono hydrochloride and AAS determination.

PubMed

El-Shahawi, M S; Bashammakh, A S; Bahaffi, S O

2007-06-15

A novel and low cost liquid-liquid extraction procedure for the separation of gold(III) at trace level from aqueous medium of pH 5-9 has been developed. The method has been based upon the formation of a yellow colored ternary complex ion associate of tetrachloro gold(III) complex anion, AuCl(4)(-) with the ion-pair reagent 1-(3,5-diamino-6-chloropyrazinecarboxyl) guanidine hydrochloride monohydrate, namely amiloride, DPG(+).Cl(-). The effect of various parameters, e.g. pH, organic solvent, shaking time, etc. on the preconcentration of gold(III) from the aqueous media by the DPG(+).Cl(-) reagent has been investigated. The colored gold species was quantitatively extracted into 4-methyl pentan-2-one. The chemical composition of the ion associate of DPG(+).Cl(-) with AuCl(4)(-) in the organic solvent has been determined by the Job's method. The molar absorptivity (2.19x10(4)Lmol(-1)cm(-1)) of the associate DPG(+).AuCl(4)(-) at 362nm enabled a convenient application of the developed extraction procedure for the separation and AAS determination of traces of aurate ions. Mono-valence gold ions after oxidation to gold(III) with bromine water in HCl (1.0molL(-1)) media have been also extracted quantitatively from the aqueous media by the developed procedure. The chemical speciation of mono- and/or tri-valence gold species spiked to fresh and industrial wastewater samples has been achieved. The method has been also applied successfully from the separation of gold(I) and gold(III) species from metallic ions and silver. The developed method has also the advantage of freedom from most diverse ions.

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

PubMed

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

2005-01-01

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

Competitive Dominance among Strains of Luminous Bacteria Provides an Unusual Form of Evidence for Parallel Evolution in Sepiolid Squid-Vibrio Symbioses

PubMed Central

Nishiguchi, Michele K.; Ruby, Edward G.; McFall-Ngai, Margaret J.

1998-01-01

One of the principal assumptions in symbiosis research is that associated partners have evolved in parallel. We report here experimental evidence for parallel speciation patterns among several partners of the sepiolid squid-luminous bacterial symbioses. Molecular phylogenies for 14 species of host squids were derived from sequences of both the nuclear internal transcribed spacer region and the mitochondrial cytochrome oxidase subunit I; the glyceraldehyde phosphate dehydrogenase locus was sequenced for phylogenetic determinations of 7 strains of bacterial symbionts. Comparisons of trees constructed for each of the three loci revealed a parallel phylogeny between the sepiolids and their respective symbionts. Because both the squids and their bacterial partners can be easily cultured independently in the laboratory, we were able to couple these phylogenetic analyses with experiments to examine the ability of the different symbiont strains to compete with each other during the colonization of one of the host species. Our results not only indicate a pronounced dominance of native symbiont strains over nonnative strains, but also reveal a hierarchy of symbiont competency that reflects the phylogenetic relationships of the partners. For the first time, molecular systematics has been coupled with experimental colonization assays to provide evidence for the existence of parallel speciation among a set of animal-bacterial associations. PMID:9726861

Boron uptake, localization, and speciation in marine brown algae.

PubMed

Miller, Eric P; Wu, Youxian; Carrano, Carl J

2016-02-01

In contrast to the generally boron-poor terrestrial environment, the concentration of boron in the marine environment is relatively high (0.4 mM) and while there has been extensive interest in its use as a surrogate of pH in paleoclimate studies in the context of climate change-related questions, the relatively depth independent, and the generally non-nutrient-like concentration profile of this element have led to boron being neglected as a potentially biologically relevant element in the ocean. Among the marine plant-like organisms the brown algae (Phaeophyta) are one of only five lineages of photosynthetic eukaryotes to have evolved complex multicellularity. Many of unusual and often unique features of brown algae are attributable to this singular evolutionary history. These adaptations are a reflection of the marine coastal environment which brown algae dominate in terms of biomass. Consequently, brown algae are of fundamental importance to oceanic ecology, geochemistry, and coastal industry. Our results indicate that boron is taken up by a facilitated diffusion mechanism against a considerable concentration gradient. Furthermore, in both Ectocarpus and Macrocystis some boron is most likely bound to cell wall constituent alginate and the photoassimilate mannitol located in sieve cells. Herein, we describe boron uptake, speciation, localization and possible biological function in two species of brown algae, Macrocystis pyrifera and Ectocarpus siliculosus.

Head space solid phase microextraction based on nano-structured lead dioxide: application to the speciation of volatile organoselenium in environmental and biological samples.

PubMed

Ghasemi, Ensieh; Farahani, Hadi

2012-10-05

A novel and efficient speciation method based on the nano-structured lead dioxide as stationary phase of head space solid phase microextraction combined with gas chromatography mass spectrometry (GC-MS) was developed for the determination of volatile organoselenium compounds (dimethylselenide (DMSe) and dimethyldiselenide (DMDSe)) in different biological and environmental samples. PbO(2) particles with a diameter in the range of 50-70 nm have been grown on platinum wire via elechtrochemical deposition. The effect of different variables on the extraction efficiency was studied simultaneously using an experimental design. The variables of interest in the HS-SPME were condition of coating preparation, desorption time, stirring rate, desorption temperature, ionic strength, time and temperature of extraction. A Plackett-Burman design was performed for screening in order to determine the significant variables affecting the extraction efficiency. Then, the significant factors were optimized by a Box-Behnken design (BBD) and the response surface equations were derived. The detection limit and relative standard deviation (RSD) (n=5, c=50 μgL(-1)) for DMSe were 16 ngL(-1) and 4.3%, respectively. They were also obtained for DMDSe as 11ngL(-1) and 4.6%, respectively. The developed technique was found to be applicable to spiked environmental and biological samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Speciation and distribution characteristics of heavy metals and pollution assessments in the sediments of Nashina Lake, Heilongjiang, China.

PubMed

Li, Miao; Zang, Shuying; Xiao, Haifeng; Wu, Changshan

2014-05-01

Sediment core samples from Nashina Lake, Heilongjiang, China were collected using a gravity sampler. The cores were sliced horizontally at 1 cm each to determine the particle size, total concentrations and speciation of Cd, Cr, Cu, Mn, Ni, Pb, and Zn. Total concentrations of heavy metals were extracted using an acid mixture (containing hydro fluoric acid, nitric acid, and sulphuric acid) and analyzed using an inductively coupled plasma spectrometry. A sequential extraction procedure was employed to separate chemical species. Analysis of results indicate that the concentrations of heavy metals in the sediments of Nashina Lake in descending order are Mn, Cr, Zn, Pb, Ni, Cu, and Cd. The ratios of the average concentrations of four heavy metals (e.g.Cr, Cu, Ni, Zn) to their background values were >1; and those of Mn, Cd, and Pb were >1. Moreover, some toxic metals were mainly distributed in bioavailable fractions. For instance, both Cd and Mn were typically found in Acid-extractable species or Fe-Mn oxide species, and thus can be easily remobilized and enter the food chain. Finally, the analysis of geo-accumulation index showed that anthropogenic pollution levels of Cr, Cu, Mn, Ni, Zn were low, but those of Pb and Cd were at the moderate level. As both Pb and Cd are toxic metals, it is highly necessary to prohibit their transformation and accumulation in the sediments.

Direct comparison of XAFS spectroscopy and sequential extraction for arsenic speciation in coal

USGS Publications Warehouse

Huggins, Frank E.; Huffman, G.P.; Kolker, A.; Mroczkowski, S.; Palmer, C.A.; Finkelman, R.B.

2000-01-01

The speciation of arsenic in an Ohio bituminous coal and a North Dakota lignite has been examined by the complementary methods of arsenic XAFS spectroscopy and sequential extraction by aqueous solutions of ammonium acetate, HCl, HF, and HNO3. In order to facilitate a more direct comparison of the two methods, the arsenic XAFS spectra were obtained from aliquots of the coal prepared after each stage of the leaching procedure. For the aliquots, approximately linear correlations (r2 > 0.98 for the Ohio coal, > 0.90 for the ND lignite) were observed between the height of the edge-step in the XAFS analysis and the concentration of arsenic measured by instrumental neutron activation analysis. Results from the leaching sequence indicate that there are two major arsenic forms present in both coals; one is removed by leaching with HCl and the other by HNO3. Whereas the XAFS spectral signatures of the arsenic leached by HCl are compatible with arsenate for both coals, the arsenic leached by HNO3 is identified as arsenic associated with pyrite for the Ohio coal and as an As3+ species for the North Dakota lignite. Minor arsenate forms persist in both coals after the final leaching with nitric acid. The arsenate forms extracted in HCl are believed to be oxidation products derived from the other major arsenic forms upon exposure of the pulverized coals to air.

Arsenic speciation and fucoxanthin analysis from seaweed dietary supplements using LC-MS.

PubMed

Avula, Bharathi; Wang, Yan-Hong; Khan, Ikhlas A

2015-01-01

The study involves the analysis of total arsenic (As) in metallic form, and organic and inorganic As species from seaweeds and dietary supplements. The analysis provides data for dietary exposure estimates of inorganic species that are considered more toxic to humans than organic and total As. Total As was determined by acid digestion followed by inductively coupled plasma (ICP)-MS. To characterize the As species, solvent extraction with sonication and microwave extraction using various aqueous and aqueous/organic solvent mixtures were initially evaluated. The optimum As speciation method was determined to be water extraction followed by anion exchange HPLC coupled with ICP-MS. Optimization of chromatographic conditions led to baseline separation for six As species, including As acid, arsenous acid, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, in approximately 8 min using gradient elution. Detection limits for all six compounds were in the range of 10-15 ng/mL. The data presented here will be valuable for the QA of analytical method development and surveys of total As and As species in dietary supplements. The most abundant As species found were arsenite [As(III)] and arsenate [As(V)]. The sum of inorganic As species present in the dietary supplements ranged from 1.2 to 31 μg/day. In addition, the dietary supplements purported to contain fucoxanthin, a carotenoid having pharmacological activities, were analyzed using ultra-performance LC-UV/MS.

Characterization and measurement of natural gas trace constituents. Volume 1. Arsenic. Final report, June 1989-October 1993

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

Chao, S.S.; Attari, A.

1995-01-01

The discovery of arsenic compounds, as alkylarsines, in natural gas prompted this research program to develop reliable measurement techniques needed to assess the efficiency of removal processes for these environmentally sensitive substances. These techniques include sampling, speciation, quantitation and on-line instrumental methods for monitoring the total arsenic concentration. The current program has yielded many products, including calibration standards, arsenic-specific sorbents, sensitive analytical methods and instrumentation. Four laboratory analytical methods have been developed and successfully employed for arsenic determination in natural gas. These methods use GC-AED and GC-MS instruments to speciate alkylarsines, and peroxydisulfate extraction with FIAS, special carbon sorbent withmore » XRF and an IGT developed sorbent with GFAA for total arsenic measurement.« less

Radiation of the Drosophila nannoptera species group in Mexico.

PubMed

Lang, M; Polihronakis Richmond, M; Acurio, A E; Markow, T A; Orgogozo, V

2014-03-01

The Drosophila nannoptera species group, a taxon of Mexican cactophilic flies, is an excellent model system to study the influence of abiotic and biotic factors on speciation, the genetic causes of ecological specialization and the evolution of unusual reproductive characters. However, the phylogenetic relationships in the nannoptera species group and its position within the virilis-repleta phylogeny have not been thoroughly investigated. Using a multilocus data set of gene coding regions of eight nuclear and three mitochondrial genes, we found that the four described nannoptera group species diverged rapidly, with very short internodes between divergence events. Phylogenetic analysis of repleta group lineages revealed that D. inca and D. canalinea are sister to all other repleta group species, whereas the annulimana species D. aracataca and D. pseudotalamancana are sister to the nannoptera and bromeliae species groups. Our divergence time estimates suggest that the nannoptera species group radiated following important geological events in Central America. Our results indicate that a single evolutionary transition to asymmetric genitalia and to unusual sperm storage may have occurred during evolution of the nannoptera group. © 2014 The Authors. Journal of Evolutionary Biology © 2014 European Society For Evolutionary Biology.

Stability of toxic arsenic species and arsenosugars found in the dry alga Hijiki and its water extracts.

PubMed

García-Salgado, Sara; Quijano, M Ángeles

2014-10-01

The achievement of reliable results in speciation analysis requires not only sensitive techniques but also sureness of species stability. Therefore, it is necessary to carry out stability studies because it is important to know with absolute certainty that there is not any species transformation during sample treatment and/or storage. Although several procedures have been recommended for the preservation of species integrity, there is no general agreement, as arsenic species stability depends on the sample matrix, the concentration level and the sample treatment procedure, so it is necessary to assess the arsenic species stability for each case. Thus, the present paper reports the stability tests of arsenic species carried out on the commercially available edible alga Hijiki (Hizikia fusiformis), from Japan, in both the dry sample and its water extracts, which were stored in amber glass and polystyrene containers at -18 and +4°C in the dark. Extractions were carried out with deionized water by microwave-assisted extraction, at a temperature of 90°C and three extraction steps of 5 min each, whereas arsenic speciation analysis was performed by anion exchange high performance liquid chromatography-photo-oxidation-hydride generation-atomic fluorescence spectrometry. The results obtained for the dry alga showed that the arsenic species present in it (arsenate (As(V)), dimethylarsinic acid (DMA) and the arsenosugars glycerol (Gly-sug), phosphate (PO4-sug), sulfonate (SO3-sug) and sulfate (SO4-sug)) were stable for at least 12 months when the sample was stored in polystyrene containers at +20°C in the dark. Regarding water extracts, the best storage conditions consisted of the use of polystyrene containers and a temperature of +4°C, for a maximum storage time of seven days. Therefore, the immediate analysis of Hijiki water extracts would not be necessary, and they could be stored for one week before analysis, ensuring arsenic species stability. This information about species integrity in extracts is especially useful when the sample treatment for arsenic species extraction is time-consuming. Copyright © 2014 Elsevier B.V. All rights reserved.

Actinomyces meyeri brain abscess following dental extraction

PubMed Central

Clancy, U; Ronayne, A; Prentice, M B; Jackson, A

2015-01-01

We describe the rare occurrence of an Actinomyces meyeri cerebral abscess in a 55-year-old woman following a dental extraction. This patient presented with a 2-day history of hemisensory loss, hyper-reflexia and retro-orbital headache, 7 days following a dental extraction for apical peridonitis. Neuroimaging showed a large left parietal abscess with surrounding empyema. The patient underwent craniotomy and drainage of the abscess. A. meyeri was cultured. Actinomycosis is a rare cause of cerebral abscess. The A. meyeri subtype is particularly rare, accounting for less than 1% of specimens. This case describes an unusually brief course of the disease, which is usually insidious. Parietal lobe involvement is unusual as cerebral abscesses usually have a predilection for the frontal and temporal regions of the brain. Although there are no randomised trials to guide therapy, current consensus is to use a prolonged course of intravenous antibiotics, followed by 6–12 months of oral therapy. PMID:25870213

Transformation of zinc-concentrate in surface and subsurface environments: Implications for assessing zinc mobility/toxicity and choosing an optimal remediation strategy.

PubMed

Kwon, Man Jae; Boyanov, Maxim I; Yang, Jung-Seok; Lee, Seunghak; Hwang, Yun Ho; Lee, Ju Yeon; Mishra, Bhoopesh; Kemner, Kenneth M

2017-07-01

Zinc contamination in near- and sub-surface environments is a serious threat to many ecosystems and to public health. Sufficient understanding of Zn speciation and transport mechanisms is therefore critical to evaluating its risk to the environment and to developing remediation strategies. The geochemical and mineralogical characteristics of contaminated soils in the vicinity of a Zn ore transportation route were thoroughly investigated using a variety of analytical techniques (sequential extraction, XRF, XRD, SEM, and XAFS). Imported Zn-concentrate (ZnS) was deposited in a receiving facility and dispersed over time to the surrounding roadside areas and rice-paddy soils. Subsequent physical and chemical weathering resulted in dispersal into the subsurface. The species identified in the contaminated areas included Zn-sulfide, Zn-carbonate, other O-coordinated Zn-minerals, and Zn species bound to Fe/Mn oxides or clays, as confirmed by XAFS spectroscopy and sequential extraction. The observed transformation from S-coordinated Zn to O-coordinated Zn associated with minerals suggests that this contaminant can change into more soluble and labile forms as a result of weathering. For the purpose of developing a soil washing remediation process, the contaminated samples were extracted with dilute acids. The extraction efficiency increased with the increase of O-coordinated Zn relative to S-coordinated Zn in the sediment. This study demonstrates that improved understanding of Zn speciation in contaminated soils is essential for well-informed decision making regarding metal mobility and toxicity, as well as for choosing an appropriate remediation strategy using soil washing. Copyright © 2017 Elsevier Ltd. All rights reserved.

Speciation and isotopic exchangeability of nickel in soil solution.

PubMed

Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

2009-01-01

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. In this study, free Ni(2+) activities were determined in pore waters of long-term Ni-contaminated soils using a Donnan dialysis membrane technique. The pore water free Ni(2+) concentration as a percentage of total soluble Ni ranged from 21 to 80% (average 53%), and the average amount of Ni bound to dissolved organic matter estimated by Windermere Humic Aqueous Model VI was < or = 17%. These data indicate that complexed forms of Ni can constitute a significant fraction of total Ni in solution. Windermere Humic Aqueous Model VI provided reasonable estimates of free Ni(2+) fractions in comparison to the measured fractions (R(2) = 0.83 with a slope of 1.0). Also, the isotopically exchangeable pools (E value) of soil Ni were measured by an isotope dilution technique using water extraction, with and without resin purification, and 0.1 mol L(-1) CaCl(2) extraction, and the isotopic exchangeability of Ni species in soil water extracts was investigated. The concentrations of isotopically non-exchangeable Ni in water extracts were <9% of total water soluble Ni concentrations for all soils. The resin E values expressed as a percentage of the total Ni concentrations in soil showed that the labile Ni pool ranged from 0.9 to 32.4% (average 12.4%) of total soil Ni. Therefore the labile Ni pool in these well-equilibrated contaminated soils appears to be relatively small in relation to total Ni concentrations.

Transformation of zinc-concentrate in surface and subsurface environments: Implications for assessing zinc mobility/toxicity and choosing an optimal remediation strategy

DOE PAGES

Kwon, Man Jae; Boyanov, Maxim I.; Yang, Jung -Seok; ...

2017-03-24

Zinc contamination in near- and sub-surface environments is a serious threat to many ecosystems and to public health. Sufficient understanding of Zn speciation and transport mechanisms is therefore critical to evaluating its risk to the environment and to developing remediation strategies. The geochemical and mineralogical characteristics of contaminated soils in the vicinity of a Zn ore transportation route were thoroughly investigated using a variety of analytical techniques (sequential extraction, XRF, XRD, SEM, and XAFS). Imported Zn-concentrate (ZnS) was deposited in a receiving facility and dispersed over time to the surrounding roadside areas and rice-paddy soils. Subsequent physical and chemical weatheringmore » resulted in dispersal into the subsurface. The species identified in the contaminated areas included Zn-sulfide, Zn-carbonate, other O-coordinated Zn-minerals, and Zn species bound to Fe/Mn oxides or clays, as confirmed by XAFS spectroscopy and sequential extraction. The observed transformation from S-coordinated Zn to O-coordinated Zn associated with minerals suggests that this contaminant can change into more soluble and labile forms as a result of weathering. For the purpose of developing a soil washing remediation process, the contaminated samples were extracted with dilute acids. The extraction efficiency increased with the increase of O-coordinated Zn relative to S-coordinated Zn in the sediment. Furthermore, this study demonstrates that improved understanding of Zn speciation in contaminated soils is essential for well-informed decision making regarding metal mobility and toxicity, as well as for choosing an appropriate remediation strategy using soil washing.« less

A non-multimacrocyclic heteroditopic receptor that cooperatively binds and effectively extracts KAcO salt.

PubMed

Zakrzewski, Maciej; Kwietniewska, Natalia; Walczak, Wojciech; Piątek, Piotr

2018-06-06

Prepared in only three synthetic steps, a non-multimacrocyclic heteroditopic receptor binds potassium salts of halides and carboxylates with unusually high cooperativity, suggesting salt binding as associated ion-pairs. Unprecedented extraction of highly hydrophilic KAcO salt from water to organic solution is also demonstrated.

Aluminium (Al) speciation in serum and urine after subcutaneous venom immunotherapy with Al as adjuvant.

PubMed

Michalke, Bernhard; Kramer, Matthias F; Brehler, Randolf

2018-02-21

Aluminium is associated with disorders and is the commonly used vaccine adjuvant. Understanding the mechanisms of how Al is transported, metabolized or of its toxicity depends on the knowledge of Al-interactions with bioligands, i.e. Al-species. Al-speciation in serum is difficult because of low concentration and the risk of exogenous Al contamination. Furthermore, Al-measurements may be hampered according to various interferences. This study aims for developing quality controlled protocols for reliable Al- and Al-species determination and for investigating probable differences in Al (-speciation) after Al-containing subcutaneous immunotherapy (SIT). Sample donors were recruited either for the control group ("class-0", they never had been treated with SIT containing an Al-depot extract) or for the SIT-group ("class-1", they previously had been treated with SIT for insect venom allergy with an Al-depot extract). Blood was drawn for medical reasons and serum prepared. Additionally, some sample donors collected 24-h-urine. They had been informed (and they consented) about the scientific use of their samples. The study was approved by the ethic committee of the "Medical Association Westphalia-Lippe" and of the University of Münster, evaluating the study positively (No. 2013-667-f-S). We applied quality controlled sample preparation and interference-free Al detection by ICP sectorfield-mass spectrometry. Al-species were analysed using size-exclusion-chromatography-ICP-qMS. Al-concentrations or speciation in urine samples showed no differences between class-0 and class-1. Al-citrate was the main uric Al-species. In serum elevated Al-concentrations were found for both classes, with class-1 samples being significantly higher than class-0 (p = 0.041), but class-0 samples being approximately 10-fold too high compared to reference values from non-exposed persons. We identified gel-monovettes as contamination source. In contamination-free samples from HNO 3 -prewashed gel-free monovettes (n = 27) there was no difference in the serum Al concentration between the two patient groups (p = 0.669) INTERPRETATION: Thorough cleaning of sample preparation ware and use of gel-free monovettes is decisive for an accurate Al analysis in serum. Without these steps, wrong analysis and wrong conclusions are likely. We conclude that gel-monovettes are unsuitable for blood sampling with subsequent Al-analysis. Whether Al in serum is elevated after SIT treatment containing an Al-depot extract, or not, remains inconclusive as the non-contaminated sample size was small. Copyright © 2018 Elsevier GmbH. All rights reserved.

Simultaneous speciation of inorganic arsenic, selenium and tellurium in environmental water samples by dispersive liquid liquid microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry.

PubMed

Liu, Ying; He, Man; Chen, Beibei; Hu, Bin

2015-09-01

A new method based on dispersive liquid liquid microextraction (DLLME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the simultaneous speciation of inorganic arsenic (As), selenium (Se) and tellurium (Te) with sodium diethyldithiocarbamate (DDTC) as both chelating reagent and chemical modifier. As(III), Se(IV) and Te(IV) were transformed into DDTC-chelates at pH 7 and extracted into the fine droplets formed by injecting the binary solution of bromobenzene (extraction solvent) and methanol (dispersive solvent) into the sample solution. After phase separation by centrifugation, As(III), Se(IV) and Te(IV) preconcentrated in the organic phase were determined by ETV-ICP-MS. Total inorganic As, Se and Te were obtained by reducing As(V), Se(VI) and Te(VI) to As(III), Se(IV) and Te(IV) with L-cysteine, which were then subjected to the same DLLME-ETV-ICP-MS process. The concentration of As(V), Se(VI), Te(VI) were calculated by subtracting the concentration of As(III), Se(IV) and Te(IV) from the total inorganic As, Se and Te, respectively. The main factors affecting the microextraction efficiency and the vaporization behavior of target species were investigated in detail. Under the optimal conditions, the limits of detection were 2.5, 8.6 and 0.56 ng L(-1) for As(III), Se(IV) and Te(IV), respectively, with the relative standard deviations (n=7) of 8.5-9.7%. The developed method was applied to the speciation of inorganic As, Se and Te in Certified Reference Materials of GSBZ50004-88, GBW(E)080395 and GBW(E)080548 environmental waters, and the determined values are in good agreement with the certified values. The method was also successfully applied to the simultaneous speciation of inorganic As, Se and Te in different environmental water samples with the recoveries in the range of 86.3-107% for the spiked samples. Copyright © 2015 Elsevier B.V. All rights reserved.

A Permeable Active Amendment Concrete (PAAC) for Contaminant Remediation and Erosion Control

DTIC Science & Technology

2012-06-01

124: 131 -143. SRNL-STI-2012-00356 70 Tessier, A., Campbell, P.G.C., and Bisson, M. 1979. Sequential extraction procedure for the speciation of...Bulk Density, Dry, (AI( C-D)]* p, pcf 134.85 Bulk Dens ity after Immersion, [BI(C-D)]* p, pcf 146.65 Bulk Density after Immersion & Boiling1 jCI (C

Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments

NASA Astrophysics Data System (ADS)

Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng

2017-12-01

Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (<2 μm), the size fraction most prone to long-distance transport as dust. Samples were analyzed by sequential chemical extraction, X-ray diffraction, and diffuse reflectance spectrometry. Our results show that Fe dissolved from easily reducible iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

PubMed

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

2017-05-05

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

Sequential photocatalyst-assisted digestion and vapor generation device coupled with anion exchange chromatography and inductively coupled plasma mass spectrometry for speciation analysis of selenium species in biological samples.

PubMed

Tsai, Yun-ni; Lin, Cheng-hsing; Hsu, I-hsiang; Sun, Yuh-chang

2014-01-02

We have developed an on-line sequential photocatalyst-assisted digestion and vaporization device (SPADVD), which operates through the nano-TiO2-catalyzed photo-oxidation and reduction of selenium (Se) species, for coupling between anion exchange chromatography (LC) and inductively coupled plasma mass spectrometry (ICP-MS) systems to provide a simple and sensitive hyphenated method for the speciation analysis of Se species without the need for conventional chemical digestion and vaporization techniques. Because our proposed on-line SPADVD allows both organic and inorganic Se species in the column effluent to be converted on-line into volatile Se products, which are then measured directly through ICP-MS, the complexity of the procedure and the probability of contamination arising from the use of additional chemicals are both low. Under the optimized conditions for SPADVD - using 1g of nano-TiO2 per liter, at pH 3, and illuminating for 80 s - we found that Se(IV), Se(VI), and selenomethionine (SeMet) were all converted quantitatively into volatile Se products. In addition, because the digestion and vaporization efficiencies of all the tested selenicals were improved when using our proposed on-line LC/SPADVD/ICP-MS system, the detection limits for Se(IV), Se(VI), and SeMet were all in the nanogram-per-liter range (based on 3σ). A series of validation experiments - analysis of neat and spiked extracted samples - indicated that our proposed methods could be applied satisfactorily to the speciation analysis of organic and inorganic Se species in the extracts of Se-enriched supplements. Copyright © 2013. Published by Elsevier B.V.

Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS.

PubMed

Peng, Hanyong; Zhang, Nan; He, Man; Chen, Beibei; Hu, Bin

2015-01-01

Speciation analysis of inorganic arsenic, chromium and selenium in environmental waters is of great significance for the monitoring of environmental pollution. In this work, 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS) functionalized multi-wall carbon nanotubes (MWCNTs) were synthesized and employed as the adsorbent for simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by microcolumn solid-phase extraction (SPE)-inductively coupled plasma mass spectrometry (ICP-MS). It was found that As(V), Cr(VI) and Se(VI) could be selectively adsorbed on the microcolumn packed with AAPTS-MWCNTs adsorbent at pH around 2.2, while As(III), Cr(III) and Se(IV) could not be retained at this pH and passed through the microcolumn directly. Total inorganic arsenic, chromium and selenium was determined after the oxidation of As(III), Cr(III) and Se(IV) to As(V), Cr(VI) and Se(VI) with 10.0 μmol L(-1) KMnO4. The assay of As(III), Cr(III) and Se(IV) was based on subtracting As(V), Cr(VI) and Se(VI) from the total As, Cr and Se, respectively. Under the optimized conditions, the detection limits of 15, 38 and 16 ng L(-1) with the relative standard deviations (RSDs) of 7.4, 2.4 and 6.2% (c=1 µg L(-1), n=7) were obtained for As(V), Cr(VI) and Se(VI), respectively. The developed method was validated by analyzing four Certified Reference Materials, rainwater, Yangtze River and East Lake waters. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanisms of Arsenic Hyperaccumulation in Pteris vittata. Uptake Kinetics, Interactions with Phosphate, and Arsenic Speciation1

PubMed Central

Wang, Junru; Zhao, Fang-Jie; Meharg, Andrew A.; Raab, Andrea; Feldmann, Joerg; McGrath, Steve P.

2002-01-01

The mechanisms of arsenic (As) hyperaccumulation in Pteris vittata, the first identified As hyperaccumulator, are unknown. We investigated the interactions of arsenate and phosphate on the uptake and distribution of As and phosphorus (P), and As speciation in P. vittata. In an 18-d hydroponic experiment with varying concentrations of arsenate and phosphate, P. vittata accumulated As in the fronds up to 27,000 mg As kg−1 dry weight, and the frond As to root As concentration ratio varied between 1.3 and 6.7. Increasing phosphate supply decreased As uptake markedly, with the effect being greater on root As concentration than on shoot As concentration. Increasing arsenate supply decreased the P concentration in the roots, but not in the fronds. Presence of phosphate in the uptake solution decreased arsenate influx markedly, whereas P starvation for 8 d increased the maximum net influx by 2.5-fold. The rate of arsenite uptake was 10% of that for arsenate in the absence of phosphate. Neither P starvation nor the presence of phosphate affected arsenite uptake. Within 8 h, 50% to 78% of the As taken up was distributed to the fronds, with a higher translocation efficiency for arsenite than for arsenate. In fronds, 49% to 94% of the As was extracted with a phosphate buffer (pH 5.6). Speciation analysis using high-performance liquid chromatography-inductively coupled plasma mass spectroscopy showed that >85% of the extracted As was in the form of arsenite, and the remaining mostly as arsenate. We conclude that arsenate is taken up by P. vittata via the phosphate transporters, reduced to arsenite, and sequestered in the fronds primarily as As(III). PMID:12428020

Selenium fractions in organic matter from Se-rich soils and weathered stone coal in selenosis areas of China.

PubMed

Qin, Hai-bo; Zhu, Jian-ming; Su, Hui

2012-02-01

A high degree of association between Selenium (Se) and organic matter has been demonstrated in natural environments, but Se fractions and speciation in organic matter is unclear. In this study, a method for quantifying organic matter associated with Se (OM-Se) was developed to investigate Se fractions in organic matter in Se-rich soils and weathered stone coal from Enshi, China, where Se poisoning of humans and livestock has been documented. Initially, Se was extracted using water and a phosphate buffer. Subsequently, OM-Se was extracted using NaOH, and then speciated into Se associated with fulvic acids (FA-Se) and humic acids (HA-Se). Both FA-Se and HA-Se were further speciated into the weakly bound and strongly bound fractions using a customized hydride generation reactor. The results show that FA-Se (1.91-479 mg kg(-1)) is the predominant form of Se in all Se-rich soils and the weathered stone coal samples, accounting for more than 62% of OM-Se (3.07-484 mg kg(-1)). Weakly bound FA-Se (1.33-450 mg kg(-1)) was prevalent in the total FA-Se, while weakly bound HA-Se (0.62-26.2 mg kg(-1)) was variable in the total HA-Se (1.15-32.5 mg kg(-1)). These data indicate that OM-Se could play a significant source and sink role in the biogeochemical cycling of Se in the supergene environment. Weakly bound FA-Se seems to act as a potential source for bioavailable Se, whereas strongly bound HA-Se is a possible OM-Se sink which is not readily transformed into bioavailable Se. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

PubMed

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

2011-06-01

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

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

PubMed

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

2016-04-01

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

Liquid chromatography-hydride generation-atomic absorption spectrometry for the speciation of tin in seafoods.

PubMed

Viñas, Pilar; López-García, Ignacio; Merino-Meroño, Beatriz; Campillo, Natalia; Hernández-Cordóba, Manuel

2004-04-01

Liquid chromatography with hydride generation atomic absorption spectrometry as the detection system was applied to the separation and determination of inorganic tin, tributyltin, dibutyltin, monobutyltin, diphenyltin and monophenyltin. A reversed phase C18 column and a methanol/water/acetic acid (70:27:3, v/v/v) mixture containing 0.05%(v/v) triethylamine and 0.1%(w/v) tropolone as the mobile phase (isocratic elution) were used. Extraction of organotins from the samples was carried out using methanol containing 0.05%(w/v) tropolone, a process that was repeated twice. The supernatants were shaken with water and dichloromethane in a separating funnel and the organic phase was collected and evaporated to dryness. When the method was applied to the speciation of tin in fresh and canned mussels, no organotins above the detection limits were identified in any of the samples, inorganic tin being the only species detected. The reliability of the procedure was checked by analyzing the total tin content of the samples by electrothermal atomic absorption spectrometry and by speciation of tin in a certified reference material, mussel tissue (CRM 477). The method can be used for environmental monitoring of organotins contaminated samples.

Concentrations and speciation of heavy metals in sludge from nine textile dyeing plants.

PubMed

Liang, Xin; Ning, Xun-an; Chen, Guoxin; Lin, Meiqing; Liu, Jingyong; Wang, Yujie

2013-12-01

The safe disposal of sludge from textile dyeing industry requires research on bioavailability and concentration of heavy metals. In this study, concentrations and chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Zn, Pb) in sludge from nine different textile dyeing plants were examined. Some physiochemical features of sludge from textile dyeing industry were determined, and a sequential extraction procedure recommended by the Community Bureau of Reference (BCR) was used to study the metal speciation. Cluster analysis (CA) and principal component analysis (PCA) were applied to provide additional information regarding differences in sludge composition. The results showed that Zn and Cu contents were the highest, followed by Ni, Cr, Cd and Pb. The concentration of Cd and Ni in some sludge samples exceeded the standard suggested for acidic soils in China (GB18918-2002). In sludge from textile dyeing plants, Pb, Cd and Cr were principally distributed in the oxidizable and residual fraction, Cu in the oxidizable fraction, Ni in all four fractions and Zn in the acid soluble/exchangeable and reducible fractions. The pH and heat-drying method affected the fractionation of heavy metals in sludge. © 2013 Elsevier Inc. All rights reserved.

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

PubMed

Cauwenberg, P; Verdonckt, F; Maes, A

1998-01-19

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

Combining Textural Techniques to Explore Effects of Diagenesis and Low-grade Metamorphism on Iron Mineralogy and Iron Speciation

NASA Astrophysics Data System (ADS)

Slotznick, S. P.; Webb, S.; Eiler, J. M.; Kirschvink, J. L.; Fischer, W. W.

2016-12-01

Iron chemistry and mineralogy in the sedimentary rocks provide a valuable tool for studying paleoenvironmental conditions due to the fact that iron atoms can take on either the +II or +III valence state under geological redox conditions. One method utilizing this redox chemistry is `iron speciation', a bulk chemical sequential extraction technique that maps proportions of iron species to redox conditions empirically calibrated from modern sediments. However, all Precambrian and many Phanerozoic rocks have experienced post-depositional processes; it is vital to explore their effects on iron mineralogy and speciation. We combined light and electron microscopy, magnetic microscopy, (synchrotron-based) microprobe x-ray spectroscopy, and rock magnetic measurements in order to deconvolve secondary overprints from primary phases and provide quantitative measurement of iron minerals. These techniques were applied to excellently-preserved shale and siltstone samples of the 1.4 Ga lower Belt Supergroup, Montana and Idaho, USA, spanning a metamorphic gradient from sub-biotite to garnet zone. Previously measured Silurian-Devonian shales, sandstones, and carbonates in Maine and Vermont, USA spanning from the chlorite to kyanite zone provided additional well-constrained, quantitative data for comparison and to extend our analysis. In all of the studied samples, pyrrhotite formation occurred at the sub-biotite or sub-chlorite zone. Pyrrhotite was interpreted to form from pyrite and/or other iron phases based on lithology; these reactions can affect the paleoredox proxy. Iron carbonates can also severely influence iron speciation results since they often form in anoxic pore fluids during diagenesis; textural analyses of the Belt Supergroup samples highlighted that iron-bearing carbonates were early diagenetic cements or later diagenetic overprints. The inclusion of iron from diagenetic minerals during iron speciation analyses will skew results by providing a view of pore-fluid redox, not ancient water column chemistry. While our analyses and biological indicators suggest that the studied samples of the lower Belt Supergroup and New England were deposited in oxic water columns, iron speciation results imply anoxic/ferruginous conditions due to diagenetic alterations affecting the record.

Optimization of a new methodology for trace determination of elements in biological fluids: Application for speciation of inorganic selenium in children's blood.

PubMed

Akramipour, Reza; Hemati, Mitra; Fattahi, Nazir; Pirsaheb, Meghdad; Ahmadi-Jouibari, Toraj

2017-06-05

The continuous sample drop flow microextraction (CSDFME) joined with the iridium-modified tube graphite furnace atomic absorption spectrometry (GFAAS) has been developed as a highly sensitive technique for the speciation of selenium in blood samples. In this method 32.0μl carbon tetrachloride is transferred to the bottom of a conical sample cup. Then the 5.0ml of aqueous solution transforms to fine droplets while passing through the organic solvent. At this stage, Se(IV)-APDC hydrophobic complex is extracted into the organic solvent. After extraction, the conical sample cup is transferred to the GFAAS and 20μl of extraction solvent was injected into the graphite tube by the aim of autosampler. Under the optimum conditions, the calibration graph was linear in the range of 0.06-3.0μgl -1 with detection limit of 0.02μgl -1 . The enrichment factor and enhancement factor were 106 and 91, respectively. Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 2.5μgl -1 of selenium were 3.7% and 4.2%, respectively. Total inorganic Se(IV, VΙ) was measured after reduction of Se(VΙ) with gentle boiling in 5M HCl medium for 50min and adjusting pH to 3, and the concentration of Se(VΙ) was calculated by subtracting the Se(IV) concentration from the total selenium concentration. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination, speciation and distribution of mercury in soil in the surroundings of a former chlor-alkali plant: assessment of sequential extraction procedure and analytical technique

PubMed Central

2013-01-01

Background The paper presents the evaluation of soil contamination with total, water-available, mobile, semi-mobile and non-mobile Hg fractions in the surroundings of a former chlor-alkali plant in connection with several chemical soil characteristics. Principal Component Analysis and Cluster Analysis were used to evaluate the chemical composition variability of soil and factors influencing the fate of Hg in such areas. The sequential extraction EPA 3200-Method and the determination technique based on capacitively coupled microplasma optical emission spectrometry were checked. Results A case study was conducted in the Turda town, Romania. The results revealed a high contamination with Hg in the area of the former chlor-alkali plant and waste landfills, where soils were categorized as hazardous waste. The weight of the Hg fractions decreased in the order semi-mobile > non-mobile > mobile > water leachable. Principal Component Analysis revealed 7 factors describing chemical composition variability of soil, of which 3 attributed to Hg species. Total Hg, semi-mobile, non-mobile and mobile fractions were observed to have a strong influence, while the water leachable fraction a weak influence. The two-dimensional plot of PCs highlighted 3 groups of sites according to the Hg contamination factor. The statistical approach has shown that the Hg fate in soil is dependent on pH, content of organic matter, Ca, Fe, Mn, Cu and SO42- rather than natural components, such as aluminosilicates. Cluster analysis of soil characteristics revealed 3 clusters, one of which including Hg species. Soil contamination with Cu as sulfate and Zn as nitrate was also observed. Conclusions The approach based on speciation and statistical interpretation of data developed in this study could be useful in the investigation of other chlor-alkali contaminated areas. According to the Bland and Altman test the 3-step sequential extraction scheme is suitable for Hg speciation in soil, while the used determination method of Hg is appropriate. PMID:24252185

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

PubMed

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

2015-01-06

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

Changes in metal availability, desorption kinetics and speciation in contaminated soils during repeated phytoextraction with the Zn/Cd hyperaccumulator Sedum plumbizincicola.

PubMed

Li, Zhu; Jia, Mingyun; Wu, Longhua; Christie, Peter; Luo, Yongming

2016-02-01

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Bio-transformation of selenium in Se-enriched bacterial strains of Lactobacillus casei.

PubMed

Kurek, Eliza; Ruszczyńska, Anna; Wojciechowski, Marcin; Łuciuk, Anna; Michalska-Kacymirow, Magdalena; Motyl, Ilona; Bulska, Ewa

Selenium is an element of very great importance for the proper functioning of the human body, mainly due to its antioxidant properties. Selenium exhibits a preventive effect in the case of cardiovascular disease, the immune system, male infertility and inhibits the toxic action of other agents. Selenium is important for Hashimoto's disease. Intake of selenium in the diet slows the aging process. The biological and toxicological effects of selenium strongly depend on its chemical form. Some organisms for example: plant, yeast, are capable of metabolizing low bioavailable selenium compounds (inorganic selenium) into its high bioavailable forms (organic selenium). The aim of this study was to investigate the bio-transformation of selenium by Lactobacillus bacteria towards the characterisation of selenium metabolites. The speciation of selenium was evaluated by high performance liquid chromatography with inductively coupled plasma mass spectrometry detector. The extraction of selenium species from lyophilized bacteria was executed with water, the mixture of lipase and protease, as well as lisozyme and sodium dodecyl sulphate. All investigated bacteria strains cultivated in the presence of Na2SeO3 effectively uptake selenium. Surprisingly, none of the applied extraction media exhibited a strong power to release the majority of the uptaken selenium compounds. Thus a maximum of 10% of the selenium was extracted from bacteria exposed to the enzymes. However, it was found that Lactobacillus bacteria are able to metabolize inorganic ions of selenium (IV) into Se-methionine, Se-methyloselenocysteine and other unidentified forms. The study confirmed the ability of probiotic bacteria to biotransform inorganic selenium into its organic derivatives. Therefore, Se-enriched bacteria can be considered as an addition to the functional food. selenium speciation, extraction procedure, Lactobacillus casei bacteria, Lactic acid bacteria (LAB), HPLC ICP-MS, functional food.

Thermal valorization of footwear leather wastes in bubbling fluidized bed combustion.

PubMed

Bahillo, A; Armesto, L; Cabanillas, A; Otero, J

2004-01-01

Transformation of hide (animal skins) into leather is a complicated process during which significant amounts of wastes are generated. Footwear is the sector that consumes the major part of leather (60%). Logically, this industry is producing the largest quantity of leather wastes. The objective of this work was to demonstrate the technical feasibility of fluidized bed technology to recover the energy from burning footwear leather wastes. Considering the characteristics of leather waste, especially the heating value (12.5-21 MJ/kg), it can be considered a fairly good fuel. Moreover, leather waste has suitable characteristics for combustion, e.g., high volatile matter (76.5%) and low ash content (5.2%). Two factors deserve special attention: N3O and NOx emissions as a consequence of its unusual high nitrogen content (14.1%) and the chromium speciation because chromium is the main element of ash (3.2%) due to its use in leather tanning. A series of experiments has been carried out in a 0.1 MWt bubbling fluidized bed pilot plant. The combustion efficiency, flue gas composition and chromium speciation were investigated. Despite having high nitrogen content, a low conversion rate of fuel-N to NOx and N2O was attained. Chromium was concentrated in the solid streams and it was consistently found as Cr(III+); no presence of Cr(VI+) was detected.

Metal speciation of environmental samples using SPE and SFC-AED analysis

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

Mitchell, S.C.; Burford, M.D.; Robson, M.

1995-12-31

Due to growing public concern over heavy metals in the environment, soil, water and air particulate samples azre now routinely screened for their metal content. Conventional metal analysis typically involves acid digestion extraction and results in the generation of large aqueous and organic solvent waste. This harsh extraction process is usually used to obtain the total metal content of the sample, the extract being analysed by atomic emission or absorption spectroscoply techniques. A more selective method of metal extraction has been investigated which uses a supercritical fluid modified with a complexing agent. The relatively mild extraction method enables both organometallicmore » and inorganic metal species to be recovered intact. The various components from the supercritical fluid extract can be chromatographically separated using supercritical fluid chromatography (SFC) and positive identification of the metals achieved using atomic emission detection (AED). The aim of the study is to develop an analytical extraction procedure which enables a rapid, sensitive and quantitative analysis of metals in environmental samples, using just one extraction (eg SFE) and one analysis (eg SFC-AED) procedure.« less

Determination and pharmacokinetic properties of arsenic speciation in Xiao-Er-Zhi-Bao-Wan by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

PubMed

Han, Xu; Luo, Jiaoyang; Zhou, Wenju; Yang, Shihai; Yang, Meihua

2016-10-01

A method of high performance liquid chromatography with a Hamilton PRP-X100 ion-exchange column (250 × 4.1 mm id, 10 μm) coupled to inductively coupled plasma mass spectrometry was employed to generate a full concentration-time profile of arsenic speciation after oral administration. The results exhibited good linearity and revealed that, in the pills, the average arsenic concentration was 10105.4 ± 380.7 mg/kg, and in the water extraction solution, the inorganic As(III) and As(V) concentrations were 220.1 ± 12.6 and 45.5 ± 2.3 mg/kg, respectively. No trace of monomethyl arsenic acid was detected in any of the plasma samples. We then successfully applied the established methodology to examine the pharmacokinetics of arsenic speciation. The resulting data revealed that, after oral administration in rats, the plasma concentration of each arsenic species reached C max shortly after initial dosing, and that the distribution and elimination of As(V) was faster than that of As(III) and dimethyl arsenic acid. Additionally, the t 1/2 values of As(V), As(III), and dimethyl arsenic acid were 3.4 ± 1.6, 14.3 ± 4.0, and 19.9 ± 1.6 h, respectively. This study provides references for the determination of arsenic speciation in mineral-containing medicines and could serve as a useful tool in measuring the true toxicity in traditional medicines that contain them. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potential application of SERS for arsenic speciation in biological matrices.

PubMed

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

2017-08-01

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

[Treatment of tannery wastewater by infiltration percolation: chromium removal and speciation in soil].

PubMed

Tiglyene, S; Jaouad, A; Mandi, L

2008-06-01

The aim of this paper was, on one hand, to study the treatment of raw tannery effluent by infiltration percolation system and, on the other hand, to determine the distribution and speciation of chromium in the used soil. The system pilot consisted of columns filled to 15 cm of gravel and 60 cm of soil (88% of sand). The columns irrigated by raw tannery wastewater with a daily hydraulic load of 5 cm per day (approximately 10 L every day). The water flowed vertically through the soil. The speciation of Cr was investigated by using selective five steps sequential extraction method. The results indicated that the pH of the treated wastewater increases by three units in comparison to the raw wastewater. The electrical conductivity of the effluent increases also after treatment. Over the whole experimental period, results revealed significant performances of infiltration percolation system for organic load reduction. The mean elimination rate was 74% for total COD. In addition, there was a significant accumulation of organic carbon (62%) in the surface strata for the system. The total chromium undergoes an overall removal of 98%. After seven months of experiment, the results indicated that the whole retention of Cr occurring in the surface horizon of the soil (69%). Furthermore, the speciation study of Cr in the soil revealed that the oxidizable fraction is the most represented 55%. The reducible and residual phases represent 17.5% and 18.5%, respectively. The carbonate fraction presented 9% while exchangeable fraction presented only 0.02%.

Phytochemical study of Helichrysum italicum (Roth) G. Don: Spectroscopic elucidation of unusual amino-phlorogucinols and antimicrobial assessment of secondary metabolites from medium-polar extract.

PubMed

D'Abrosca, Brigida; Buommino, Elisabetta; Caputo, Pina; Scognamiglio, Monica; Chambery, Angela; Donnarumma, Giovanna; Fiorentino, Antonio

2016-12-01

Three unusual amino-phloroglucinols, named helichrytalicines A-C, along with seventeen known compounds including acetophenones, tremetrone derivatives, low-molecular weight phenols, flavonol glucosides, have been isolated from the medium-polar extract of Helichrysum italicum (Roth) G. Don, a medicinal plant typical of the Mediterranean vegetation. The structures of the compounds have been elucidated based on extensive 2D-NMR spectroscopic analyses, including COSY, TOCSY, HSQC, CIGAR-HMBC, H2BC and HSQC-TOCSY, along with Q-TOF HRMS 2 analysis. Stereostructure of the new compounds has been elucidated by Mosher's method and NOESY experiment. Antimicrobial properties against Staphylococcus epidermidis of selected compounds have been evaluated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

NASA Astrophysics Data System (ADS)

Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

2010-12-01

Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix composition and thermodynamic conditions could facilitate a transformation to more crystalline iron phases and increase metal bioavailability. While preliminary data from in-creek aggregates show no clear trend in mineralogical composition with downstream transport, only the furthest downstream samples have 2-line ferrihydrite in amounts detectable by XRD.

Speciation of strontium-90 in NIST natural matrix standard reference materials

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

Thomas, J.W.L.; Inn, K.G.W.; Garcia, M.E.

1995-12-31

A sequential leaching, radiochemical separating, and low-level beta-particle counting procedure was designed to study the speciation of radionuclides in natural matrix standard reference materials, SRMs 4350B (Columbia River Sediment) and 4353 (Rocky Flats Soil-1). Strontium-90 is the first radionuclide studied because of the difficulty experienced with this nuclide in natural-matrix SRMs. The nine-step procedure extracted {sup 90}Sr from the following fractions: water solubles, exchangeables, carbonates, reducibles, organics, iron and manganese oxides, acid leachables, micas, and silicates. The majority of {sup 90}Sr in the soil samples was found in the exchangeable fraction. By contrast, the {sup 90}Sr in the sediment ismore » more evenly distributed among the various leached fractions. Information on the leach distribution of radionuclides in environmental SRMs, based on the procedure described, should lead to more cost-effective restoration strategies and more confidence in risk assessments of human health hazards.« less

Speciation of volatile arsenic at geothermal features in Yellowstone National Park

USGS Publications Warehouse

Planer-Friedrich, B.; Lehr, C.; Matschullat, J.; Merkel, B.J.; Nordstrom, D. Kirk; Sandstrom, M.W.

2006-01-01

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5-200 mg/m3 at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC-MS. The arsenic species most frequently identified in the samples is (CH3)2AsCl, followed by (CH3)3As, (CH3)2AsSCH3, and CH3AsCl2 in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown. ?? 2006 Elsevier Inc. All rights reserved.

Organic compounds in radiation fogs in Davis (California)

NASA Astrophysics Data System (ADS)

Herckes, Pierre; Hannigan, Michael P.; Trenary, Laurie; Lee, Taehyoung; Collett, Jeffrey L.

New stainless steel active fogwater collectors were designed and used in Davis (CA, USA) to collect fogwater for the speciation of organic matter. Organic compounds in fog samples were extracted by liquid-liquid extraction and analyzed by gas chromatography coupled to mass spectrometry. Numerous organic compounds, including various alkanes, polycyclic aromatic hydrocarbons (PAH) and alkanoic acids, have been identified in the fogwater samples. Higher molecular weight (MW) compounds are preferentially associated with an insoluble phase inside the fog drops, whereas lower molecular weight and more polar compounds are found predominantly in the dissolved phase. Concentrations in the dissolved phase were sometimes much higher than estimated by the compounds' aqueous solubilities.

Nanometer-sized materials for solid-phase extraction of trace elements.

PubMed

Hu, Bin; He, Man; Chen, Beibei

2015-04-01

This review presents a comprehensive update on the state-of-the-art of nanometer-sized materials in solid-phase extraction (SPE) of trace elements followed by atomic-spectrometry detection. Zero-dimensional nanomaterials (fullerene), one-dimensional nanomaterials (carbon nanotubes, inorganic nanotubes, and nanowires), two-dimensional nanomaterials (nanofibers), and three-dimensional nanomaterials (nanoparticles, mesoporous nanoparticles, magnetic nanoparticles, and dendrimers) for SPE are discussed, with their application for trace-element analysis and their speciation in different matrices. A variety of other novel SPE sorbents, including restricted-access sorbents, ion-imprinted polymers, and metal-organic frameworks, are also discussed, although their applications in trace-element analysis are relatively scarce so far.

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

Casella, Amanda J.; Hylden, Laura R.; Campbell, Emily L.

Knowledge of real-time solution properties and composition is a necessity for any spent nuclear fuel reprocessing method. Metal-ligand speciation in aqueous solutions derived from the dissolved commercial spent fuel is highly dependent upon the acid concentration/pH, which influences extraction efficiency and the resulting speciation in the organic phase. Spectroscopic process monitoring capabilities, incorporated in a counter current centrifugal contactor bank, provide a pathway for on-line real-time measurement of solution pH. The spectroscopic techniques are process-friendly and can be easily configured for on-line applications, while classic potentiometric pH measurements require frequent calibration/maintenance and have poor long-term stability in aggressive chemical andmore » radiation environments. Our research is focused on developing a general method for on-line determination of pH of aqueous solutions through chemometric analysis of Raman spectra. Interpretive quantitative models have been developed and validated under the range of chemical composition and pH using a lactic acid/lactate buffer system. The developed model was applied to spectra obtained on-line during solvent extractions performed in a centrifugal contactor bank. The model predicted the pH within 11% for pH > 2, thus demonstrating that this technique could provide the capability of monitoring pH on-line in applications such as nuclear fuel reprocessing.« less

Rapid Analysis of Microalgal Triacylglycerols with Direct-Infusion Mass Spectrometry

DOE PAGES

Christensen, Earl; Sudasinghe, Nilusha; Dandamudi, Kodanda Phani Raj; ...

2015-09-01

Cultivation of microalgae has the potential to provide lipid-derived feedstocks for conversion to liquid transportation fuels. Lipid extracts from microalgae are significantly more complex than those of traditional seed oils, and their composition changes significantly throughout the microalgal growth period. With three acyl side chains per molecule, triglycerides (TAGs) are an important fuel precursor, and the distribution of acyl chain composition for TAGs has a significant impact on fuel properties and processing. Therefore, determination of the distribution of microalgal TAG production is needed to assess the value of algal extracts designed for fuel production and to optimize strain, cultivation, andmore » harvesting practices. Methods utilized for TAG speciation commonly involve complicated and time-consuming chromatographic techniques. Here we present a method for TAG speciation and quantification based on direct-infusion mass spectrometry, which provides rapid characterization of TAG profiles without chromatographic separation. Specifically, we utilize Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to provide a reference library of TAGs for the microalgae Nannochloropsis sp. that provides the basis for high-throughput TAG quantitation by time-of-flight mass spectrometry (TOF MS). In conclusion, we demonstrate the application of this novel approach for lipid characterization with respect to TAG compound distribution, which informs both immediate and future strain and process optimization strategies.« less

Chemical Speciation and Health Risk Assessment of Fine Particulate Bound Trace Metals Emitted from Ota Industrial Estate, Nigeria

NASA Astrophysics Data System (ADS)

Anake, Winifred U.; Ana, Godson R. E. E.; Williams, Akan B.; Fred-Ahmadu, Omowunmi H.; Benson, Nsikak U.

2017-05-01

In this study carcinogenic and non-carcinogenic health risk due to exposure to PM2.5-bound trace metals from an industrial area in Southwestern Nigeria was estimated. A four-step chemical sequential extraction procedure was employed for the chemical extraction of arsenic (As), cadmium (Cd), chromium (Cr) copper (Cu), manganese (Mn), nickel (Ni), and zinc (Zn). Samples were analyzed using inductively coupled plasma mass spectrometry (ICP-MS). Results reveal Cr and Cu as the most dominant exchangeable fraction metals, indicating possibility of their being readily soluble once PM2.5 is inhaled. Cd and Cr record the highest bioavailability index of 0.7. The cumulative lifetime cancer risks due to inhalation exposure for adults (4.25×10-2), children 1-6 years old (4.87×10-3), and children 6-18 years old (1.46×10-2) were found above Environmental Protection Agency’s acceptable range of 1×10-6 to 1×10-4. The hazard index values for all studied trace metals suggest significant potential for non-carcinogenic health risks to adults and children. The choice of chemical speciation as an essential tool in facilitating a better predictive insight on metal bioavailability and toxicity for immediate remediation action has been highlighted.

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

PubMed

Torri, Silvana; Lavado, Raúl

2009-07-30

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

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

Christensen, Earl; Sudasinghe, Nilusha; Dandamudi, Kodanda Phani Raj

Cultivation of microalgae has the potential to provide lipid-derived feedstocks for conversion to liquid transportation fuels. Lipid extracts from microalgae are significantly more complex than those of traditional seed oils, and their composition changes significantly throughout the microalgal growth period. With three acyl side chains per molecule, triglycerides (TAGs) are an important fuel precursor, and the distribution of acyl chain composition for TAGs has a significant impact on fuel properties and processing. Therefore, determination of the distribution of microalgal TAG production is needed to assess the value of algal extracts designed for fuel production and to optimize strain, cultivation, andmore » harvesting practices. Methods utilized for TAG speciation commonly involve complicated and time-consuming chromatographic techniques. Here we present a method for TAG speciation and quantification based on direct-infusion mass spectrometry, which provides rapid characterization of TAG profiles without chromatographic separation. Specifically, we utilize Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to provide a reference library of TAGs for the microalgae Nannochloropsis sp. that provides the basis for high-throughput TAG quantitation by time-of-flight mass spectrometry (TOF MS). In conclusion, we demonstrate the application of this novel approach for lipid characterization with respect to TAG compound distribution, which informs both immediate and future strain and process optimization strategies.« less

Complex Forms of Soil Organic Phosphorus-A Major Component of Soil Phosphorus.

PubMed

McLaren, Timothy I; Smernik, Ronald J; McLaughlin, Mike J; McBeath, Therese M; Kirby, Jason K; Simpson, Richard J; Guppy, Christopher N; Doolette, Ashlea L; Richardson, Alan E

2015-11-17

Phosphorus (P) is an essential element for life, an innate constituent of soil organic matter, and a major anthropogenic input to terrestrial ecosystems. The supply of P to living organisms is strongly dependent on the dynamics of soil organic P. However, fluxes of P through soil organic matter remain unclear because only a minority (typically <30%) of soil organic P has been identified as recognizable biomolecules of low molecular weight (e.g., inositol hexakisphosphates). Here, we use (31)P nuclear magnetic resonance spectroscopy to determine the speciation of organic P in soil extracts fractionated into two molecular weight ranges. Speciation of organic P in the high molecular weight fraction (>10 kDa) was markedly different to that of the low molecular weight fraction (<10 kDa). The former was dominated by a broad peak, which is consistent with P bound by phosphomonoester linkages of supra-/macro-molecular structures, whereas the latter contained all of the sharp peaks that were present in unfractionated extracts, along with some broad signal. Overall, phosphomonoesters in supra-/macro-molecular structures were found to account for the majority (61% to 73%) of soil organic P across the five diverse soils. These soil phosphomonoesters will need to be integrated within current models of the inorganic-organic P cycle of soil-plant terrestrial ecosystems.

Extraction and characterization of ternary complexes between natural organic matter, cations, and oxyanions from a natural soil.

PubMed

Peel, Hannah R; Martin, David P; Bednar, Anthony J

2017-06-01

Natural organic matter (NOM) can have a significant influence on the mobility and fate of inorganic oxyanions, such as arsenic and selenium, in the environment. There is evidence to suggest that interactions between NOM and these oxyanions are facilitated by bridging cations (primarily Fe 3+ ) through the formation of ternary complexes. Building on previous work characterizing ternary complexes formed in the laboratory using purified NOM, this study describes the extraction and characterization of intact ternary complexes directly from a soil matrix. The complexes are stable to the basic extraction conditions (pH 12) and do not appear to change when the pH of the extract is adjusted back to neutral. The results suggest that ternary complexes between NOM, cations, and inorganic oxyanions exist in natural soils and could play a role in the speciation of inorganic oxyanions in environmental matrices. Published by Elsevier Ltd.

Ultrasound-assisted analyte extraction for the determination of sulfate and elemental sulfur in zinc sulfide by different liquid chromatography techniques.

PubMed

Dash, K; Thangavel, S; Krishnamurthy, N V; Rao, S V; Karunasagar, D; Arunachalam, J

2005-04-01

The speciation and determination of sulfate (SO4(2-)) and elemental sulfur (S degree) in zinc sulfide (ZnS) using ion-chromatography (IC) and reversed-phase liquid chromatography (RPLC) respectively is described. Three sample pretreatment approaches were employed with the aim of determining sulfate: (i) conventional water extraction of the analyte; (ii) solid-liquid aqueous extraction with an ultrasonic probe; and (iii) elimination of the zinc sulfide matrix via ion-exchange dissolution (IED). The separation of sulfate was carried out by an anion-exchange column (IonPac AS17), followed by suppressed conductivity detection. Elemental sulfur was extracted ultrasonically from the acid treated sample solution into chloroform and separated on a reversed phase HPLC column equipped with a diode array detector (DAD) at 264 nm. The achievable solid detection limits for sulfate and sulfur were 35 and 10 microg g(-1) respectively.

Estimating Inorganic Arsenic Exposure from U.S. Rice and Total Water Intakes.

PubMed

Mantha, Madhavi; Yeary, Edward; Trent, John; Creed, Patricia A; Kubachka, Kevin; Hanley, Traci; Shockey, Nohora; Heitkemper, Douglas; Caruso, Joseph; Xue, Jianping; Rice, Glenn; Wymer, Larry; Creed, John T

2017-05-30

Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were 4.2 μg/day and 1.4 μg/day, respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice (2.8 μg/day); the mean exposure rate for children between ages 1 and 2 years in this population is 0.104 μg/kg body weight (BW)/day. An average consumer drinking 1.5 L of water daily that contains between 2 and 3 ng iAs/mL is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418. Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were [Formula: see text] and [Formula: see text], respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice ([Formula: see text]); the mean exposure rate for children between ages 1 and 2 years in this population is [Formula: see text] body weight (BW)/day. An average consumer drinking 1.5 L of water daily that contains between 2 and [Formula: see text] is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418.

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

The impact of Pu speciation on distribution coefficients in Mayak soil.

PubMed

Skipperud, L; Oughton, D; Salbu, B

2000-08-10

To assess the long-term consequences when radionuclides are released into the environment, information on the source term, transport and transformation processes, interaction with soils (KD) and biological uptake (CF) is needed. Among the artificial radionuclides released to the environment by nuclear activities, the transuranium elements are a major concern, due to very long half-lives and their accumulation in bone as well as high radiotoxicity. Plutonium has been produced in greater quantity than other transuranic elements, however, environmental assessments are complicated by the complex environmental behaviour. Physico-chemical forms of Pu will determine the interactions with soils and, thus, the degree to which soils can act as a sink or a potential diffuse source of contaminants. In the present work, dynamic tracer experiments have been performed where different Pu-species are added to a 'Mayak soil-rainwater system' to obtain information on KD values. After a defined contact time, the samples where then sequentially extracted and results are used in a dynamic box model to estimate interaction and fixation rates. The interaction of all Pu-species with soils seems to be rapid and follows a two-step reaction. Up to contact times of a few weeks, the KD for Pu(III,IV) (730 +/- 240 l/kg) is approximately one order of magnitude higher than for Pu(V,VI) (90 +/- 20 l/kg) and Pu(III,IV)-organic (40-60 l/kg). After 3 months contact time, the KD in only the two organic-bound Pu-species were significantly lower. This shows that the initial association with the soil is dependent on the Pu-species in the rainwater. After only 1 h of contact, between 33 and 40% of the plutonium was strongly bound to the soil components, i.e. only extractable with strong HNO3. The extraction of soil-bound Pu followed a similar pattern for all the original species, suggesting that the next step of Pu interaction mechanism with soil was rather independent of the original species. For both the Pu(V,VI) and Pu-organic species, the rainwater-desorption extract gave consistently higher KD values than that calculated from the rainwater-sorption data; whereas for Pu(III,IV), desorption KD values were more similar to sorption KD values. This supports the suggestion that the observed difference in Pu adsorption to soils reflects Pu-speciation in the water soluble phase, and that actual soil-Pu interactions are rather independent of the original speciation. Modelling of the extraction data show a different in association rate for the different Pu species, where the Pu(III,IV) has the fastest association rate as expected.

SPECIATE 4.3: Addendum to SPECIATE 4.2--Speciation database development documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

SPECIATE 4.0: SPECIATION DATABASE DEVELOPMENT DOCUMENTATION--FINAL REPORT

EPA Science Inventory

SPECIATE is the U.S. EPA's repository of total organic compounds (TOC) and particulate matter (PM) speciation profiles of air pollution sources. This report documents how EPA developed the SPECIATE 4.0 database that replaces the prior version, SPECIATE 3.2. SPECIATE 4.0 includes ...

The micro-element dynamic in hortic antrosoils conditioned with polymeric materials

NASA Astrophysics Data System (ADS)

Filipov, F.; Bulgariu, D.; Jitareanu, G.; Bulgariu, L.

2009-04-01

The studies regarding the dynamic of microelements in hortic anthrosols (soils from glasshouses and solariums) are important both from scientific point of view and in special, for the implementation of durable ecological technologies of amelioration, conservation and superior capitalization of soil resources from protected areas (glasshouses and solariums). In case of hortic anthrosols, the application of intensive technologies for plants cultivation determined brusque and intense perturbations of equilibriums between microelements and mineral and organic components of anthrosols, which is reflected by a fast degradation of morphological and physic-chemical properties. But, in case of hortic anthrosols, the exploitation conditions determined a particular evolution of microelements, and of distributions and interactions way with soil components, respectively. The conditioning and the amelioration of hortic antrosols with ecologic polymeric materials is one of the method approved in this moment and according with the opinion of most of specialists, represent one of method with large applications in modern agriculture. The utilization of polymeric materials to the conditioning of soils have been studied over 50 years, their effects on morphological, physical and chemical properties of soils being know, in special for agricultural and polluted soils. Ours studied have been performed using soil profiles drawing from Copou-glass house, Iasi (Romania). Has been followed the modification of distribution for speciation forms of some micro-elements (Zn, Cu, Ni, Mn, Cr, P), between hortic antrosol horizons, and between chemical-mineralogical components of this, with the progressive salinization of superior horizons, in 2007-2008 period. For the experimental study have been used three types of water-soluble polymers, with different hydrophobicities: polyethylene glycol (molecular mass 2000, 4000 and 8000), vinyl acetate - ammonia maleate salt copolymer (AM-VA) and methylacrylate - ammonia maleate salt copolymer (AM-MMA). The separation, differentiation and determination of micro-elements speciation forms was done by combined solid-liquid sequential extraction (SPE) and extraction in aqueous polymer-inorganic salt two-phase systems (ABS) procedure, presented in some of ours previous studies. After extraction, the total contents of the micro-elements and fractions from these differential bonded by mineral and organic components of hortic antrosol have been determined by atomic absorption spectrometry. The specific interaction mechanisms of micro-elements with organic-mineral components of soils have been estimated on the basis of Raman and FT-IR spectra, recorded for fractions obtained after each extraction step. These data were correlated with those obtained by chemical analysis and UV-VIS spectrometry, and were used for to establish the type and weight of micro-elements speciation forms in studied antrosol. The conditioning with polymeric materials determined a limitation of formation and extension rate of frangipane horizon, and of salinity in superior horizons respectively, which are mainly responsible by the geochemical segregation and degradation of soils from glass houses. Under these conditions, increase the weight of mobile speciation forms of micro-elements and will be facilitated their accessibility for cultivated vegetables. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07).

Comprehensive speciation of low-molecular weight selenium metabolites in mustard seeds using HPLC-electrospray linear trap/Orbitrap tandem mass spectrometry.

PubMed

Ouerdane, Laurent; Aureli, Federica; Flis, Paulina; Bierla, Katarzyna; Preud'homme, Hugues; Cubadda, Francesco; Szpunar, Joanna

2013-09-01

An analytical methodology based on high-resolution high mass accuracy electrospray ionization (ESI) tandem MS assisted by Se-specific detection using inductively coupled plasma mass spectrometry (ICP MS) was developed for speciation of selenium (Se) in seeds of black mustard (Brassica nigra) grown on Se-rich soil. Size-exclusion LC-ICP MS allowed the determination of the Se distribution according to the molecular mass and the control of the species stability during extraction. The optimization of hydrophilic interaction of LC and cation-exchange HPLC resulted in analytical conditions making it possible to detect and characterize over 30 Se species using ESI MS, including a number of minor (<0.5%) metabolites. Selenoglucosinolates were found to be the most important class of species accounting for at least 15% of the total Se present and over 50% of all the metabolites. They were found particularly unstable during aqueous extraction leading to the loss of Se by volatilization as methylselenonitriles and methylselenoisothiocyanates identified using gas chromatography (GC) with the parallel ICP MS and atmospheric pressure chemical ionization (APCI) MS/MS detection. However, selenoglucosinolates could be efficiently recovered by extraction with 70% methanol. Other classes of identified species included selenoamino acids, selenosugars, selenosinapine and selenourea derivatives. The three types of reactions leading to the formation of selenometabolites were: the Se-S substitution in the metabolic pathway, oxidative reactions of -SeH groups with endogenous biomolecules, and chemical reactions, e.g., esterification, of Se-containing molecules and other biomolecules through functional groups not involving Se.

3D-printed, TiO2 NP-incorporated minicolumn coupled with ICP-MS for speciation of inorganic arsenic and selenium in high-salt-content samples.

PubMed

Su, Cheng-Kuan; Chen, Wei-Cheng

2018-04-25

To extend the applicability of solid phase extraction devices manufactured using 3D printing technologies, a stereolithographic 3D printer and resins incorporating titanium dioxide nanoparticles (TiO 2 NPs) were employed to fabricate a demountable minicolumn with TiO 2 NP-incorporated packing as a sample pretreatment device for the selective extraction of inorganic As and Se species from high-salt-content samples, and to facilitate their analyses when coupled to an inductively coupled plasma mass spectrometer. After optimization, the automatic system enabled highly sensitive determinations of As and Se species with detection limits as low as 0.004-0.033 μg L -1 for As and 0.061-0.128 μg L -1 for Se. Reliability was confirmed through analyses of the reference materials 1643f, SLEW-3, CASS-4, and 2670a, as well as spike analyses of samples of water and human urine. These 3D-printed minicolumns appear to be very useful for multi-elemental speciation of these elements from high-salt-content samples. Thus, the incorporation of active nanomaterials into raw printing resins can enable 3D printing technologies-not only to fabricate functionalized devices for diverse sample pretreatment applications but also to encourage the future development of multifunctional devices for analytical science. Graphical abstract Schematic presentation of a demountable minicolumn fabricated using a stereolithographic 3D printer and the resins incorporating with TiO 2 NPs. They were used to selectively extract As and Se species through controlling the sample acidities.

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

EPA Pesticide Factsheets

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

Development of analytical procedures for the determination of hexavalent chromium in corrosion prevention coatings used in the automotive industry.

PubMed

Séby, F; Castetbon, A; Ortega, R; Guimon, C; Niveau, F; Barrois-Oudin, N; Garraud, H; Donard, O F X

2008-05-01

The European directive 2000/53/EC limits the use of Cr(VI) in vehicle manufacturing. Although a maximum of 2 g of Cr(VI) was authorised per vehicle for corrosion prevention coatings of key components, since July 2007 its use has been prohibited except for some particular applications. Therefore, the objective of this work was to develop direct analytical procedures for Cr(VI) determination in the different steel coatings used for screws. Instead of working directly with screws, the optimisation of the procedures was carried out with metallic plates homogeneously coated to improve the data comparability. Extraction of Cr(VI) from the metallic parts was performed by sonication. Two extraction solutions were tested: a direct water extraction solution used in standard protocols and an ammonium/ammonia buffer solution at pH 8.9. The extracts were further analysed for Cr speciation by high-performance liquid chromatography (HPLC) inductively coupled plasma (ICP) atomic emission spectrometry or HPLC ICP mass spectrometry depending on the concentration level. When possible, the coatings were also directly analysed by solid speciation techniques (X-ray photoelectron spectroscopy, XPS, and X-ray absorption near-edge structure, XANES) for validation of the results. Very good results between the different analytical approaches were obtained for the sample of coating made up of a heated paint containing Zn, Al and Cr when using the extracting buffer solution at pH 8.9. After a repeated four-step extraction procedure on the same portion test, taking into account the depth of the surface layer reached, good agreement with XPS and XANES results was obtained. In contrast, for the coatings composed of an alkaline Zn layer where Cr(VI) and Cr(III) are deposited, only the extraction procedure using water allowed the detection of Cr(VI). To elucidate the Cr(VI) reduction during extraction at pH 8.9, the reactivity of Cr(VI) towards different species of Zn generally present in the coatings (metallic Zn and zinc oxide) was studied. The results showed that metallic Zn rapidly reduces Cr(VI), whereas this reaction is less evident in the presence of zinc oxide. Water was then retained for coatings containing metallic Zn.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

The quantitative assessment of species in COH fluids is crucial in modelling mantle processes. For instance, H2O/CO2 ratio in the fluid phase influences the location of the solidus and of carbonation/decarbonation reactions in peridotitic systems . In the scientific literature, the speciation of COH fluids has been generally assumed on the basis of thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4). Only few authors dealt with the experimental determination of high-pressure COH fluid species at different conditions, using diverse experimental and analytical approaches (e.g., piston cylinder+capsule-piercing+gas-chromatography/mass-spectrometry; cold-seal+silica glass capsules+Raman). We performed experiments on COH fluids using a capsule-piercing device coupled with a quadrupole mass spectrometry. This type of analyzer ensures superior performances in terms of selectivity of molecules to be detected, high acquisition rates and extended linear response range. Experiments were carried out in a rocking piston cylinder apparatus at pressure of 1 GPa and temperatures from 800 to 900°C. Carbon-saturated fluids were generated through the addition of oxalic acid dihydrate and graphite. Single/double capsules and different packing materials (BN and MgO) were used to evaluate the divergence from the thermodynamic speciation model. Moreover, to assess the effect of solutes on COH fluid speciation we also performed a set of experiments adding synthetic forsterite to the charge. To determine the speciation we assembled a capsule-piercing device that allows to puncture the capsule in a gas-tight vessel at 80°C. The extraction Teflon vessel is composed of a base part, where the capsule is allocated on a steel support, and a top part where a steel drill is mounted. To release the quenched fluids from the capsule, the base part of vessel is hand-tighten to the top part, allowing the steel pointer to pierce the capsule. The 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.

HPLC-ICP-MS speciation analysis and risk assessment of arsenic in Cordyceps sinensis.

PubMed

Zuo, Tian-Tian; Li, Yao-Lei; Jin, Hong-Yu; Gao, Fei; Wang, Qi; Wang, Ya-Dan; Ma, Shuang-Cheng

2018-01-01

Cordyceps sinensis , one of the most valued traditional herbal medicines in China, contains high amount of arsenic. Considering the adverse health effects of arsenic, this is of particular concern. The aim of this study was to determine and analyze arsenic speciation in C. sinensis , and to measure the associated human health risks. We used microwave extraction and high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry to determine and analyze the arsenic content in C. sinensis , and measured the associated human health risks according to the hazard index (HI), lifetime cancer risk (CR), and target hazard quotient (THQ). The main arsenic speciation in C. sinensis were not the four organic arsenic compounds, including dimethyl arsenic, monomethyl arsenic, arsenobetaine, and arsenocholine, but comprised inorganic arsenic and other unknown risk arsenic compounds. HI scores indicated that the risk of C. sinensis was acceptable. CR results suggested that the cancer risk was greater than the acceptable lifetime risk of 10 -5 , even at low exposure levels. THQ results indicated that at the exposure level < 2.0 months/year, the arsenic was not likely to harm human health during a lifetime; however, if the exposure rate was > 3.0 months/year, the systemic effects of the arsenic in C. sinensis was of great concern. The arsenic in C. sinensis might not be free of risks. The suggested C. sinensis consumption rate of 2.0 months/year provided important insights into the ways by which to minimize potential health risks. Our study not only played the role of "cast a brick to attract jade" by which to analyze arsenic speciation in C. sinensis but also offered a promising strategy of risk assessment for harmful residues in traditional herbal medicines.

Chromium speciation in environmental samples using a solid phase spectrophotometric method

NASA Astrophysics Data System (ADS)

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.

Chromium(III)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICP-MS detection.

PubMed

Zhang, Nan; Suleiman, Jibrin Sabo; He, Man; Hu, Bin

2008-04-15

A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples.

SPECIATE and using the Speciation Tool to prepare VOC and PM chemical speciation profiles for air quality modeling

EPA Science Inventory

This product provides training to air pollution inventory and modeling professionals to understand the US EPA's SPECIATE database base and Speciation Tool and their use to develop speciated emission inventories.

SPECIATE's VOC and PM Speciation Profiles and Their use to Prepare for Air quality Modeling (2017 EIC)

EPA Pesticide Factsheets

This training provides general concepts on chemical speciation, the SPECIATE database and browser, and how to use the Speciation Tool to create model ready speciation inputs for a photochemical air quality model.

SPECIATE 4.2: speciation Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

Speciation analysis of inorganic arsenic by magnetic solid phase extraction on-line with inductively coupled mass spectrometry determination.

PubMed

Montoro Leal, P; Vereda Alonso, E; López Guerrero, M M; Cordero, M T Siles; Cano Pavón, J M; García de Torres, A

2018-07-01

Arsenic, one of the main environmental pollutants and potent natural poison, is a chemical element that is spread throughout the Earth's crust. It is well known that the toxicity of arsenic is highly dependent on its chemical forms. Generally, the inorganic species are more toxic than its organics forms, and As(III) is 60 times more toxic than As(V). In environmental waters, arsenic exists predominantly in two chemical forms: As(III) and As(V). In view of these facts, fast, sensitive, accurate and simple analytical methods for the speciation of inorganic arsenic in environmental waters are required. In this work, a new magnetic solid phase extraction with a hydride generation system was coupled on line with inductively coupled plasma mass spectrometry (MSPE-HG-ICP-MS). The new system was based on the retention of As(III) and As(V) in two knotted reactors filled with (Fe 3 O 4 ) magnetic nanoparticles functionalized with [1,5-bis (2-pyridyl) 3-sulfophenylmethylene] thiocarbonohydrazide (PSTH-MNPs). As(III) and total inorganic As were sequentially eluted in different reduction conditions. The concentration of As(V) was obtained by subtracting As(III) from total As. The system runs in a fully automated way and the method has proved to have a wide linear range and to be precise, sensitive and fast. The detection limits found were 2.7 and 3.2 ng/L for As(III) and total As, respectively; with relative standard deviations (RSDs) of 2.5% and 2.7% and a sample throughput of 14.4 h -1 . In order to validate the developed method, several certified reference samples of environmental waters including sea water, were analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in well-water and sea water. Copyright © 2018 Elsevier B.V. All rights reserved.

Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples.

PubMed

Ma, Shishuai; He, Man; Chen, Beibei; Deng, Wenchao; Zheng, Qi; Hu, Bin

2016-01-01

In this work, γ-mercaptopropyltrimethoxysilane (γ-MPTS) modified Fe3O4@SiO2 magnetic nanoparticles (MNPs) was successfully prepared, and characterized by Fourier transform infrared spectrometer (FT-IR), Transmission electron microscope (TEM) and Vibrating sample magnetometer (VSM). The sorption performance of the prepared Fe3O4@SiO2@γ-MPTS MNPs towards methylmercury (CH3Hg(+)) and inorganic mercury (Hg(2+)) was investigated. It was found that CH3Hg(+) and Hg(2+) could be simultaneously retained on the prepared Fe3O4@SiO2@γ-MPTS MNPs, and the quantitative elution of CH3Hg(+) and total mercury (THg) was achieved by using 1.5 mol L(-1) HCl containing 0.01% and 3% thiourea (m/v), respectively. And the levels of Hg(2+) were obtained by subtracting CH3Hg(+) from THg. Based on the above facts, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of CH3Hg(+) and Hg(2+). Various experimental parameters affecting MSPE of CH3Hg(+) and Hg(2+) such as pH, eluent, sample volume, and co-existing ions have been studied. Under the optimized conditions, the limits of detection (LODs) for CH3Hg(+) and THg were 1.6 and 1.9 ng L(-1), respectively. The accuracy of the proposed method was validated by analysis of a Certified Reference Material NRCC DORM-2 dogfish muscle, and the determined values are in good agreement with the certified values. The proposed method has also been successfully applied for the speciation of CH3Hg(+) and Hg(2+) in environmental water and human hair samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Graphene oxide-TiO2 composite solid phase extraction combined with graphite furnace atomic absorption spectrometry for the speciation of inorganic selenium in water samples.

PubMed

Zhang, Yanan; Chen, Beibei; Wu, Shaowei; He, Man; Hu, Bin

2016-07-01

In this paper, a method of graphene oxide (GO)-TiO2 composite solid phase extraction followed by graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the speciation of inorganic selenium in environmental waters. The adsorption behavior of inorganic Se(IV) and Se(VI) on the GO-TiO2(1:1) composite was investigated. It was found that Se(IV) was quantitatively retained on the GO-TiO2 composites within a wide pH range of 0.5-10, while Se(VI) was quantitatively adsorbed on GO-TiO2(1:1) composite at pH 0.5-2, and no obvious adsorption of Se(VI) within the pH range of 4-10 was found. By selecting pH 6.0, Se(IV) could be easily determined. After reduction of Se(VI), total Se was determined by the proposed method, and Se(VI) was calculated as the difference between the total Se and Se(IV). The factors affecting the separation/preconcentration of Se(IV) and Se(VI) were studied. Under the optimum conditions, the isothermal adsorption of Se(IV) on the GO-TiO2(1:1) composite fitted Langmuir model; a linear range over 0.1-12ngmL(-1) was obtained. The limit of detection (LOD) and precision of the method for Se(IV) was 0.04ngmL(-1) and 9.4% (cSe(IV)=0.5ngmL(-1), n=7), respectively. In order to verify the accuracy of the method, a standard water sample (GSBZ50031-94) was analyzed, and the determined value was in a good agreement to the certified value. The established method was applied to inorganic Se speciation in environmental water samples and the recovery of 87.4-102% was obtained for the spiked samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Arsenic Speciation of Solvent-Extracted Leachate from New and Weathered CCA-Treated Wood

PubMed Central

KHAN, BERNINE I.; SOLO - GABRIELE, HELENA M.; DUBEY, BRAJESH K.; TOWNSEND, TIMOTHY G.; CAI, YONG

2009-01-01

For the past 60 yr, chromate-copper-arsenate (CCA) has been used to pressure-treat millions of cubic meters of wood in the United States for the construction of many outdoor structures. Leaching of arsenic from these structures is a possible health concern as there exists the potential for soil and groundwater contamination. While previous studies have focused on total arsenic concentrations leaching from CCA-treated wood, information pertaining to the speciation of arsenic leached is limited. Since arsenic toxicity is dependent upon speciation, the objective of this study was to identify and quantify arsenic species leaching from new and weathered CCA-treated wood and CCA-treated wood ash. Solvent-extraction experiments were carried out by subjecting the treated wood and the ash to solvents of varying pH values, solvents defined in the EPA’s Synthetic Precipitation Leaching Procedure (SPLP) and Toxicity Characteristic Leaching Procedure (TCLP), rainwater, deionized water, and seawater. The generated leachates were analyzed for inorganic As(III) and As(V) and the organoarsenic species, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), using high-performance liquid chromatography followed by hydride generation and atomic fluorescence spectrometry (HPLC–HG-AFS). Only the inorganic species were detected in any of the wood leachates; no organoarsenic species were found. Inorganic As(V) was the major detectable species leaching from both new and weathered wood. The weathered wood leached relatively more overall arsenic and was attributed to increased inorganic As(III) leaching. The greater presence of As(III) in the weathered wood samples as compared to the new wood samples may be due to natural chemical and biological transformations during the weathering process. CCA-treated wood ash leached more arsenic than unburned wood using the SPLP and TCLP, and ash samples leached more inorganic As(III) than the unburned counterparts. Increased leaching was due to higher concentrations of arsenic within the ash and to the conversion of some As(V) to As(III) during combustion. PMID:15461159

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

NASA Astrophysics Data System (ADS)

Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

Heat-assisted aqueous extraction of rice flour for arsenic speciation analysis.

PubMed

Narukawa, Tomohiro; Chiba, Koichi

2010-07-28

A versatile heat-assisted pretreatment aqueous extraction method for the analysis of arsenic species in rice was developed. Rice flour certified reference materials NIST SRM1568a and NMIJ CRM 7503-a and a flour made from polished rice were used as samples, and HPLC-ICP-MS was employed for the determination of arsenic species. Arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) were detected in NIST SRM, and As(III), As(V) and DMAA were found in NMIJ CRM and the prepared polished rice flour. The sums of the concentrations of all species in each rice flour sample were 97-102% of the total arsenic concentration in each sample.

Legionella feeleii: an unusual organism associated with cutaneous infection in an immunocompromised patient.

PubMed

Verykiou, S; Goodhead, C; Parry, G; Meggitt, S

2018-04-01

We report a 23-year-old immunocompromised woman who, following cardiac transplantation, presented with an unusual cutaneous eruption. She developed a widespread pustular rash, systemic symptoms and a high temperature with raised inflammatory markers. The diagnosis was reached when a skin biopsy was cultured onto Legionella agar (buffered charcoal yeast extract) and Legionella feeleii was isolated. The patient was treated with 6 weeks of moxifloxacin and her cutaneous lesions gradually resolved. Cutaneous Legionella infections are uncommon and usually affect immunocompromised patients. © 2017 British Association of Dermatologists.

Meningitis and Riga-Fede disease: an unusual condition.

PubMed

Picciotti, M; DiVece, L; Viviano, M; Giorgio, A; Lorenzini, G

2014-07-01

Riga-Fede disease (RFD) is a benign inflammatory disorder characterised by the appearance of a traumatic ulceration of the oral mucosa. Early detection of RFD and its adequate management are very important. The authors present a an unusual case of RFD with concomitant Staphylococcus aureus meningitis. A 36-day-old female infant was referred to the emergency room of the Hospital of the University of Siena for a 4-day history of high fever. Clinical evaluation revealed the presence of lingual ulceration caused by natal tooth. Few hours later, clinical manifestations were overshadowed by neurological symptoms. The cerebrospinal fluid examination showed the presence of Staphylococcus aureus. The wound healing after extraction of the tooth and the antibiotic therapy have been important for the resolution of this case. A conservative approach is preferable for natal teeth, but in this case the extraction was suggested since a more radical treatment was more likely to avoid major complications.

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

PubMed

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 and Localization of Arsenic in White and Brown Rice Grains

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

Meharg, Andrew A.; Lombi, Enzo; Williams, Paul N.

2008-06-30

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As inmore » the outer grain of brown rice was confirmed by laser ablation ICP?MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (?-XANES) and bulk extraction followed by anion exchange HPLC?ICP?MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n = 39) and brown (n = 45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.« less

Nanometer-sized alumina packed microcolumn solid-phase extraction combined with field-amplified sample stacking-capillary electrophoresis for the speciation analysis of inorganic selenium in environmental water samples.

PubMed

Duan, Jiankuan; Hu, Bin; He, Man

2012-10-01

In this paper, a new method of nanometer-sized alumina packed microcolumn SPE combined with field-amplified sample stacking (FASS)-CE-UV detection was developed for the speciation analysis of inorganic selenium in environmental water samples. Self-synthesized nanometer-sized alumina was packed in a microcolumn as the SPE adsorbent to retain Se(IV) and Se(VI) simultaneously at pH 6 and the retained inorganic selenium was eluted by concentrated ammonia. The eluent was used for FASS-CE-UV analysis after NH₃ evaporation. The factors affecting the preconcentration of both Se(IV) and Se(VI) by SPE and FASS were studied and the optimal CE separation conditions for Se(IV) and Se(VI) were obtained. Under the optimal conditions, the LODs of 57 ng L⁻¹ (Se(IV)) and 71 ng L⁻¹ (Se(VI)) were obtained, respectively. The developed method was validated by the analysis of a certified reference material of GBW(E)080395 environmental water and the determined value was in a good agreement with the certified value. It was also successfully applied to the speciation analysis of inorganic selenium in environmental water samples, including Yangtze River water, spring water, and tap water. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Speciation of lipids and humus-like colloidal compounds in a forest soil reclaimed with municipal solid waste compost.

PubMed

Zancada, M Cristina; Almendros, Gonzalo; Sanz, Jesús; Román, Román

2004-02-01

The progressive transformations of lipid and humus-like fractions in soil after massive input (400 Mg ha(-1)) of urban waste have been studied during an 87-week experiment in field plots of a degraded Calcic Regosol in Central Spain. Structural changes in the macromolecular fractions were small when compared with the qualitative and quantitative changes in lipid composition. The intense depletion of the lipid fraction with time and the decrease of the humic acid to fulvic acid ratio were the most significant quantitative indices of the compost transformation in soil. Changes in soil lipid fractions were especially noted in relation to their speciation status and distribution patterns (carbon preference index and relative chain length). Three subfractions were considered: (I) direct extraction with petroleum ether, (II) liquid-liquid extraction after soil treatment with 2 M H3PO4 and (III) after soil treatment with 0.1 M NaOH. Although lipid concentration tends to decrease with time, lipids in the fraction tightly bonded to soil (III) remained qualitatively and quantitatively constant in the course of the field experiment. Gas chromatographic-mass spectrometric analyses showed that the more stable the association of lipid to the soil matrix, the fewer the changes observed in the distribution pattern of the fatty acids during the progressive transformation stages.

Application of thermal desorption for the identification of mercury species in solids derived from coal utilization.

PubMed

Rumayor, M; Diaz-Somoano, M; Lopez-Anton, M A; Martinez-Tarazona, M R

2015-01-01

The speciation of mercury is currently attracting widespread interest because the emission, transport, deposition and behaviour of toxic mercury species depend on its chemical form. The identification of these species in low concentrations is no easy task and it is even more complex in coal combustion products due to the fact that these products contain organic and mineral matter that give rise to broad peaks and make it difficult to carry out qualitative and quantitative analysis. In this work, a solution to this problem is proposed using a method based on thermal desorption. A sequential extraction procedure was employed for the comparison and validation of the method developed. Samples of fly ashes and soils were analyzed by both of these methods, and thermal desorption was found to be an appropriate technique for mercury speciation. Even in the case of low mercury contents, recovery percentages were close to 100%. The main mercury species identified in the samples studied were HgS and, to a lesser extent, HgO and HgSO4. In addition, although the presence of mercury complexes cannot be demonstrated, the desorption behaviour and sequential extraction results suggest that this element might be associated with the mineral matrix or with carbon particles in some of the solids. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fate, bioavailability and toxicity of silver in estuarine environments

USGS Publications Warehouse

Luoma, S.N.; Ho, Y.B.; Bryan, G.W.

1995-01-01

The chemistry and bioavailability of Ag contribute to its high toxicity in marine and estuarine waters. Silver is unusual, in that both the dominant speciation reaction in seawater and the processes important in sorbing Ag in sediments favour enhanced bioavailability. Formation of a stable chloro complex favours dispersal of dissolved Ag, and the abundant chloro complex is available to biota. Sequestration by sediments also occurs, but with relatively slow kinetics. Amorphous aggregated coatings enhance Ag accumulation in sediments, as well as Ag uptake from sediments by deposit feeders. In estuaries, the bioaccumulation of Ag increases 56-fold with each unit of increased Ag concentration in sediments. Toxicity for sensitive marine species occurs at absolute concentrations as low as those observed for any nonalkylated metal, partly because bioaccumulation increases so steeply with contamination. The environmental window of tolerance to Ag in estuaries could be narrower than for many elements.

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

PubMed

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

2012-08-20

Four of the five species of Telopea (Proteaceae) are distributed in a latitudinal replacement pattern on the south-eastern Australian mainland. In similar circumstances, a simple allopatric speciation model that identifies the origins of genetic isolation within temporal geographic separation is considered as the default model. However, secondary contact between differentiated lineages can result in similar distributional patterns to those arising from a process of parapatric speciation (where gene flow between lineages remains uninterrupted during differentiation). Our aim was to use the characteristic distributional patterns in Telopea to test whether it reflected the evolutionary models of allopatric or parapatric speciation. Using a combination of genetic evidence and environmental niche modelling, we focused on three main questions: do currently described geographic borders coincide with genetic and environmental boundaries; are there hybrid zones in areas of secondary contact between closely related species; did species distributions contract during the last glacial maximum resulting in distributional gaps even where overlap and hybridisation currently occur? Total genomic DNA was extracted from 619 individuals sampled from 36 populations representing the four species. Seven nuclear microsatellites (nSSR) and six chloroplast microsatellites (cpSSR) were amplified across all populations. Genetic structure and the signature of admixture in overlap zones was described using the Bayesian clustering methods implemented in STUCTURE and NewHybrids respectively. Relationships between chlorotypes were reconstructed as a median-joining network. Environmental niche models were produced for all species using environmental parameters from both the present day and the last glacial maximum (LGM).The nSSR loci amplified a total of 154 alleles, while data for the cpSSR loci produced a network of six chlorotypes. STRUCTURE revealed 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. 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.

Comparative study on Ce (III) and La (III) solvent extraction and separation from a nitric acid medium by D2EHPA and Cyanex272

NASA Astrophysics Data System (ADS)

Habibpour, R.; Dargahi, M.; Kashi, E.; Bagherpour, M.

2018-01-01

The solvent extraction of Cerium(III) and Lanthanum(III) from nitric acid solution using the organophosphorous extractants Di-(2-ethyl hexyl) phosphate (D2EHPA) and di-2,4,4- trimethylpentyl phosphoric acid (Cyanex272) in kerosene was investigated. In this study, the magnitude of the extraction of Ce(III) was found to be more significant with Cyanex272 than D2EHPA. D2EHPA was found to be a better extractant for La(III). Among the two extractants, Cyanex272 was used for the separation of Ce from La in three stages with an extraction efficiency of 90.2% for Ce. A 556 mg/L Ce solution was used for the scrubbing of La with an efficiency of ≈34%, which required multi stage scrubbing. The study of thermodynamic parameters such as enthalpy, entropy, and Gibbs free energy impart the exothermic and non-spontaneous process. The chemical speciation curves for lanthanum and cerium in the aqueous phase as a function of pH showed that the free La(III) and Ce(III) metal ion species were largely predominate between a pH = 0 and pH = 7.

An approach for identification and determination of arsenic species in the extract of kelp.

PubMed

Yu, Lee L; Wei, Chao; Zeisler, Rolf; Tong, Junting; Oflaz, Rabia; Bao, Haixia; Wang, Jun

2015-05-01

The National Institute of Standards and Technology is developing a kelp powder standard reference material (SRM) in support of dietary supplement measurements. Edible seaweeds such as kelp and laver consumed as diet or dietary supplement contain tens of mg/kg arsenic. The speciation information of arsenic in the seaweed should be provided because the total arsenic alone does not fully address the safety issue of the dietary supplement as the value assignment is originally intended. The inability to avail all arsenic species for value assignment measurements prevented the certification of arsenic species in the candidate SRM; however, approximately 70 % of total arsenic extracted with a 1:1 volume fraction of methanol:water mixture allowed arsenic speciation values to be assigned to a procedure-defined extract, which may be used for method validation in research to improve upon current extraction and measurement practices. Arsenic species in kelp and laver were identified using electrospray ionization ion trap time of flight mass spectrometry (ESI-IT-TOF). Arsenosugars As(328), As(482), and As(392) were found in the kelp candidate SRM while As(328) and As(482) were found in GBW 08521, a certified reference material (CRM) of laver produced by the National Institute of Metrology of China (NIM). A discovery that the digests of kelp and laver contained only dimethylarsinic acid led to the conclusion that the seaweeds did not contain detectible levels of arsenobetaine, arsenocholine or trimethylarsine oxide that could overlap with the peaks of arsenosugars in the separation. The mean ± s of (5.68 ± 0.28) mg/kg and (13.43 ± 0.31) mg/kg found for As(482) and As(392) in kelp, respectively, using instrumental neutron activation analysis (INAA) demonstrated that value assignment measurement of arsenosugars was possible without arsenosugar calibration standards.

Speciation of As(III) and As(V) in water samples by graphite furnace atomic absorption spectrometry after solid phase extraction combined with dispersive liquid-liquid microextraction based on the solidification of floating organic drop.

PubMed

Shamsipur, Mojtaba; Fattahi, Nazir; Assadi, Yaghoub; Sadeghi, Marzieh; Sharafi, Kiomars

2014-12-01

A solid phase extraction (SPE) coupled with dispersive liquid-liquid microextraction based on the solidification of floating organic drop (DLLME-SFO) method, using diethyldithiphosphate (DDTP) as a proper chelating agent, has been developed as an ultra preconcentration technique for the determination of inorganic arsenic in water samples prior to graphite furnace atomic absorption spectrometry (GFAAS). Variables affecting the performance of both steps were thoroughly investigated. Under optimized conditions, 100mL of As(ΙΙΙ) solution was first concentrated using a solid phase sorbent. The extract was collected in 2.0 mL of acetone and 60.0 µL of 1-undecanol was added into the collecting solvent. The mixture was then injected rapidly into 5.0 mL of pure water for further DLLME-SFO. Total inorganic As(III, V) was extracted similarly after reduction of As(V) to As(III) with potassium iodide and sodium thiosulfate and As(V) concentration was calculated by difference. A mixture of Pd(NO3)2 and Mg(NO3)2 was used as a chemical modifier in GFAAS. The analytical characteristics of the method were determined. The calibration graph was linear in the rage of 10-100 ng L(-1) with detection limit of 2.5 ng L(-1). Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 80 ng L(-1) of As(ΙΙΙ) were 6.8% and 7.5%, respectively. The method was successfully applied to speciation of As(III), As(V) and determination of the total amount of As in water samples and in a certified reference material (NIST RSM 1643e). Copyright © 2014 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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 unexpected mineral-mineral associations, which may dynamically impact the temporal fate of tropical soil C.

Application of infrared thermography for online monitoring of wall temperatures in inductively coupled plasma torches with conventional and low-flow gas consumption

NASA Astrophysics Data System (ADS)

Engelhard, Carsten; Scheffer, Andy; Maue, Thomas; Hieftje, Gary M.; Buscher, Wolfgang

2007-10-01

Inductively coupled plasma (ICP) sources typically used for trace elemental determination and speciation were investigated with infrared (IR) thermography to obtain spatially resolved torch temperature distributions. Infrared thermographic imaging is an excellent tool for the monitoring of temperatures in a fast and non-destructive way. This paper presents the first application of IR thermography to inductively coupled plasma torches and the possibility to investigate temperatures and thermal patterns while the ICP is operating and despite background emission from the plasma itself. A fast and easy method is presented for the determination of temperature distributions and stress features within ICP torches. Two different ICP operating torches were studied: a commercially available Fassel-type ICP unit with 14 L min - 1 total Ar consumption and a SHIP torch with the unusually low Ar flow of 0.6 L min - 1 . Spatially resolved infrared images of both torches were obtained and laterally resolved temperature profiles were extracted. After temperature-resolved calibration of the emissivity (between 0.5 and 0.35 at 873-1323 K) and transmission (20% between 3.75 and 4.02 μm) of the fused quartz used in the torch construction, an image correction was applied. Inhomogeneous temperature distributions with locally defined stress areas in the conventional Fassel-type torch were revealed. As a general trend, it was found that the SHIP torch exhibited higher temperatures ( Tmax = 1580 K) than the conventional torch ( Tmax = 730 K). In the former case, torch sites with efficient and inefficient cooling were discovered and the external flow of cooling air (24-48 m s - 1 ) was identified as the limiting factor.

Arsenic Speciation and Accumulation in Selected Organs after Oral Administration of Rice Extracts in Wistar Rats.

PubMed

Lewchalermvong, Kittima; Rangkadilok, Nuchanart; Nookabkaew, Sumontha; Suriyo, Tawit; Satayavivad, Jutamaad

2018-03-28

Despite its nutritional values, rice also contains arsenic. There has been increasing concern about health implications associated with exposure to arsenic through rice consumption. The present study evaluated arsenic accumulation and its speciation in selected organs of Wistar rats after 28 day repeated oral administrations of polished or unpolished rice and their control arsenic compounds (sodium arsenite or dimethylarsinic acid; DMA). Only the treatment of sodium arsenite (2 μg/kg body weight), significantly increased total arsenic concentrations in blood when compared to the distilled water control group. In all groups, total arsenic concentrations were highest in kidney (1.54-1.90 mg/kg) followed by liver (0.85-1.52 mg/kg), and the predominant arsenic form in these organs was DMA. However, there was no significant difference in arsenic accumulation in the measured organs among the control and rice-treated groups. Therefore, the repeated 28 day administration of arsenic-contaminated rice did not cause significant arsenic accumulation in the animal organs.

Reversed Phase Column HPLC-ICP-MS Conditions for Arsenic Speciation Analysis of Rice Flour.

PubMed

Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

2015-01-01

New measurement conditions for arsenic speciation analysis of rice flour were developed using HPLC-ICP-MS equipped with a reversed phase ODS column. Eight arsenic species, namely, arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA), arsenobetaine (AsB) and arsenocholine (AsC), were separated and determined under the proposed conditions. In particular, As(III) and MMAA and DMAA and AsB were completely separated using a newly proposed eluent containing ammonium dihydrogen phosphate. Importantly, the sensitivity changes, in particular those of As(V) and As(III) caused by coexisting elements and by complex matrix composition, which had been problematical in previously reported methods, were eliminated. The new eluent can be applied to C8, C18 and C30 ODS columns with the same effectiveness and with excellent repeatability. The proposed analytical method was successfully applied to extracts of rice flour certified reference materials.

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

PubMed

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

2014-08-01

Recovery of metals occurring in significant amounts in municipal solid waste incineration fly ash, such as copper, could offer several advantages: a decreased amount of potentially mobile metal compounds going to landfill, saving of natural resources and a monetary value. A combination of leaching and solvent extraction may constitute a feasible recovery path for metals from municipal solid waste incineration fly ash. However, it has been shown that the initial dissolution and leaching is a limiting step in such a recovery process. The work described in this article was focused on elucidating physical and chemical differences between two ash samples with the aim of explaining the differences in copper release from these samples in two leaching methods. The results showed that the chemical speciation is an important factor affecting the release of copper. The occurrence of copper as phosphate or silicate will hinder leaching, while sulphate and chloride will facilitate leaching. © The Author(s) 2014.

The actin multigene family and livestock speciation using the polymerase chain reaction.

PubMed

Fairbrother, K S; Hopwood, A J; Lockley, A K; Bardsley, R G

1998-01-01

Actins constitute a family of highly-conserved multifunctional intracellular proteins, best known as myofibrillar components in striated muscle fibres. Most vertebrate genomes contain numerous actin genes with high sequence homology in protein coding regions but considerable variability in intron number and sizes. This genetic diversity can be utilised for livestock speciation purposes. The high sequence conservation has enabled a single pair of oligonucleotides to be used to prime the polymerase chain reaction (PCR) with DNA extracted from all animals so far studied. Multiple amplification products were obtained which on gel electrophoresis constituted characteristic species-specific 'fingerprints'. The patterns were reproducible, did not vary between individuals of the same breed or between different breeds within a species, and could be generated even from heat-processed muscle held at 120 degrees C for one hour. Given the capacity of PCR to amplify relatively short sequences in highly-degraded DNA, this approach may be suitable for authentication of processed meat products.

Aberrant Classopollis pollen reveals evidence for unreduced (2n) pollen in the conifer family Cheirolepidiaceae during the Triassic-Jurassic transition.

PubMed

Kürschner, Wolfram M; Batenburg, Sietske J; Mander, Luke

2013-10-07

Polyploidy (or whole-genome doubling) is a key mechanism for plant speciation leading to new evolutionary lineages. Several lines of evidence show that most species among flowering plants had polyploidy ancestry, but it is virtually unknown for conifers. Here, we study variability in pollen tetrad morphology and the size of the conifer pollen type Classopollis extracted from sediments of the Triassic-Jurassic transition, 200 Ma. Classopollis producing Cheirolepidiaceae were one of the most dominant and diverse groups of conifers during the Mesozoic. We show that aberrant pollen Classopollis tetrads, triads and dyads, and the large variation in pollen size indicates the presence of unreduced (2n) pollen, which is one of the main mechanisms in modern polyploid formation. Polyploid speciation may explain the high variability of growth forms and adaptation of these conifers to different environments and their resistance to extreme growth conditions. We suggest that polyploidy may have also reduced the extinction risk of these conifers during the End-Triassic biotic crisis.

Geochemical partitioning of Cu and Ni in mangrove sediments: relationships with their bioavailability.

PubMed

Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita

2015-04-15

Sequential extraction study was performed to determine the concentrations of non-residual metal-complexes in the mangrove sediments from the Divar Island, (west coast of India). Accumulation of metal in the mangrove roots (from the same location) was determined and used as an indicator of bioavailability of metal. An attempt was made to establish a mechanistic linkage between the non-residual metal complexes and their bioavailability in the mangrove system. The non-residual fractions of Cu and Ni were mainly associated with Fe/Mn oxyhydroxide and organic phases in the sediments. A part of these metal fractions were bioavailable in the system. These two phases were the major controlling factors for Ni speciation and their bioavailability in the studied sediments. However, Cu was found to interact more strongly with the organic phases than Ni in the mangrove sediments. Organic phases in the mangrove sediments acted as buffer to control the speciation and bioavailability of Cu in the system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Speciation of As(III) and As(V) in water and sediment using reverse-phase ion-pair high-performance liquid chromatography-neutron activation analysis (HPLC-NAA).

PubMed

Tulasi, Delali; Adotey, Dennis; Affum, Andrews; Carboo, Derick; Serfor-Armah, Yaw

2013-10-01

Total As content and the As species distribution in water and sediments from the Kwabrafo stream, a major water body draining the Obuasi gold mining community in southwestern Ghana, have been investigated. Total As content was determined by instrumental neutron activation analysis (INAA). Ion-pair reverse phase high-performance liquid chromatography-neutron activation analysis (HPLC-NAA) was used for speciation of As species. Solid phase extraction with phosphate buffer was used to extract soluble As species from lyophilized sediment. The mass balance after phosphate extraction of soluble As species in sediment varied from 89 to 96 %. Compositionally appropriate reference material International Atomic Energy Agency (IAEA)-Lake Sediment (SL)-1 was used to check the validity of INAA method for total As determination. The measured values are in good agreement with the IAEA recommended value and also within the 95 % confidence interval. The accuracy of the measurement in terms of relative deviation from the IAEA recommended value was ±0.83 %. "In-house" prepared As(III) and As(V) standards were used to validate the HPLC-INAA method used for the As species determination. Total As concentration in the water samples ranged from 1.15 to 9.20 mg/L. As(III) species in water varied from 0.13 to 0.7 mg/L, while As(V) species varied from 0.79 to 3.85 mg/L. Total As content in sediment ranged from 2,134 to 3,596 mg/kg dry mass. The levels of As(III) and As(V) species in the sediment ranges from 138 to 506 mg/kg dry mass and 156 to 385 mg/kg dry mass, respectively.

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

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

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

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

Comparative study on the bioaccumulation and biotransformation of arsenic by some northeastern Atlantic and northwestern Mediterranean sponges.

PubMed

Orani, Anna Maria; Barats, Aurélie; Zitte, Wendy; Morrow, Christine; Thomas, Olivier P

2018-06-01

The bioaccumulation and biotransformation of arsenic (As) were studied in six representative marine sponges from the French Mediterranean and Irish Atlantic coasts. Methodologies were carefully optimized in one of the species on Haliclona fulva sponges for two critical steps: the sample mineralization for total As analysis by ICP-MS and the extraction of As species for HPLC-ICP-MS analysis. During the optimization, extractions performed with 0.6 mol L -1 H 3 PO 4 were shown to be the most efficient. Extraction recovery of 81% was obtained which represents the best results obtained until now in sponge samples. Total As analyses and As speciation were performed on certified reference materials and allow confirming the measurement quality both during the sample preparation and analysis. Additionally, this study represents an environmental survey demonstrating a high variability of total As concentrations among the different species, probably related to different physiological or microbial features. As speciation results showed the predominance of arsenobetaine (AsB) regardless of the sponge species, as well as the occurrence of low amounts of dimethylarsinic acid (DMA), arsenate (As(+V)), and unknown As species in some samples. The process responsible for As transformation in sponges is most likely related to sponges metabolism itself or the action of symbiont organisms. AsB is supposed to be implied in the protection against osmolytic stress. This study demonstrates the ability of sponges to accumulate and bio-transform As, proving that sponges are relevant bio-monitors for As contamination in the marine environment, and potential tools in environmental bio-remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

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

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

1995-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

As the most abundant transition metal in the Earth's crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite's identification depended on the extraction techniques utilized. The presence of diagenetic iron carbonates in many samples severely affected the proxy even at low grade, engendering an interpretation of ferruginous conditions in all lithologies, but particularly in carbonate-bearing rocks. Increasing metamorphic grades transformed iron in carbonates into iron in silicate minerals, which when combined with a slight increase in the amount of pyrrhotite, drove the proxy toward more oxic and more euxinic conditions. Broad-classes of metamorphic reactions (e.g. decarbonation, silicate formation) occurred at distinct temperatures-pressures in carbonates versus siliciclastics, and could be either abrupt between metamorphic facies or more gradual in nature. Notably, these analyses highlighted the importance of trace iron in phases like calcite, which otherwise might not be included in iron-focused research i.e. ore-system petrogenesis, metamorphic evolution, or normative calculations of mineral abundance. The observations show that iron is mobile and reactive during diagenesis and metamorphism, and these post-depositional processes can readily overprint primary redox information held by iron speciation. However, in principle, additional mineralogical and petrographic approaches can be combined with iron speciation data to help untangle many of these post-depositional processes and arrive at more accurate estimates of paleoenvironmental redox conditions and processes, even for metamorphosed samples.

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

Extraction techniques for arsenic species in rice flour and their speciation by HPLC-ICP-MS.

PubMed

Narukawa, Tomohiro; Suzuki, Toshihiro; Inagaki, Kazumi; Hioki, Akiharu

2014-12-01

The extraction of arsenic (As) species present in rice flour samples was investigated using different extracting solvents, and the concentration of each species was determined by HPLC-ICP-MS after heat-assisted extraction. The extraction efficiencies for total arsenic species and especially for arsenite [As(III)] and arsenate [As(V)] were investigated. As(III), As(V) and dimethylarsinic acid (DMAA) were found in the samples, and the concentration of DMAA did not vary with treatment conditions. However, the concentrations of extracted total arsenic and those of As(III) and As(V) depended on the extracting solvents. When an extracting solvent was highly acidic, the concentrations of extracted total arsenic were in good agreement with the total arsenic concentration determined by ICP-MS after microwave-assisted digestion, though a part of the As(V) was reduced to As(III) during the highly acidic extraction process. Extraction under neutral conditions increased the extracted As(V), but extracted total arsenic was decreased because a part of the As(III) could not be extracted. Optimum conditions for the extraction of As(III) and As(V) from rice flour samples are discussed to allow the accurate determinations of As(III), As(V) and DMAA in the rice flour samples. Heat block extraction techniques using 0.05 mol L(-1) HClO4 and silver-containing 0.15 mol L(-1) HNO3 were also developed. Copyright © 2014 Elsevier B.V. All rights reserved.

Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction.

PubMed

Cruz-Hernández, Yusniel; Ruiz-García, Mismel; Villalobos, Mario; Romero, Francisco Martin; Meza-Figueroa, Diana; Garrido, Fernando; Hernández-Alvarez, Elizabeth; Pi-Puig, Teresa

2018-06-01

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values. The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry. Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides). Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found. Copyright © 2018 Elsevier Ltd. All rights reserved.

Can we trust mass spectrometry for determination of arsenic peptides in plants: comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata.

PubMed

Bluemlein, Katharina; Raab, Andrea; Meharg, Andrew A; Charnock, John M; Feldmann, Jörg

2008-04-01

The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step.

Chelant extraction of heavy metals from contaminated soils.

PubMed

Peters, R W

1999-04-23

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique. Copyright 1999 Published by Elsevier Science B.V.

Does boiling affect the bioaccessibility of selenium from cabbage?

PubMed

Funes-Collado, Virginia; Rubio, Roser; López-Sánchez, J Fermín

2015-08-15

The bioaccessible selenium species from cabbage were studied using an in vitro physiologically-based extraction test (PBET) which establishes conditions that simulate the gastric and gastrointestinal phases of human digestion. Samples of cabbage (Brassica oleracea) grown in peat fortified with different concentrations of Se(IV) and Se(VI) were analysed, and several enzymes (pepsin, pancreatin and amylase) were used in the PBET. The effect of boiling before extraction was also assayed. Selenium speciation in the PBET extracts was determined using anionic exchange and LC-ICP/MS. The selenocompounds in the extracts were Se(IV), SeMet and, mostly, Se(VI) species. The results show that the activity of the enzymes increased the concentration of the selenocompounds slightly, although the use of amylase had no effect on the results. The PBET showed the concentration of inorganic selenium in the extracts from boiled cabbage decreased as much as 4-fold while the release of SeMet and its concentration increased (up to 6-fold), with respect to raw cabbage. Copyright © 2015 Elsevier Ltd. All rights reserved.

Overestimation of organic phosphorus in wetland soils by alkaline extraction and molybdate colorimetry.

PubMed

Turner, Benjamin L; Newman, Susan; Reddy, K Ramesh

2006-05-15

Accurate information on the chemical nature of soil phosphorus is essential for understanding its bioavailability and fate in wetland ecosystems. Solution phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy was used to assess the conventional colorimetric procedure for phosphorus speciation in alkaline extracts of organic soils from the Florida Everglades. Molybdate colorimetry markedly overestimated organic phosphorus by between 30 and 54% compared to NMR spectroscopy. This was due in large part to the association of inorganic phosphate with organic matter, although the error was exacerbated in some samples by the presence of pyrophosphate, an inorganic polyphosphate that is not detected by colorimetry. The results have important implications for our understanding of phosphorus biogeochemistry in wetlands and suggest that alkaline extraction and solution 31p NMR spectroscopy is the only accurate method for quantifying organic phosphorus in wetland soils.

Speciation of organic and inorganic selenium in selenium-enriched rice by graphite furnace atomic absorption spectrometry after cloud point extraction.

PubMed

Sun, Mei; Liu, Guijian; Wu, Qianghua

2013-11-01

A new method was developed for the determination of organic and inorganic selenium in selenium-enriched rice by graphite furnace atomic absorption spectrometry detection after cloud point extraction. Effective separation of organic and inorganic selenium in selenium-enriched rice was achieved by sequentially extracting with water and cyclohexane. Under the optimised conditions, the limit of detection (LOD) was 0.08 μg L(-1), the relative standard deviation (RSD) was 2.1% (c=10.0 μg L(-1), n=11), and the enrichment factor for selenium was 82. Recoveries of inorganic selenium in the selenium-enriched rice samples were between 90.3% and 106.0%. The proposed method was successfully applied for the determination of organic and inorganic selenium as well as total selenium in selenium-enriched rice. Copyright © 2013 Elsevier Ltd. All rights reserved.

An unusual case of severe primary molar infraocclusion.

PubMed

Gondim, Juliana Oliveira; Neto, José Jeová Siebra Moreira; de Carvalho, Fernanda Matias; da Costa, Raquel Campelo Ferreira; Monteiro, Aline Levi Baratta; Giro, Elisa Maria Aparecida

2013-01-01

Dentoalveolar ankylosis is described as the direct union between root cementum/dentin and alveolar bone. Its etiology is unknown, and conflicting opinions have been presented to explain it. Late detection of ankylosed primary teeth may cause serious problems to the occlusion and generally demands a more complex treatment approach. The purpose of this report is to present an unusual case of severe infraocclusion of the primary maxillary right second molar associated with a posterior crossbite in a 6-year-old child. The initial treatment option was tooth extraction, but the tooth resumed eruption spontaneously. After correction of the posterior crossbite and a 1-year follow-up, the tooth remained in occlusion and the permanent successor was developing without problems. From this unusual outcome, it may be concluded that further investigation of this anomaly of eruption is needed.

Comparative tests of the role of dewlap size in Anolis lizard speciation

PubMed Central

Harrison, Alexis; Mahler, D. Luke; Castañeda, María del Rosario; Glor, Richard E.; Herrel, Anthony; Stuart, Yoel E.; Losos, Jonathan B.

2016-01-01

Phenotypic traits may be linked to speciation in two distinct ways: character values may influence the rate of speciation or diversification in the trait may be associated with speciation events. Traits involved in signal transmission, such as the dewlap of Anolis lizards, are often involved in the speciation process. The dewlap is an important visual signal with roles in species recognition and sexual selection, and dewlaps vary among species in relative size as well as colour and pattern. We compile a dataset of relative dewlap size digitized from photographs of 184 anole species from across the genus' geographical range. We use phylogenetic comparative methods to test two hypotheses: that larger dewlaps are associated with higher speciation rates, and that relative dewlap area diversifies according to a speciational model of evolution. We find no evidence of trait-dependent speciation, indicating that larger signals do not enhance any role the dewlap has in promoting speciation. Instead, we find a signal of mixed speciational and gradual trait evolution, with a particularly strong signal of speciational change in the dewlaps of mainland lineages. This indicates that dewlap size diversifies in association with the speciation process, suggesting that divergent selection may play a role in the macroevolution of this signalling trait. PMID:28003450

The analytical biochemistry of chromium.

PubMed Central

Katz, S A

1991-01-01

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

EPA’s SPECIATE 4.4 Database:Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

EPA’s SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

US EPA's SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, volatile o...

EPA’s SPECIATE 4.4 Database: Bridging Data Sources and Data Users

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

Optimization of cloud point extraction and solid phase extraction methods for speciation of arsenic in natural water using multivariate technique.

PubMed

Baig, Jameel A; Kazi, Tasneem G; Shah, Abdul Q; Arain, Mohammad B; Afridi, Hassan I; Kandhro, Ghulam A; Khan, Sumaira

2009-09-28

The simple and rapid pre-concentration techniques viz. cloud point extraction (CPE) and solid phase extraction (SPE) were applied for the determination of As(3+) and total inorganic arsenic (iAs) in surface and ground water samples. The As(3+) was formed complex with ammonium pyrrolidinedithiocarbamate (APDC) and extracted by surfactant-rich phases in the non-ionic surfactant Triton X-114, after centrifugation the surfactant-rich phase was diluted with 0.1 mol L(-1) HNO(3) in methanol. While total iAs in water samples was adsorbed on titanium dioxide (TiO(2)); after centrifugation, the solid phase was prepared to be slurry for determination. The extracted As species were determined by electrothermal atomic absorption spectrometry. The multivariate strategy was applied to estimate the optimum values of experimental factors for the recovery of As(3+) and total iAs by CPE and SPE. The standard addition method was used to validate the optimized methods. The obtained result showed sufficient recoveries for As(3+) and iAs (>98.0%). The concentration factor in both cases was found to be 40.

Invasive species and biodiversity crises: testing the link in the late devonian.

PubMed

Stigall, Alycia L

2010-12-29

During the Late Devonian Biodiversity Crisis, the primary driver of biodiversity decline was the dramatic reduction in speciation rates, not elevated extinction rates; however, the causes of speciation decline have been previously unstudied. Speciation, the formation of new species from ancestral populations, occurs by two primary allopatric mechanisms: vicariance, where the ancestral population is passively divided into two large subpopulations that later diverge and form two daughter species, and dispersal, in which a small subset of the ancestral population actively migrates then diverges to form a new species. Studies of modern and fossil clades typically document speciation by vicariance in much higher frequencies than speciation by dispersal. To assess the mechanism behind Late Devonian speciation reduction, speciation rates were calculated within stratigraphically constrained species-level phylogenetic hypotheses for three representative clades and mode of speciation at cladogenetic events was assessed across four clades in three phyla: Arthropoda, Brachiopoda, and Mollusca. In all cases, Devonian taxa exhibited a congruent reduction in speciation rate between the Middle Devonian pre-crisis interval and the Late Devonian crisis interval. Furthermore, speciation via vicariance is almost entirely absent during the crisis interval; most episodes of speciation during this time were due to dispersal. The shutdown of speciation by vicariance during this interval was related to widespread interbasinal species invasions. The lack of Late Devonian vicariance is diametrically opposed to the pattern observed in other geologic intervals, which suggests the loss of vicariant speciation attributable to species invasions during the Late Devonian was a causal factor in the biodiversity crisis. Similarly, modern ecosystems, in which invasive species are rampant, may be expected to exhibit similar shutdown of speciation by vicariance as an outcome of the modern biodiversity crisis.

Speciation network in Laurasiatheria: retrophylogenomic signals.

PubMed

Doronina, Liliya; Churakov, Gennady; Kuritzin, Andrej; Shi, Jingjing; Baertsch, Robert; Clawson, Hiram; Schmitz, Jürgen

2017-06-01

Rapid species radiation due to adaptive changes or occupation of new ecospaces challenges our understanding of ancestral speciation and the relationships of modern species. At the molecular level, rapid radiation with successive speciations over short time periods-too short to fix polymorphic alleles-is described as incomplete lineage sorting. Incomplete lineage sorting leads to random fixation of genetic markers and hence, random signals of relationships in phylogenetic reconstructions. The situation is further complicated when you consider that the genome is a mosaic of ancestral and modern incompletely sorted sequence blocks that leads to reconstructed affiliations to one or the other relative, depending on the fixation of their shared ancestral polymorphic alleles. The laurasiatherian relationships among Chiroptera, Perissodactyla, Cetartiodactyla, and Carnivora present a prime example for such enigmatic affiliations. We performed whole-genome screenings for phylogenetically diagnostic retrotransposon insertions involving the representatives bat (Chiroptera), horse (Perissodactyla), cow (Cetartiodactyla), and dog (Carnivora), and extracted among 162,000 preselected cases 102 virtually homoplasy-free, phylogenetically informative retroelements to draw a complete picture of the highly complex evolutionary relations within Laurasiatheria. All possible evolutionary scenarios received considerable retrotransposon support, leaving us with a network of affiliations. However, the Cetartiodactyla-Carnivora relationship as well as the basal position of Chiroptera and an ancestral laurasiatherian hybridization process did exhibit some very clear, distinct signals. The significant accordance of retrotransposon presence/absence patterns and flanking nucleotide changes suggest an important influence of mosaic genome structures in the reconstruction of species histories. © 2017 Doronina et al.; Published by Cold Spring Harbor Laboratory Press.

Sources, spatial variation, and speciation of heavy metals in sediments of the Tamagawa River in Central Japan.

PubMed

Shikazono, N; Tatewaki, K; Mohiuddin, K M; Nakano, T; Zakir, H M

2012-01-01

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.

Speciation network in Laurasiatheria: retrophylogenomic signals

PubMed Central

Doronina, Liliya; Churakov, Gennady; Kuritzin, Andrej; Shi, Jingjing; Baertsch, Robert; Clawson, Hiram; Schmitz, Jürgen

2017-01-01

Rapid species radiation due to adaptive changes or occupation of new ecospaces challenges our understanding of ancestral speciation and the relationships of modern species. At the molecular level, rapid radiation with successive speciations over short time periods—too short to fix polymorphic alleles—is described as incomplete lineage sorting. Incomplete lineage sorting leads to random fixation of genetic markers and hence, random signals of relationships in phylogenetic reconstructions. The situation is further complicated when you consider that the genome is a mosaic of ancestral and modern incompletely sorted sequence blocks that leads to reconstructed affiliations to one or the other relative, depending on the fixation of their shared ancestral polymorphic alleles. The laurasiatherian relationships among Chiroptera, Perissodactyla, Cetartiodactyla, and Carnivora present a prime example for such enigmatic affiliations. We performed whole-genome screenings for phylogenetically diagnostic retrotransposon insertions involving the representatives bat (Chiroptera), horse (Perissodactyla), cow (Cetartiodactyla), and dog (Carnivora), and extracted among 162,000 preselected cases 102 virtually homoplasy-free, phylogenetically informative retroelements to draw a complete picture of the highly complex evolutionary relations within Laurasiatheria. All possible evolutionary scenarios received considerable retrotransposon support, leaving us with a network of affiliations. However, the Cetartiodactyla–Carnivora relationship as well as the basal position of Chiroptera and an ancestral laurasiatherian hybridization process did exhibit some very clear, distinct signals. The significant accordance of retrotransposon presence/absence patterns and flanking nucleotide changes suggest an important influence of mosaic genome structures in the reconstruction of species histories. PMID:28298429

Chromated copper arsenate-treated fence posts in the agronomic landscape: soil properties controlling arsenic speciation and spatial distribution.

PubMed

Schwer Iii, Donald R; McNear, David H

2011-01-01

Soils adjacent to chromated copper arsenate (CCA)-treated fence posts along a fence line transecting different soil series, parent material, drainage classes, and slope were used to determine which soil properties had the most influence on As spatial distribution and speciation. Metal distribution was evaluated at macroscopic (total metal concentration contour maps) and microscopic scales (micro-synchrotron X-ray fluorescence maps), As speciation was determined using extended X-ray absorption fine structure spectroscopy, and redox status and a myriad of other basic soil properties were elucidated. All geochemical parameters measured point to a condition in which the mobilization of As becomes more favorable moving down the topographic gradient, likely resulting through competition (Meh-P, SOM), neutral or slightly basic pH, and redox conditions that are favorable for As mobilization (higher Fe(II) and total-Fe concentrations in water extracts). On the landscape scale, with hundreds of kilometers of fence, the arsenic loading into the soil can be substantial (∼8-12 kg km). Although a significant amount of the As is stable, extended use of CCA-treated wood has resulted in elevated As concentrations in the local environment, increasing the risk of exposure and ecosystem perturbation. Therefore, a move toward arsenic-free alternatives in agricultural applications for which it is currently permitted should be considered. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Non-labile silver species in biosolids remain stable throughout ...

EPA Pesticide Factsheets

Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that biosolids Ag concentrations have decreased significantly over recent decades. XANES revealed the importance of reduced-sulfur binding environments for Ag speciation in materials ranging from freshly produced sludge to biosolids weathered under ambient environmental conditions for more than 50 years. Isotopic dilution with 110mAg showed that Ag was predominantly non-labile in both fresh and aged biosolids (13.7% mean lability), with E-values ranging from 0.3 to 60 mg/kg and 5 mM CaNO3 extractable Ag from 1.2 to 609 µg/kg (0.002 - 3.4% of the total Ag). This study indicates that at the time of soil application, biosolids Ag will be predominantly Ag-sulfides and characterised by low isotopic lability. This paper presents an overview of biosolids Ag chemistry in historic and contemporary biosolids sourced from the UK, USA and Australia from the 1950s until today by drawing on a unique collection of archived, stockpiled and contemporary biosolids samples. Characteristics of biosolids Ag chemistry determined in this study included total Ag measurement by neutron activation analysis (NAA); the assessment of Ag lability by 110mAg isotopic dilution (E-values); and Ag speciation by X-ray Absorp

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

PubMed

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.

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

PubMed Central

2011-01-01

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. PMID:21473744

Mercury speciation and microbial transformations in mine wastes, stream sediments, and surface waters at the Almaden Mining District, Spain

USGS Publications Warehouse

Gray, John E.; Hines, Mark E.; Higueras, Pablo L.; Adatto, Isaac; Lasorsa, Brenda K.

2004-01-01

Speciation of Hg and conversion to methyl-Hg were evaluated in mine wastes, sediments, and water collected from the Almade??n District, Spain, the world's largest Hg producing region. Our data for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from the Almade??n area. Concentrations of Hg and methyl-Hg in mine waste, sediment, and water from Almade??n are among the highest found at Hg mines worldwide. Mine wastes from Almade??n contain highly elevated Hg concentrations, ranging from 160 to 34 000 ??g/g, and methyl-Hg varies from <0.20 to 3100 ng/g. Isotopic tracer methods indicate that mine wastes at one site (Almadenejos) exhibit unusually high rates of Hg-methylation, which correspond with mine wastes containing the highest methyl-Hg concentrations. Streamwater collected near the Almade??n mine is also contaminated, containing Hg as high as 13 000 ng/L and methyl-Hg as high as 30 ng/L; corresponding stream sediments contain Hg concentrations as high as 2300 ??g/g and methyl-Hg concentrations as high as 82 ng/g. Several streamwaters contain Hg concentrations in excess of the 1000 ng/L World Health Organization (WHO) drinking water standard. Methyl-Hg formation and degradation was rapid in mines wastes and stream sediments demonstrating the dynamic nature of Hg cycling. These data indicate substantial downstream transport of Hg from the Almade??n mine and significant conversion to methyl-Hg in the surface environment.

Changes in heavy metal mobility and availability from contaminated wetland soil remediated with combined biochar-compost.

PubMed

Liang, Jie; Yang, Zhaoxue; Tang, Lin; Zeng, Guangming; Yu, Man; Li, Xiaodong; Wu, Haipeng; Qian, Yingying; Li, Xuemei; Luo, Yuan

2017-08-01

The combination of biochar and compost has been proven to be effective in heavy metals contaminated wetland soil restoration. However, the influence of different proportions between biochar and compost on immobilization of heavy metals in soil has been less studied up to date. Therefore, we investigated the effect of different ratios of biochar-compost mixtures on availability and speciation distribution of heavy metals (Cd, Zn and Cu) in wetland soil. The results showed that applying all amendment combinations into wetland soil increased gradually the total organic carbon (TOC) and water-extract organic carbon (WEOC) as the compost percentage rose in biochar-composts. The higher pH was obtained in a certain biochar addition (20% and 40%) in combinations due to efficient interaction of biochar with compost. All amendments could significantly decrease availability of Cd and Zn mainly from pH change, but increase available Cu concentration as the result of increased water-extract organic carbon and high total Cu content in compost. Moreover, amendments can decrease easily exchangeable fraction and increase reducible of Cd and Zn greatly with increase of compost content in combinations, while amendments containing compost promote transformation of Cu from Fe/Mn oxide and residual fractions to organic bindings. These results demonstrate that different ratios of biochar and compost have a significant effect on availability and speciation of heavy metals in multi-metal-contaminated wetland soil. Copyright © 2017 Elsevier Ltd. All rights reserved.

Estimation and influence of physicochemical properties and chemical fractions of surface sediment on the bioaccessibility of Cd and Hg contaminant in Langat River, Malaysia.

PubMed

Kadhum, Safaa A; Ishak, Mohd Yusoff; Zulkifli, Syaizwan Zahmir

2017-10-01

This study applied the use of sequential extraction technique and simple bioaccessibility extraction test to quantify the bioavailable fractions and the human bioaccessible concentration of metals collected from nine stations in surface sediment of the Langat River. The concentrations of total and bioaccessible metals from different stations were in the range of 0.49-1.04, 0.10-0.32 μg g -1 for T-Cd, Bio-Cd, respectively, and 12.9-128.03, 2.06-8.53 μg kg -1 for T-Hg, Bio-Hg, respectively. The results revealed highest R-Bio-Cd in Banting station (55.3 %), while the highest R-Bio-Hg was in Kajang station (49.61 %). The chemical speciation of Cd in most sampling stations was in the order of oxidisable-organic > residual > exchangeable > acid-reducible, while speciation of Hg was in the order of exchangeable > residual > oxidisable-organic > acid-reducible. The correlation matric of mean content showed that the TOM, particle size and Mg ++ in polluted surface sediments was highly correlated with total mercury. The PCA showed that the main factors influencing the bioaccessibility of Hg in surface sediments were the sediment TOM, F1 (EFLE) and F3 (oxidation-organic), while the factor influencing the bioaccessibility of Cd was the F3 (oxidation-organic) and T-Cd.

Simultaneous speciation and preconcentration of ultra traces of inorganic tellurium and selenium in environmental samples by hollow fiber liquid phase microextraction prior to electrothermal atomic absorption spectroscopy determination.

PubMed

Ghasemi, Ensieh; Najafi, Nahid Mashkouri; Raofie, Farhad; Ghassempour, Alireza

2010-09-15

A simple and effective speciation and preconcentration method based on hollow fiber liquid phase microextraction (HF-LPME) was developed for simultaneous separation of trace inorganic tellurium and selenium in environmental samples prior to electrothermal atomic absorption spectroscopy (ETAAS) determination. The method involves the selective extraction of the Te (IV) and Se (IV) species by HF-LPME with the use of ammonium pyrrolidinecarbodithioate (APDC) as the chelating agent. The complex compounds were extracted into 10 microL of toluene and the solutions were injected into a graphite furnace for the determination of Te (IV) and Se (IV). To determine the total tellurium and selenium in the samples, first Te (VI) and Se (VI) were reduced to Te (IV) and Se (IV), and then the microextraction method was performed. The experimental parameters of HF-LPME were optimized using a central composite design after a 2(n-1) fractional factorial experimental design. Under optimum conditions, enrichment factors of up to 520 and 480 were achieved for Te (IV) and Se (IV), respectively. The detection limits were 4 ng L(-1) with 3.5% RSD (n=5, c=2.0 microg L(-1)) for Te (IV) and 5 ng L(-1) with 3.1% RSD for Se (IV). The applicability of the developed technique was evaluated by application to spiked, environmental water and soil samples. Copyright 2010 Elsevier B.V. All rights reserved.

Assessment of the hazard posed by metal forms in water and sediments.

PubMed

Wojtkowska, Małgorzata; Bogacki, Jan; Witeska, Anna

2016-05-01

This study aimed to describe the prevalence heavy metals (Zn, Cu, Pb, and Cd) forms in the ecosystem of the Utrata river in order to determine the mobile forms and bioavailability of metals. To extract the dissolved forms of metals in the water of the Utrata PHREEQC2 geochemical speciation model was used. The river waters show a high percentage of mobile and eco-toxic forms of Zn, Cu and Pb. The percentage of carbonate forms for all the studied metals was low (<1%). The content of carbonates in the water and the prevailing physical and chemical conditions (pH, hardness, alkalinity) reduce the share of toxic metal forms, which precipitate as hardly soluble carbonate salts of Zn, Cu, Cd and Pb. Cu in the water in 90% of cases appeared in the form of hydroxyl compounds. To identify the forms of metal occurrence in the sediments Tessier's sequential extraction was used, allowing to assay bound metals in five fractions (ion exchange, carbonate, adsorption, organic, residual), whose nature and bioavailability varies in aquatic environments. The study has shown a large share of metals in labile and bioavailable forms. The speciation analysis revealed an absolute dominance of the organic fraction in the binding of Cu and Pb. Potent affinity for this fraction was also exhibited by Cd. The rations of exchangeable Zn and Cu forms in the sediments were similar. Both these metals had the lowest share in the most mobile ion exchange fraction. Copyright © 2016. Published by Elsevier B.V.

Levels and speciation of heavy metals in soils of industrial Southern Nigeria.

PubMed

Olajire, A A; Ayodele, E T; Oyedirdan, G O; Oluyemi, E A

2003-06-01

A knowledge of the total content of trace metals is not enough to fully assess the environmental impact of polluted soils. For this reason, the determination of metal species in solution is important to evaluate their behaviour in the environment and their mobilization capacity. Sequential extraction procedure was used to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) from four contaminated soils of Southern Nigeria into six operationally defined geochemical species: water soluble, enchangeable, carbonates, Fe-Mn oxide, organic and residual. Metal recoveries were within +/- 10% of the independently determined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractions was found in the exchangeable fraction, while Cu and Zn were significantly associated with the organic fraction. The carbonate fraction contained on average 14, 18.6, 12.6, 13 and 11% and the residual fraction contained on average 47, 18, 33, 50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming that mobility and bioavailability of these metals are related to the solubility of the geochemical form of the metals, and that they decrease in the order of extraction sequence, the apparent mobility and potential bioavailability for these five metals in the soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes of copper and nickel correlated positively and significantly with the total content of metals, while mobility indexes of cadmium and zinc correlated negatively and significantly with the total content of metals.

Arsenic Speciation in Groundwater: Role of Thioanions

EPA Science Inventory

The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

Mercury behaviour and C, N, and P biogeochemical cycles during ecological restoration processes of old mining sites in French Guiana.

PubMed

Couic, Ewan; Grimaldi, Michel; Alphonse, Vanessa; Balland-Bolou-Bi, Clarisse; Livet, Alexandre; Giusti-Miller, Stéphanie; Sarrazin, Max; Bousserrhine, Noureddine

2018-04-25

Several decades of gold mining extraction activities in the Amazonian rainforest have caused deforestation and pollution. While ecological rehabilitation is essential for restoring biodiversity and decreasing erosion on deforested lands, few studies note the behaviour or toxicity of trace elements during the rehabilitation process. Our original study focused on the potential use of microbial activity and Hg speciation and compared them with As, Cu, Zn and Cr speciation in assessing the chemical and biological quality of ecological restoration efforts. We sampled two sites in French Guyana 17 years after rehabilitation efforts began. The former site was actively regenerated (R) with the leguminous species Clitoria racemosa and Acacia mangium, and the second site was passively regenerated with spontaneous vegetation (Sv). We also sampled soil from a control site without a history of gold mining (F). We performed microcosm soil experiments for 30 days, where trace element speciation and enzyme activities (i.e., FDA, dehydrogenase, β-glucosidase, urease, alkaline and acid phosphatase) were estimated to characterise the behaviour of trace elements and the soil microbial activity. As bioindicators, the use of soil microbial carbon biomass and soil enzyme activities related to the carbon and phosphorus cycles seems to be relevant for assessing soil quality in rehabilitated and regenerated old mining sites. Our results showed that restoration with leguminous species had a positive effect on soil chemical quality and on soil microbial bioindicators, with activities that tended toward natural non-degraded soil (F). Active restoration processes also had a positive effect on Hg speciation by reducing its mobility. While in Sv we found more exchangeable and soluble mercury, in regenerated sites, Hg was mostly bound to organic matter. These results also suggested that enzyme activities and mercury cycles are sensitive to land restoration and must be considered when evaluating the efficiency of restoration processes.

Effect of biochar amendment on compost organic matter composition following aerobic composting of manure.

PubMed

Hagemann, Nikolas; Subdiaga, Edisson; Orsetti, Silvia; de la Rosa, José María; Knicker, Heike; Schmidt, Hans-Peter; Kappler, Andreas; Behrens, Sebastian

2018-02-01

Biochar, a material defined as charred organic matter applied in agriculture, is suggested as a beneficial additive and bulking agent in composting. Biochar addition to the composting feedstock was shown to reduce greenhouse gas emissions and nutrient leaching during the composting process, and to result in a fertilizer and plant growth medium that is superior to non-amended composts. However, the impact of biochar on the quality and carbon speciation of the organic matter in bulk compost has so far not been the focus of systematic analyses, although these parameters are key to determine the long-term stability and carbon sequestration potential of biochar-amended composts in soil. In this study, we used different spectroscopic techniques to compare the organic carbon speciation of manure compost amended with three different biochars. A non-biochar-amended compost served as control. Based on Fourier-transformed infrared (FTIR) and 13 C nuclear magnetic resonance (NMR) spectroscopy we did not observe any differences in carbon speciation of the bulk compost independent of biochar type, despite a change in the FTIR absorbance ratio 2925cm -1 /1034cm -1 , that is suggested as an indicator for compost maturity. Specific UV absorbance (SUVA) and emission-excitation matrixes (EEM) revealed minor differences in the extractable carbon fractions, which only accounted for ~2-3% of total organic carbon. Increased total organic carbon content of biochar-amended composts was only due to the addition of biochar-C and not enhanced preservation of compost feedstock-C. Our results suggest that biochars do not alter the carbon speciation in compost organic matter under conditions optimized for aerobic decomposition of compost feedstock. Considering the effects of biochar on compost nutrient retention, mitigation of greenhouse gas emissions and carbon sequestration, biochar addition during aerobic composting of manure might be an attractive strategy to produce a sustainable, slow release fertilizer. Copyright © 2017 Elsevier B.V. All rights reserved.

Chromium speciation in environmental samples using a solid phase spectrophotometric method.

PubMed

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 H(2)SO(4) 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 2.11×10(7) and 3.90×10(7) 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. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of arsenic species in solid matrices utilizing supercritical fluid extraction coupled with gas chromatography after derivatization with thioglycolic acid n-butyl ester.

PubMed

Wang, Zhifeng; Cui, Zhaojie

2016-12-01

A method using derivatization and supercritical fluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n-butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO 2 , extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n-butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO 2 can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X-405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO 2 modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estimating Inorganic Arsenic Exposure from U.S. Rice and Total Water Intakes

PubMed Central

Mantha, Madhavi; Yeary, Edward; Trent, John; Creed, Patricia A.; Kubachka, Kevin; Hanley, Traci; Shockey, Nohora; Heitkemper, Douglas; Caruso, Joseph; Xue, Jianping; Rice, Glenn; Wymer, Larry

2017-01-01

Background: Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. Objectives: Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. Methods: The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. Results: Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were 4.2μg/day and 1.4μg/day, respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice (2.8μg/day); the mean exposure rate for children between ages 1 and 2 years in this population is 0.104μg/kg body weight (BW)/day. Conclusions: An average consumer drinking 1.5 L of water daily that contains between 2 and 3 ng iAs/mL is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418 PMID:28572075

Bats (Chiroptera: Noctilionoidea) Challenge a Recent Origin of Extant Neotropical Diversity.

PubMed

Rojas, Danny; Warsi, Omar M; Dávalos, Liliana M

2016-05-01

The mechanisms underlying the high extant biodiversity in the Neotropics have been controversial since the 19th century. Support for the influence of period-specific changes on diversification often rests on detecting more speciation events during a particular period. The timing of speciation events may reflect the influence of incomplete taxon sampling, protracted speciation, and null processes of lineage accumulation. Here we assess the influence of these factors on the timing of speciation with new multilocus data for New World noctilionoid bats (Chiroptera: Noctilionoidea). Biogeographic analyses revealed the importance of the Neotropics in noctilionoid diversification, and the critical role of dispersal. We detected no shift in speciation rate associated with the Quaternary or pre-Quaternary periods, and instead found an increase in speciation linked to the evolution of the subfamily Stenodermatinae (∼18 Ma). Simulations modeling constant speciation and extinction rates for the phylogeny systematically showed more speciation events in the Quaternary. Since recording more divergence events in the Quaternary can result from lineage accumulation, the age of extant sister species cannot be interpreted as supporting higher speciation rates during this period. Instead, analyzing the factors that influence speciation requires modeling lineage-specific traits and environmental, spatial, and ecological drivers of speciation. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

Arsenic mobility and speciation in contaminated kitchen garden and lawn soils: an evaluation of water for assessment of As phytoavailability.

PubMed

Waterlot, Christophe; Douay, Francis

2015-04-01

Emissions from primary lead smelters have been recognized as one of the mainly factor which has contributed to the contamination of soils by metals. Less attention has been paid to volatile metalloids such as arsenic (As) which accompanies lead (Pb) smelting activities. One of the objectives of this study was to determine the As concentrations in various extracting solutions using a collection of urban soils located no far away from two former Pb and zinc plants in the North of France. The procedure for the determination of As, As(III), and As(V) with hydride vapor generator atomic absorption spectrometry was described in details. Pseudo-total concentrations of As in the studied soils ranged from 5.3 to 65.9 mg kg(-1). Good correlations were found between As and lead, zinc, and cadmium concentrations in soils. These depended on the soil uses and the soil distance from the source of contamination. Because the form of As may pose a health risk to human population, its speciation was determined in each urban top soils. Very good correlations were found between As(III) and As(V) versus As concentrations in soils studied, but the results did no permit to establish a relation between the location of soils and their uses. In contrast, it was shown that the highest mobility factor and lowest partitioning index values were related to the location. The mobilty of As depended on the assimilated phosphorus (P), carbonate contents, and pH. The percentages of the water-extractable As concentrations ranged from 0.3 to 3.0% of the As concentrations in soils. Very good positive correlations between water-extractable As(III) and As(V) versus water-extractable As concentrations were obtained. It was shown that the water-extractable As(III) concentrations depended on the soil uses. The results revealed that soils for which the As was the most mobile presented the highest water-extractable As concentrations. Principal component analysis indicated that mechanisms related to the release of As depended on the physico-chemical parameters of the soils, particularly on the assimilated P, organic matter, and/or iron oxides/hydroxides contents. Finally, the glasshouse experiments using ryegrass as plant model and three soils with similar physico-chemical parameters with regard to the PCA analysis showed that the water extracting solution could be a good indicator to evaluate the As phytoavailability.

Utility of ultrasound assisted-cloud point extraction and spectophotometry as a preconcentration and determination tool for the sensitive quantification of mercury species in fish samples

NASA Astrophysics Data System (ADS)

Altunay, Nail

2018-01-01

The current study reports, for the first time, the development of a new analytical method employing ultrasound assisted-cloud point extraction (UA-CPE) for the extraction of CH3Hg+ and Hg2 + species from fish samples. Detection and quantification of mercury species were performed at 550 nm by spectrophotometry. The analytical variables affecting complex formation and extraction efficiency were extensively evaluated and optimized by univariate method. Due to behave 14-fold more sensitive and selective of thiophene 2,5-dicarboxylic acid (H2TDC) to Hg2 + ions than CH3Hg+ in presence of mixed surfactant, Tween 20 and SDS at pH 5.0, the amounts of free Hg2 + and total Hg were spectrophotometrically established at 550 nm by monitoring Hg2 + in the pretreated- and extracted-fish samples in ultrasonic bath to speed up extraction using diluted acid mixture (1:1:1, v/v, 4 mol L- 1 HNO3, 4 mol L- 1 HCl, and 0.5 mol L- 1 H2O2), before and after pre-oxidation with permanganate in acidic media. The amount of CH3Hg+ was calculated from difference between total Hg and Hg2 + amounts. The UA-CPE method showed to be suitable for the extraction and determination of mercury species in certified reference materials. The results were in a good agreement (with Student's t-test at 95% confidence limit) with the certified values, and the relative standard deviation was lower than 3.2%. The limits of detection have been 0.27 and 1.20 μg L- 1, for Hg2 + from aqueous calibration solutions and matrix-matched calibration solutions spiked before digestion, respectively, while it is 2.43 μg L- 1 for CH3Hg+ from matrix-matched calibration solutions. A significant matrix effect was not observed from comparison of slopes of both calibration curves, so as to represent the sample matrix. The method was applied to fish samples for speciation analysis of Hg2 + and CH3Hg+. In terms of speciation, while total Hg is detected in range of 2.42-32.08 μg kg- 1, the distribution of mercury in fish were in range of 0.7-11.06 μg kg- 1 for CH3Hg+ and in range of 1.72-24.56 μg kg- 1 for Hg2 +.

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

USGS Publications Warehouse

Balistrieri, L.S.; Blank, R.G.

2008-01-01

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

Assessment of a sequential extraction protocol by examining solution chemistry and mineralogical evolution

NASA Astrophysics Data System (ADS)

Maubec, Nicolas; Pauwels, Hélène; Noël, Hervé; Bourrat, Xavier

2015-04-01

Knowledge of the behavior of heavy metals, such as copper and zinc in sediments, is a key factor to improve the management of rivers. The mobility of these metals, which may be harmful to the environment, depends directly on their concentration and speciation , which in turn depend on physico-chemical parameters such as mineralogy of the sediment fraction, pH, redox potential, salinity etc ... (Anderson et al., 2000; Sterckeman et al., 2004; Van Oort et al., 2008). Several methods based on chemical extractions are currently applied to assess the behavior of heavy metals in soils and sediments. Among them, sequential extraction procedure is widely used in soil and sediment science and provides details about the origin, biological and physicochemical availability, mobilization and transports of trace metals elements. It is based on the use of a series of extracting reagents to extract selectively heavy metals according to their association within the solid phase (Cornu and Clozel, 2000) including the following different fraction : exchangeable, bound to carbonates, associated to oxides (reducible fraction), linked to organic matter and sulfides (oxidizable fraction) as well as silicate minerals so called residual fraction (Hickey and Kittrick, 1984; Tessier et al., 1979). Consequently sequential extraction method is expected to simulate a lot of potential natural and anthropogenic modifications of environmental conditions (Arey et al., 1999; Brannon and Patrick, 1987; Hickey and Kittrick, 1984; La Force et al., 1999; Tessier et al., 1979). For three decades, a large number of protocols has been proposed, characterized by specific reagents and experimental conditions (concentrations, number of steps, extraction orders and solid/solution ratio) (Das et al., 1995; Gomez Ariza et al., 2000; Quevauviller et al., 1994; Rauret, 1998; Tack and Verloo, 1995), but it appeared that several of them suffer from a lack of selectivity of applied reagents: besides target ones, some of them are able to leach several solid phases. In this context, the aim of the present study is to investigate the effectiveness and the selectivity of different reagents for metal extraction from target geochemical fraction. It is based on solid analyses with the use of X-ray diffraction and a scanning electron microscopy (SEM) coupled to a microRaman spectrometer in conjunction with chemical analyses of extracting solutions at each step. This methodology provides the opportunity to assess more accurately the effect of each reagent. The study focuses on extraction of Cu and Zn from sediment samples collected at two sites from river banks and characterized by presence of Quartz, Feldspar K, Micas, Kaolinite but with differences regarding accessory phases (pyrite, organic matter, iron oxy- hydroxide, calcite). The interaction of the samples with eight different reagents was assessed and compared (Ca(NO3)2 and CaCl2 for the exchangeable fraction; buffered solutions of sodium acetate/acetic acid at pH = 5.5 and pH = 5 for the acido-soluble fraction; hydroxylamine hydrochloride and a solution of ammonium oxalate/oxalic acid for reducible fraction; hydrogen peroxide and sodium hypochlorite for the oxidizable fraction. In-depth characterization of solid residue at each step allowed proposing the best protocol for both metals. Anderson, P., Davidson, C. M., Duncan, A. L., Littlejohn, D., Ure, A. M., and Garden, L. M. (2000). Column leaching and sorption experiments to assess the mobility of potentially toxic elements in industrially contaminated land. Journal of Environmental Monitoring, 2. Arey, J. S., Seaman, J. C., and Bertsch, P. M. (1999). Immobilization of uranium in contaminated sediments by hydroxyapatite addition. Environmental Science & Technology, 33, 337-342. Brannon, J. M., and Patrick, W. H. (1987). Fixation, transformation, and mobilization of arsenic in sediments.Environmental Science & Technology, 21, 450-459. Cornu, S., and Clozel, B. (2000). Extractions séquentielles et spéciation des éléments trace métalliques dans les sols naturels. Analyse critique. 7, 179-189. Das, A. K., Chakraborty, R., Cervera, M. L., and Delaguardia, M. (1995). Metal speciation in solid matrices. Talanta, 42. Gomez Ariza, J. L., Giraldez, I., Sanchez-Rodas, D., and Morales, E. (2000). Selectivity assessment of a sequential extraction procedure for metal mobility characterization using model phases. Talanta, 52, 545-554. Hickey, M. G., and Kittrick, J. A. (1984). Chemical partitioning of cadmium, copper, nickel and zinc in soils and sediments containing high-levels of heavy metals. Journal of Environmental Quality, 13, 372-376. La Force, M. J., Fendorf, S., Li, G. C., and Rosenzweig, R. F. (1999). Redistribution of trace elements from contaminated sediments of Lake Coeur d'Alene during oxygenation. Journal of Environmental Quality, 28, 1195-1200. Quevauviller, P., Rauret, G., Muntau, H., Ure, A. M., Rubio, R., Lopezsanchez, J. F., Fiedler, H. D., and Griepink, B. (1994). Evaluation of a sequential extraction procedure for the determination of extractable trace-metal contents in sediments. Fresenius Journal of Analytical Chemistry, 349. Rauret, G. (1998). Extraction procedures for the determination of heavy metals in contaminated soil and sediment. Talanta, 46(3), 449-455. Sterckeman, T., Douay, F., Baize, D., Fourrier, H., Proix, N., and Schvartz, C. (2004). Factors affecting trace element concentrations in soils developed on recent marine deposits from northern France. Applied Geochemistry, 19. Tack, F. M. G., and Verloo, M. G. (1995). Chemical speciation and fraéctination in soil and sediment heavy-metal analysis - a review. International Journal of Environmental Analytical Chemistry, 59, 225-238. Tessier, A., Campbell, P. G. C., and Bisson, M. (1979). Sequential extraction procedure for the speciation of particulate trace-metals. Analytical Chemistry, 51. Van Oort, F., Jongmans, A. G., Lamy, I., Baize, D., and Chevallier, P. (2008). Impacts of long-term waste-water irrigation on the development of sandy Luvisols: consequences for metal pollutant distributions. European Journal of Soil Science, 59.

Water selenium speciation and sediment fractionation in a California flow-through wetland system

USGS Publications Warehouse

Gao, S.; Tanii, K.K.; Peters, D.W.; Herbel, M.J.

2000-01-01

A flow-through wetland system was established in the Tulare Lake Drainage District (TLDD) in California to determine if selenium (Se) from saline irrigation drainage can be removed prior to impoundment in evaporation basins to reduce potential toxicity to waterbirds. The objective of this research was to evaluate Se speciation, accumulation, and fractionation in the waters and sediments of the newly developed wetland system. The inlet water was dominated by selenate [Se(VI), 92%], with smaller percentages of selenite [Se(IV), 5%] and organic Se [org-Se(-II), 3%]. For the outflow water, the average percentage of Se(VI) was 72% in November 1997 and 59% in February 1999. This change may be due to an increase in either residence time and/or accumulation of organic detrital matter, which may enhance Se(VI) reduction processes. Selenium accumulation, transformation, and incorporation with the solid phase were all intensified in the surface sediment (<20 cm). The highest total Se concentrations in the sediments were found in the top 5 cm and concentrations dramatically decreased with depth. Elemental Se [Se(0)], as extracted by Na2SO3, was the largest fraction (average of 46%) of the total sediment Se, followed by organic matter-associated Se (OM-Se) extracted by NaOH (average of 34%). Soluble, adsorbed, and carbonate-associated Se, as extracted by KCl, K2HPO4 (pH 8.0), and NaOAc (pH 5.0), were about 3, 10, and 3% of the total sediment Se, respectively. After establishing the wetland for 2 yr, significant Se removal from the flowing water was observed. The major sink mechanisms in the sediment are reduction to Se(0) and immobilization into the organic phase.A flow-through wetland system was established in the Tulare Lake Drainage District (TLDD) in California to determine if selenium (Se) from saline irrigation drainage can be removed prior to impoundment in evaporation basins to reduce potential toxicity to waterbirds. The objective of this research was to evaluate Se speciation, accumulation, and fractionation in the waters and sediments of the newly developed wetland system. The inlet water was dominated by selenate [Se(VI), 92%], with smaller percentages of selenite [Se(IV), 5%] and organic Se [org-Se(-II), 3%]. For the outflow water, the average percentage of Se(VI) was 72% in November 1997 and 59% in February 1999. This change may be due to an increase in either residence time and/or accumulation of organic detrital matter, which may enhance Se(VI) reduction processes. Selenium accumulation, transformation, and incorporation with the solid phase were all intensified in the surface sediment (<20 cm). The highest total Se concentrations in the sediments were found in the top 5 cm and concentrations dramatically decreased with depth. Elemental Se [Se(0)], as extracted by Na2SO3, was the largest fraction (average of 46%) of the total sediment Se, followed by organic matter-associated Se (OM-Se) extracted by NaOH (average of 34%). Soluble, adsorbed, and carbonate-associated Se, as extracted by KCl, K2HPO4 (pH 8.0), and NaOAc (pH 5.0), were about 3, 10, and 3% of the total sediment Se, respectively. After establishing the wetland for 2 yr, significant Se removal from the flowing water was observed. The major sink mechanisms in the sediment are reduction to Se(0) and immobilization into the organic phase.

EPAs SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of source category-specific particulate matter (PM), volatile organic gas, and other gas speciation profiles of air pollutant emissions. Abt Associates, Inc. developed SPECIATE 4.4 through a collaborat...

SPECIATE Version 4.4 Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for regi...

SPECIATE - EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of total organic compound (TOC) and particulate matter (PM) speciation profiles for emissions from air pollution sources. The data base has recently been updated and an associated report has recently been re...

Speciation has a spatial scale that depends on levels of gene flow.

PubMed

Kisel, Yael; Barraclough, Timothy G

2010-03-01

Area is generally assumed to affect speciation rates, but work on the spatial context of speciation has focused mostly on patterns of range overlap between emerging species rather than on questions of geographical scale. A variety of geographical theories of speciation predict that the probability of speciation occurring within a given region should (1) increase with the size of the region and (2) increase as the spatial extent of intraspecific gene flow becomes smaller. Using a survey of speciation events on isolated oceanic islands for a broad range of taxa, we find evidence for both predictions. The probability of in situ speciation scales with island area in bats, carnivorous mammals, birds, flowering plants, lizards, butterflies and moths, and snails. Ferns are an exception to these findings, but they exhibit high frequencies of polyploid and hybrid speciation, which are expected to be scale independent. Furthermore, the minimum island size for speciation correlates across groups with the strength of intraspecific gene flow, as is estimated from a meta-analysis of published population genetic studies. These results indicate a general geographical model of speciation rates that are dependent on both area and gene flow. The spatial scale of population divergence is an important but neglected determinant of broad-scale diversity patterns.

Phosphorus Speciation of Sequential Extracts of Organic Amendments using NMR Spectroscopy

NASA Astrophysics Data System (ADS)

Akinremi, O.

2009-04-01

O.O. 1Akinremi Babasola Ajiboye and Donald N. Flaten 1Department of Soil Science, University of Manitoba, Winnipeg, R3T 2NT, Canada We carried out this study in order to determine the forms of phosphorus in various organic amendments using state-of-the art spectroscopic technique. Anaerobically digested biosolids (BIO), hog (HOG), dairy (DAIRY), beef (BEEF) and poultry (POULTRY) manures were subjected to sequential extraction. The extracts were analyzed by solution 31P nuclear magnetic resonance (NMR) spectroscopy. Most of the total P analysed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) in the sequential extracts of organic amendments were orthophosphate, except POULTRY, which was dominated by organic P. The labile P fraction in all the organic amendments, excluding POULTRY, was mainly orthophosphate P from readily soluble calcium and some aluminum phosphates. In the poultry litter, however, Ca phytate was the main P species controlling P solubility. Such knowledge of the differences in the chemical forms of phosphorus in organic amendments are essential for proper management of these amendments for agro-environmental purposes Key words: organic amendments, solution NMR, sequential fractionation, labile phosphorus

Speciation of chromium using reversed phase-high performance liquid chromatography coupled to different spectrometric detection methods

NASA Astrophysics Data System (ADS)

Andrle, C. M.; Jakubowski, N.; Broekaert, J. A. C.

1997-02-01

Speciation of Cr(III) and Cr(VI) based on the formation of different complexes with ammonium-pyrrolidinedithioate (APDC) in a continuous flow technique and their preconcentration using solid phase extraction (SPE) have been elaborated and applied to the analysis of waste waters from the galvanic industry. The Cr complexes were separated and determined using reversed phase-high performance liquid chromatography (RP-HPLC) coupled to different detection methods, namely UV-detection, graphite furnace-atomic absorption spectrometry (GF-AAS) and inductively coupled plasma mass spectrometry with hydraulic high pressure nebulization (HHPN/ICP-MS). After optimization the detection limits for Cr(III) and Cr(VI) of all methods are at the μg 1 -1 level and the precision in terms of RSD is 5% ( cCr = 100 μg 1 -1, N = 10). The procedure was applied to the determination of Cr(III) and Cr(VI) at the μg 1 -1 level in galvanic waste waters, and its accuracy was approved by comparing the results with those of independent methods.

Phytoavailability and geospeciation of cadmium in contaminated soil remediated by Rhodobacter sphaeroides.

PubMed

Fan, Wenhong; Jia, Yingying; Li, Xiaomin; Jiang, Wei; Lu, Lin

2012-07-01

A microorganism was isolated from oil field injection water and identified as Rhodobacter sphaeroides. It was used for the remediation of simulated cadmium-contaminated soil. The phytoavailability of Cd was investigated through wheat seedling method to determine the efficiency of remediation. It was found that after remediation, the accumulation of Cd in wheat roots and leaves decreased by 67% and 53%, respectively. The Cd speciation in soil was determined with Tessier extraction procedure. It was found that the total Cd content in soil did not change during the experiments, but the geo-speciation of Cd changed remarkably. Among the five fractions, the concentration of exchangeable phases decreased by 27-46% and that of the phases bound to Fe-Mn oxides increased by 22-44%. The decrease of Cd accumulation in wheat showed significant positive correlation with the decrease of exchangeable phases. It could be concluded that the remediation of R. sphaeroides was carried out through the conversion of Cd to more stable forms. The decrease of sulfate concentration in supernatant indicated that the R. sphaeroides consumed sulfate. Copyright © 2012 Elsevier Ltd. All rights reserved.

Arsenic uptake and speciation in the rootless duckweed Wolffia globosa.

PubMed

Zhang, Xin; Zhao, Fang-Jie; Huang, Qing; Williams, Paul N; Sun, Guo-Xin; Zhu, Yong-Guan

2009-01-01

Duckweeds are a common macrophyte in paddy and aquatic environments. Here, we investigated arsenic (As) accumulation, speciation and tolerance of the rootless duckweed Wolffia globosa and its potential for As phytofiltration. When grown with 1 microm arsenate, W. globosa accumulated two to 10 times more As than four other duckweed or Azolla species tested. W. globosa was able to accumulate > 1000 mg As kg(-1) in frond dry weight (DW), and tolerate up to 400 mg As kg(-1) DW. At the low concentration range, uptake rate was similar for arsenate and arsenite, but at the high concentration range, arsenite was taken up at a faster rate. Arsenite was the predominant As species (c. 90% of the total extractable As) in both arsenate- and arsenite-exposed duckweed. W. globosa was more resistant to external arsenate than arsenite, but showed a similar degree of tolerance internally. W. globosa decreased arsenate in solution rapidly, but also effluxed arsenite. Wolffia globosa is a strong As accumulator and an interesting model plant to study As uptake and metabolism because of the lack of a root-to-frond translocation barrier.

Aberrant Classopollis pollen reveals evidence for unreduced (2n) pollen in the conifer family Cheirolepidiaceae during the Triassic–Jurassic transition

PubMed Central

Kürschner, Wolfram M.; Batenburg, Sietske J.; Mander, Luke

2013-01-01

Polyploidy (or whole-genome doubling) is a key mechanism for plant speciation leading to new evolutionary lineages. Several lines of evidence show that most species among flowering plants had polyploidy ancestry, but it is virtually unknown for conifers. Here, we study variability in pollen tetrad morphology and the size of the conifer pollen type Classopollis extracted from sediments of the Triassic–Jurassic transition, 200 Ma. Classopollis producing Cheirolepidiaceae were one of the most dominant and diverse groups of conifers during the Mesozoic. We show that aberrant pollen Classopollis tetrads, triads and dyads, and the large variation in pollen size indicates the presence of unreduced (2n) pollen, which is one of the main mechanisms in modern polyploid formation. Polyploid speciation may explain the high variability of growth forms and adaptation of these conifers to different environments and their resistance to extreme growth conditions. We suggest that polyploidy may have also reduced the extinction risk of these conifers during the End-Triassic biotic crisis. PMID:23926159

Speciation of plutonium and other metals under UREX process conditIONS

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

Paulenova, Alena; Tkac, Peter; Matteson, Brent S.

2007-07-01

The extractability of various Pu and Np species into tri-n-butyl phosphate (TBP) was investigated. The concentration effects of aceto-hydroxamic acid, nitric acid and nitrate on the distribution ratio of U, Pu and Np were investigated. The considerable ability of AHA to form complexes with the studied elements even under strong acidic conditions was found. While the difference in the extraction of uranyl in the presence and absence of AHA is minimal, extraction yields of Pu and Np decrease significantly. The UV-Vis-NIR and FT-IR spectroscopic investigations of uranium, plutonium, and neptunium species in the presence and absence of AHA in bothmore » aqueous and organic extraction phase were also performed. Spectroscopic analysis showed that the organic phase can contain a substantial amount of metal-hydroxamate species. A solvated ternary complex of uranium UO{sub 2}.AHA.NO{sub 3}.2TBP was observed only after prolonged contact between the aqueous and organic phases, whereas the plutonium hydroxamate species, presumably Pu(AHA){sub x}(NO{sub 3}){sub 4-x}.2TBP, appeared in the organic phase after a four minute extraction. (authors)« less

SPECIATE--EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is EPA's repository of Total Organic Compound and Particulate Matter speciated profiles for a wide variety of sources. The profiles in this system are provided for air quality dispersion modeling and as a library for source-receptor and source apportionment type models. ...

SPECIATE 4.4: The Bridge Between Emissions Characterization and Modeling

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for...

The importance of trace element speciation in biomedical science.

PubMed

Templeton, Douglas M

2003-04-01

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

Unusual treatment of bimaxillary dentoalveolar protrusion via miniscrews and molar extraction

PubMed Central

Al-Fraidi, Ahmad; Afify, Ahmed R.

2012-01-01

This case report describes the treatment of a Saudi female patient, aged 13 years 8 months at the start of treatment, with a Class I bimaxillary dentoalveolar protrusion and extracted maxillary first molars. Miniscrews were placed bilaterally in the interdental space between both the upper and the lower posterior teeth. The treatment plan consisted of extraction of both lower first permanent molars, distalization of upper and lower premolars using miniscrews followed by en masse retraction of the upper and lower six anterior teeth. The active treatment period was 2 years 8 months. Arch retention was done using upper wrap-around retainer and lower fixed 3-3 retainer. The use of miniscrews helped to resolve the bimaxillary protrusion regardless of extraction pattern used. PMID:24987626

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

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

EPA Science Inventory

Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

Stachybotrys: An unusual mold associated with water-damaged buildings.

PubMed

Jarvis, B; Hinkley, S; Nielsen, K

2000-03-01

Chemical analyses of extracts of cultures ofS. chartarum show that this fungus has two chemotypes: producers of the potent cytotoxic macrocyclic trichothecenes (e. g. satratoxins) and those that produce the diterpenoid atranones and the simple trichothecenes, trichodermol and trichodermin. All isolates ofS. chartarum produce the immunosuppressant spirocyclic drimanes.

Production of unusual dispiro metabolites in Pestalotiopsis virgatula endophyte cultures: HPLC-SPE-NMR, electronic circular dichroism, and time-dependent density-functional computation study.

PubMed

Kesting, Julie R; Olsen, Lars; Staerk, Dan; Tejesvi, Mysore V; Kini, Kukkundoor R; Prakash, Harishchandra S; Jaroszewski, Jerzy W

2011-10-28

The endophytic fungus Pestalotiopsis virgatula, derived from the plant Terminalia chebula and previously found to produce a large excess of a single metabolite when grown in the minimal M1D medium, was induced to produce a variety of unusual metabolites by growing in potato dextrose broth medium. Analysis of the fermentation medium extract was performed using an HPLC-PDA-MS-SPE-NMR hyphenated system, which led to the identification of a total of eight metabolites (1-8), six of which are new. Most of the metabolites are structurally related and are derivatives of benzo[c]oxepin, rare among natural products. This includes dispiro derivatives 7 and 8 (pestalospiranes A and B), having a novel 1,9,11,18-tetraoxadispiro[6.2.6.2]octadecane skeleton. Relative and absolute configurations of the latter were determined by a combination of NOESY spectroscopy and electronic circular dichroism spectroscopy supported by time-dependent density-functional theory calculations (B3LYP/TZVP level). This work demonstrates that a largely complete structure elucidation of numerous metabolites present in a raw fermentation medium extract can be performed by the HPLC-SPE-NMR technique using only a small amount of the extract, even with unstable metabolites that are difficult to isolate by traditional methods.

Speciation genetics: current status and evolving approaches

PubMed Central

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

2010-01-01

The view of species as entities subjected to natural selection and amenable to change put forth by Charles Darwin and Alfred Wallace laid the conceptual foundation for understanding speciation. Initially marred by a rudimental understanding of hereditary principles, evolutionists gained appreciation of the mechanistic underpinnings of speciation following the merger of Mendelian genetic principles with Darwinian evolution. Only recently have we entered an era where deciphering the molecular basis of speciation is within reach. Much focus has been devoted to the genetic basis of intrinsic postzygotic isolation in model organisms and several hybrid incompatibility genes have been successfully identified. However, concomitant with the recent technological advancements in genome analysis and a newfound interest in the role of ecology in the differentiation process, speciation genetic research is becoming increasingly open to non-model organisms. This development will expand speciation research beyond the traditional boundaries and unveil the genetic basis of speciation from manifold perspectives and at various stages of the splitting process. This review aims at providing an extensive overview of speciation genetics. Starting from key historical developments and core concepts of speciation genetics, we focus much of our attention on evolving approaches and introduce promising methodological approaches for future research venues. PMID:20439277

Evolution of sulfur speciation in bitumen through hydrous pyrolysis induced thermal maturation of Jordanian Ghareb Formation oil shale

USGS Publications Warehouse

Birdwell, Justin E.; Lewan, Michael; Bake, Kyle D.; Bolin, Trudy B.; Craddock, Paul R.; Forsythe, Julia C.; Pomerantz, Andrew E.

2018-01-01

Previous studies on the distribution of bulk sulfur species in bitumen before and after artificial thermal maturation using various pyrolysis methods have indicated that the quantities of reactive (sulfide, sulfoxide) and thermally stable (thiophene) sulfur moieties change following consistent trends under increasing thermal stress. These trends show that sulfur distributions change during maturation in ways that are similar to those of carbon, most clearly illustrated by the increase in aromatic sulfur (thiophenic) as a function of thermal maturity. In this study, we have examined the sulfur moiety distributions of retained bitumen from a set of pre- and post-pyrolysis rock samples in an organic sulfur-rich, calcareous oil shale from the Upper Cretaceous Ghareb Formation. Samples collected from outcrop in Jordan were subjected to hydrous pyrolysis (HP). Sulfur speciation in extracted bitumens was examined using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The most substantial changes in sulfur distribution occurred at temperatures up to the point of maximum bitumen generation (∼300 °C) as determined from comparison of the total organic carbon content for samples before and after extraction. Organic sulfide in bitumen decreased with increasing temperature at relatively low thermal stress (200–300 °C) and was not detected in extracts from rocks subjected to HP at temperatures above around 300 °C. Sulfoxide content increased between 200 and 280 °C, but decreased at higher temperatures. The concentration of thiophenic sulfur increased up to 300 °C, and remained essentially stable under increasing thermal stress (mg-S/g-bitumen basis). The ratio of stable-to-reactive+stable sulfur moieties ([thiophene/(sulfide+sulfoxide+thiophene)], T/SST) followed a sigmoidal trend with HP temperature, increasing slightly up to 240 °C, followed by a substantial increase between 240 and 320 °C, and approaching a constant value (∼0.95) at temperatures above 320 °C. This sulfur moiety ratio appears to provide complementary thermal maturity information to geochemical parameters derived from other analyses of extracted source rocks.

Assessment of Important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...

Extraordinarily rapid speciation in a marine fish

PubMed Central

Momigliano, Paolo; Jokinen, Henri; Fraimout, Antoine; Florin, Ann-Britt; Norkko, Alf; Merilä, Juha

2017-01-01

Divergent selection may initiate ecological speciation extremely rapidly. How often and at what pace ecological speciation proceeds to yield strong reproductive isolation is more uncertain. Here, we document a case of extraordinarily rapid speciation associated with ecological selection in the postglacial Baltic Sea. European flounders (Platichthys flesus) in the Baltic exhibit two contrasting reproductive behaviors: pelagic and demersal spawning. Demersal spawning enables flounders to thrive in the low salinity of the Northern Baltic, where eggs cannot achieve neutral buoyancy. We show that demersal and pelagic flounders are a species pair arising from a recent event of speciation. Despite having a parapatric distribution with extensive overlap, the two species are reciprocally monophyletic and show strongly bimodal genotypic clustering and no evidence of contemporary migration, suggesting strong reproductive isolation. Divergence across the genome is weak but shows strong signatures of selection, a pattern suggestive of a recent ecological speciation event. We propose that spawning behavior in Baltic flounders is the trait under ecologically based selection causing reproductive isolation, directly implicating a process of ecological speciation. We evaluated different possible evolutionary scenarios under the approximate Bayesian computation framework and estimate that the speciation process started in allopatry ∼2,400 generations ago, following the colonization of the Baltic by the demersal lineage. This is faster than most known cases of ecological speciation and represents the most rapid event of speciation ever reported for any marine vertebrate. PMID:28533412

Selenium speciation using capillary electrophoresis coupled with modified electrothermal atomic absorption spectrometry after selective extraction with 5-sulfosalicylic acid functionalized magnetic nanoparticles.

PubMed

Yan, Lizhen; Deng, Biyang; Shen, Caiying; Long, Chanjuan; Deng, Qiufen; Tao, Chunyao

2015-05-22

A new method for selenium speciation in fermented bean curd wastewater and juice was described. This method involved sample extraction with 5-sulfosalicylic acid (SSA)-functionalized silica-coated magnetic nanoparticles (SMNPs), capillary electrophoresis (CE) separation, and online detection with a modified electrothermal atomic absorption spectrometry (ETAAS) system. The modified interface for ETAAS allowed for the introduction of CE effluent directly through the end of the graphite tube. Elimination of the upper injection hole of the graphite tube reduced the loss of the anlayte and enhanced the detection sensitivity. The SSA-SMNPs were synthesized and used to extract trace amounts of selenite [Se(IV)], selenite [Se(VI)], selenomethionine (SeMet), and selenocystine (SeCys2) from dilute samples. The concentration enrichment factors for Se(VI), Se(IV), SeMet, and SeCys2 were 21, 29, 18, and 12, respectively, using the SSA-SMNPs extraction. The limits of detection for Se(VI), Se(IV), SeMet, and SeCys2 were 0.18, 0.17, 0.54, 0.49ngmL(-1), respectively. The RSD values (n=6) of method for intraday were observed between 0.7% and 2.9%. The RSD values of method for interday were less than 3.5%. The linear range of Se(VI) and Se(IV) were in the range of 0.5-200ngmL(-1), and the linear ranges of SeMet and SeCys2 were 2-500 and 2-1000ngmL(-1), respectively. The detection limits of this method were improved by 10 times due to the enrichment by the SSA-SMNP extraction. The contents of Se(VI) and Se(IV) in fermented bean curd wastewater were measured as 3.83 and 2.62ngmL(-1), respectively. The contents of Se(VI), Se(IV), SeMet, and SeCys2 in fermented bean curd juice were determined as 6.39, 4.08, 2.77, and 4.00ngmL(-1), respectively. The recoveries were in the range of 99.14-104.5% and the RSDs (n=6) of recoveries between 0.82% and 3.5%. Copyright © 2015 Elsevier B.V. All rights reserved.

Differential extraction of radiocarbon associated with soil biomass and humus

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

Tsao, C.W.; Bartha, R.

To detect the humification of organic compounds in soil that bypasses biomass incorporation, selective extraction procedures for radiocarbon from soil biomass and humus were evaluated. Following the incubation of [sup 14]C-glucose and [sup 14]C-benzoate in soil, fumigation--0.5 M K[sub 2]SO[sub 4] extraction and 0.15 M Na[sub 4]P[sub 2]O[sub 7] extraction selectively removed biomass-associated and humus-associated radiocarbon, respectively. Applying the recovery correction of 3.4[times] to biomass and 3.5[times] to humus, radiocarbon balances of 95 to 107% were obtained during a time window following the degradation of these substrates. Negligible overlap between the extractions renders the technique suitable for investigating the fatemore » of organics that, through cometabolism, attain unusual radiocarbon distributions in soil.« less

Partial structural characterization and antioxidant activity of a phenolic-xylan from Castanea sativa hardwood.

PubMed

Renault, Emmanuel; Barbat-Rogeon, Aline; Chaleix, Vincent; Calliste, Claude-Alain; Colas, Cyril; Gloaguen, Vincent

2014-09-01

4-O-Methylglucuronoxylans (MGX) were isolated from chestnut wood sawdust using two different procedures: chlorite delignification followed by the classical alkaline extraction step, and an unusual green chemistry process of delignification using phthalocyanine/H2O2 followed by a simple extraction with hot water. Antioxidant properties of both MGX were evaluated against the stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) by electronic spin resonance (ESR). IC50 of water-extracted MGX was found to be less than 225 μg mL(-1), in contrast with alkali-extracted MGX for which no radical scavenging was observed. Characterization of extracts by colorimetric assay, GC, LC-MS and NMR spectroscopy provided some clues to understanding structure-function relationships of MGX in connection with their antioxidant activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction of selenium for speciation in foods and beverages.

PubMed

Wang, Xiaojun; Wu, Long; Cao, Jiaqi; Hong, Xincheng; Ye, Rui; Chen, Weiji; Yuan, Ting

2016-07-01

A novel, simple and rapid method based on magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction (MEA-IL-DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) determination was established for the speciation of selenium in various food and beverage samples. In the procedure, a special magnetic effervescent tablet containing CO2 sources (sodium carbonate and sodium dihydrogenphosphate), ionic liquids and Fe3O4 magnetic nanoparticles (MNPs) was used to combine extractant dispersion and magnetic recovery procedures into a single step. The parameters influencing the microextraction efficiency, such as pH of the sample solution, volume of ionic liquid, amount of MNPs, concentration of the chelating agent, salt effect and matrix effect were investigated and optimised. Under the optimised conditions, the limits of detection (LODs) for Se(IV) were 0.021 μg l(-)(1) and the linear dynamic range was 0.05-5.0 μg l(-)(1). The relative standard deviation for seven replicate measurements of 1.0 μg l(-)(1) of Se(IV) was 2.9%. The accuracy of the developed method was evaluated by analysis of the standard reference materials (GBW10016 tea, GBW10017 milk powder, GBW10043 Liaoning rice, GBW10046 Henan wheat, GBW10048 celery). The proposed method was successfully applied to food and beverage samples including black tea, milk powder, mushroom, soybean, bamboo shoots, energy drink, bottled water, carbonated drink and mineral water for the speciation of Se(IV) and Se(VI) with satisfactory relative recoveries (92.0-108.1%).

Content of trace elements and chromium speciation in Neem powder and tea infusions.

PubMed

Novotnik, Breda; Zuliani, Tea; Ščančar, Janez; Milačič, Radmila

2015-01-01

Total concentrations of selected trace elements in Neem powder and in Neem tea were determined by inductively coupled plasma mass spectrometry (ICP-MS). The data revealed that despite high total concentrations of the potentially toxic elements Al and Ni in Neem powder, their amounts dissolved in Neem tea were low. Total concentrations of the other toxic elements Pb, As and Cd were also very low and do not represent a health hazard. In contrast, total concentrations of the essential elements Fe, Cu, Zn, Se Mo and Cr in Neem powder were high and also considerable in Neem tea. Consuming one cup of Neem tea (2g per 200 mL of water) covers the recommended daily intakes for Cr and Se and represents an important source of Mo and Cu. Speciation analysis of Cr by high performance liquid chromatography (HPLC) coupled to ICP-MS with the use of enriched Cr isotopic tracers to follow species interconversions during the analytical procedure demonstrated that toxic Cr(VI) was not present either in Neem powder or in Neem tea. Its concentrations were below the limits of detection of the HPLC-ICP-MS procedure applied. The speciation analysis data confirmed that even Cr(VI) was added, it was rapidly reduced by the presence of antioxidants in Neem leaves. By the use of enriched Cr isotopic spike solutions it was also demonstrated that for obtaining reliable analytical data it is essential to apply the extraction procedures which prevent Cr species interconversions, or to correct for species transformation. Copyright © 2015 Elsevier GmbH. All rights reserved.

Implications for metal and volatile cycles from the pH of subduction zone fluids

NASA Astrophysics Data System (ADS)

Galvez, Matthieu E.; Connolly, James A. D.; Manning, Craig E.

2016-11-01

The chemistry of aqueous fluids controls the transport and exchange—the cycles—of metals and volatile elements on Earth. Subduction zones, where oceanic plates sink into the Earth’s interior, are the most important geodynamic setting for this fluid-mediated chemical exchange. Characterizing the ionic speciation and pH of fluids equilibrated with rocks at subduction zone conditions has long been a major challenge in Earth science. Here we report thermodynamic predictions of fluid-rock equilibria that tie together models of the thermal structure, mineralogy and fluid speciation of subduction zones. We find that the pH of fluids in subducted crustal lithologies is confined to a mildly alkaline range, modulated by rock volatile and chlorine contents. Cold subduction typical of the Phanerozoic eon favours the preservation of oxidized carbon in subducting slabs. In contrast, the pH of mantle wedge fluids is very sensitive to minor variations in rock composition. These variations may be caused by intramantle differentiation, or by infiltration of fluids enriched in alkali components extracted from the subducted crust. The sensitivity of pH to soluble elements in low abundance in the host rocks, such as carbon, alkali metals and halogens, illustrates a feedback between the chemistry of the Earth’s atmosphere-ocean system and the speciation of subduction zone fluids via the composition of the seawater-altered oceanic lithosphere. Our findings provide a perspective on the controlling reactions that have coupled metal and volatile cycles in subduction zones for more than 3 billion years7.

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

PubMed

Tytła, Malwina; Widziewicz, Kamila; Zielewicz, Ewa

2016-01-01

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

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

USGS Publications Warehouse

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

2002-01-01

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

The effect of environmental conditions and soil physicochemistry on phosphate stabilisation of Pb in shooting range soils.

PubMed

Sanderson, Peter; Naidu, Ravi; Bolan, Nanthi

2016-04-01

The stabilisation of Pb in the soil by phosphate is influenced by environmental conditions and physicochemical properties of the soils to which it is applied. Stabilisation of Pb by phosphate was examined in four soils under different environmental conditions. The effect of soil moisture and temperature on stabilisation of Pb by phosphate was examined by measurement of water extractable and bioaccessible Pb, sequential fractionation and X-ray absorption spectroscopy. The addition of humic acid, ammonium nitrate and chloride was also examined for inhibition or improvement of Pb stability with phosphate treatment. The effect of moisture level varied between soils. In soil MB and DA a soil moisture level of 50% water holding capacity was sufficient to maximise stabilisation of Pb, but in soil TV and PE reduction in bioaccessible Pb was inhibited at this moisture level. Providing moisture at twice the soil water holding capacity did not enhance the effect of phosphate on Pb stabilisation. The difference of Pb stability as a result of incubating phosphate treated soils at 18 °C and 37 °C was relatively small. However wet-dry cycles decreased the effectiveness of phosphate treatment. The reduction in bioaccessible Pb obtained was between 20 and 40% with the most optimal treatment conditions. The reduction in water extractable Pb by phosphate was substantial regardless of incubation conditions and the effect of different temperature and soil moisture regimes was not significant. Selective sequential extraction showed phosphate treatment converted Pb in fraction 1 (exchangeable, acid and water soluble) to fraction 2 (reducible). There were small difference in fraction 4 (residual) Pb and fraction 1 as a result of treatment conditions. X-ray absorption spectroscopy of stabilised PE soil revealed small differences in Pb speciation under varying soil moisture and temperature treatments. The addition of humic acid and chloride produced the greatest effect on Pb speciation in phosphate treated soils. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

Arsenic Concentrations and Speciation in Shellfishes from Korea

NASA Astrophysics Data System (ADS)

Yoon, C.; Yoon, H.

2005-12-01

Speciation of arsenic has received significant attention over the past 20 years in both mechanistic and exposure assessment research. Because the toxicity of arsenic is related to its oxidation state and its chemical forms, the determination of the total arsenic contents in a sample is not adequate to allow its impact on living organisms to be estimated. The inorganic arsenic species, arsenite (As3+) and arsenate (As5+), have been classified as carcinogenic and the methylated forms, monomethyl arsonic acid (MMA) and dimethyl arsinic acid (DMA) have recently been identified as cancer promoters. The highly methylated compounds like as arsenobetaine (AsB) and arsenocholine (AsC) are considered to be nontoxic. Although organisms in marine environment contain high amounts of total arsenic (ppm level), it is not usually present as inorganic arsenic or simple methylated forms well known as one of the toxic species. Arsenobetaine is the dominant species in marine animals and arsenosugars are most abundant in marine algae. This study aims to clarify those arsenic species present in the whole body of eleven different shellfishes from Korea. And those arsenic species were separated and measured by characterization using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) coupled system. The separation of arsenic species was achieved on anion exchange column and cation exchange column using phosphate and pyridine eluent, respectively. The ultrasonic extraction was employed for extraction of arsenic from whole body of shellfishes. The method was validated by analyzing three certified reference materials (DORM-2, TORT-2, 1566b). Total arsenic concentrations ranged from 0.1 mg/kg dry mass to 21.7 mg/kg dry mass. Most marine shellfishes contained higher arsenobetaine and arsenocholine with the exception of two shellfishes living in river. The lower amounts of inorganic arsenic species were also found in the some sample extracts. Detection of inorganic arsenic can be explained by the conversion of inorganic arsenic to organic arsenic compounds in digestion system in the body may be occurring.

[Transformation and mobility of arsenic in the rhizosphere and non-rhizosphere soils at different growth stages of rice].

PubMed

Yang, Wen-Tao; Wang, Ying-Jie; Zhou, Hang; Yi, Kai-Xin; Zeng, Min; Peng, Pei-Qin; Liao, Bo-Han

2015-02-01

Speciation and bioavailability of arsenic in the rhizosphere and non-rhizosphere soils at different growth stages (tillering stage, jointing stage, booting stage, filling stage and maturing stage) of rice (Oryza sativa L.) were studied using toxicity characteristic leaching procedure (TCLP) and arsenic speciation analysis. Pot experiments were conducted and the soil samples were taken from a certain paddy soil in Hunan Province contaminated by mining industry. The results showed that: (1) With the extension of rice growth period, pH values and TCLP extractable arsenic levels in the rhizosphere and non-rhizosphere soils increased gradually. Soil pH and TCLP extractable arsenic levels in non-rhizosphere soils were higher than those in the rhizosphere soils at the same growth stage. (2) At the different growth stages of rice, contents of exchangeable arsenic (AE-As) in rhizosphere and non-rhizosphere soils were lower than those before the rice planting, and increased gradually with the extension of the rice growing period. Contents of Al-bound arsenic (Al-As), Fe-bound arsenic (Fe-As) and Ca-bound arsenic (Ca-As) increased gradually after rice planting, but not significantly. Residual arsenic (O-As) and total arsenic (T-As) decreased gradually after rice planting, by 37.30% and 14.69% in the rhizosphere soils and by 31.38% and 8.67% in the non-rhizosphere soils, respectively. (3) At the different growth stages of rice, contents of various forms of arsenic in the soils were in the following order: residual arsenic (O-As) > Fe-bound arsenic ( Fe-As) > Al-bound arsenic (Al-As) > Ca-bound arsenic (Ca-As) > exchangeable arsenic (AE-As). In the pH range of 5.0- 5.8, significant positive linear correlations were found between most forms of arsenic or TCLP extractable arsenic levels and pH values, while the Ca-bound arsenic was poorly correlated with pH values in the rhizosphere soils.

Speciation of 210Po and 210Pb in air particulates determined by sequential extraction.

PubMed

Al-Masri, M S; Al-Karfan, K; Khalili, H; Hassan, M

2006-01-01

Speciation of (210)Po and (210)Pb in air particulates of two Syrian phosphate sites with different climate conditions has been studied. The sites are the mines and Tartous port at the Mediterranean Sea. Air filters were collected during September 2000 until February 2002 and extracted chemically using different selective fluids in an attempt to identify the different forms of these two radionuclides. The results have shown that the inorganic and insoluble (210)Po and (210)Pb (attached to silica and soluble in mineral acids) portion was found to be high in both sites and reached a maximum value of 94% and 77% in the mine site and Tartous port site, respectively. In addition, only 24% of (210)Pb in air particulates was found to be associated with organic materials probably produced from the incomplete burning of fuel vehicle and similar activities. Moreover, the (210)Po/(210)Pb activity ratio in air particulates was higher than that in all samples at both sites and varied between 3.85 in November 2000 at Tartous port site and 20 in April 2001 at the mine area. These activity ratios were also higher than the natural levels. The (210)Po/(210)Pb activity ratio was also determined in each portion resulting from the selective extraction and found to be higher than that in most samples. The sources of (210)Po excess in these portions are discussed. Soil suspension, which is common in the dry climate dominant in the area, sea water spray and heating of phosphate ores were considered; polonium is more volatile than the lead compounds at even moderate temperature. Furthermore, variations in the chemical forms of (210)Po and (210)Pb during the year were also investigated. However, the results of this study can also be utilized for dose assessment to phosphate industry workers.

Assessment of important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps (US EPA 2017 International Emissions Inventory Conference)

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...

A complex speciation–richness relationship in a simple neutral model

PubMed Central

Desjardins-Proulx, Philippe; Gravel, Dominique

2012-01-01

Speciation is the “elephant in the room” of community ecology. As the ultimate source of biodiversity, its integration in ecology's theoretical corpus is necessary to understand community assembly. Yet, speciation is often completely ignored or stripped of its spatial dimension. Recent approaches based on network theory have allowed ecologists to effectively model complex landscapes. In this study, we use this framework to model allopatric and parapatric speciation in networks of communities. We focus on the relationship between speciation, richness, and the spatial structure of communities. We find a strong opposition between speciation and local richness, with speciation being more common in isolated communities and local richness being higher in more connected communities. Unlike previous models, we also find a transition to a positive relationship between speciation and local richness when dispersal is low and the number of communities is small. We use several measures of centrality to characterize the effect of network structure on diversity. The degree, the simplest measure of centrality, is the best predictor of local richness and speciation, although it loses some of its predictive power as connectivity grows. Our framework shows how a simple neutral model can be combined with network theory to reveal complex relationships between speciation, richness, and the spatial organization of populations. PMID:22957181

Characteristics of arsenic in humic substances extracted from natural organic sediments.

PubMed

Hara, Junko; Norota, Susumu; Kawebe, Yoshishige; Sugita, Hajime; Zhang, Ming

2018-06-01

The stability and dispersion of naturally occurring As have been receiving increasing attention, because As is toxic and its contamination is a widespread problem in many countries. This study investigated As fractionation and speciation in organic sediments collected from different depositional settings to elucidate the existence of stable As in humic substances. Eleven organic sediment samples were collected from marine and terrestrial alluvial regions in Hokkaido prefecture, Japan, and the chemical fraction of As and species of humic substances were identified by sequential extraction. In addition, stable As bound in organic matter was evaluated by FT-IR spectroscopy. The As fraction mainly comprised inorganic substances, especially sulfur, iron, and manganese, and terrestrial sediments (lacustrine and inland deposits) were rich in sulfides and Fe and Al (hydr)oxides. When the residual fraction was excluded, the organic fraction of As was higher in seawater sediments than in terrestrial sediments. Among humic substances, cellulose, humic acid, and hydrophilic fulvic acid were clearly associated with As accumulation, and As speciation showed that the As was of organic origin. Cellulose, an organic compound of plant origin, was abundant in As=S and As (III)=O bonds, and As accumulation was higher in sulfur-rich peat sediments, corresponding with the physiological activities of As in plants. Hydrophilic fulvic acid and humic acid in these sediments, originating from small animals and microorganisms in addition to plants, denote higher As contents and abound in As (III, V)=C and C-H, CH 3 bonds even in sulfur-rich sediments. The methylated As bonds reflect the ecological transition of organisms.

Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

2008-02-15

A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

Broiler diet modification and litter storage: impacts on phosphorus in litters, soils, and runoff.

PubMed

McGrath, Joshua M; Sims, J Thomas; Maguire, Rory O; Saylor, William W; Angel, C Roselina; Turner, Benjamin L

2005-01-01

Modifying broiler diets to mitigate water quality concerns linked to excess phosphorus (P) in regions of intensive broiler production has recently increased. Our goals were to evaluate the effects of dietary modification, using phytase and reduced non-phytate phosphorus (NPP) supplementation, on P speciation in broiler litters, changes in litter P forms during long-term storage, and subsequent impacts of diets on P in runoff from litter-amended soils. Four diets containing two levels of NPP with and without phytase were fed to broilers in a three-flock floor pen study. After removal of the third flock, litters were stored for 440 d at their initial moisture content (MC; 24%) and at a MC of 40%. Litter P fractions and orthophosphate and phytate P concentrations were determined before and after storage. After storage, litters were incorporated with a sandy and silt loam and simulated rainfall was applied. Phytase and reduced dietary NPP significantly reduced litter total P. Reducing dietary NPP decreased water-extractable inorganic phosphorus (IP) and the addition of dietary phytase reduced NaOH- and HCl-extractable organic P in litter, which correlated well with orthophosphate and phytic acid measured by 31P nuclear magnetic resonance (NMR), respectively. Although dry storage caused little change in P speciation, wet storage increased concentrations of water-soluble IP, which increased reactive P in runoff from litter-amended soils. Therefore, diet modification with phytase and reduced NPP could be effective in reducing P additions on a watershed scale. Moreover, efforts to minimize litter MC during storage may reduce the potential for dissolved P losses in runoff.

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

PubMed

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.

Erosive processes after tectonic uplift stimulate vicariant and adaptive speciation: evolution in an Afrotemperate-endemic paper daisy genus

PubMed Central

2014-01-01

Background The role of tectonic uplift in stimulating speciation in South Africa’s only alpine zone, the Drakensberg, has not been explicitly examined. Tectonic processes may influence speciation both through the creation of novel habitats and by physically isolating plant populations. We use the Afrotemperate endemic daisy genus Macowania to explore the timing and mode (geographic versus adaptive) of speciation in this region. Between sister species pairs we expect high morphological divergence where speciation has happened in sympatry (adaptive) while with geographic (vicariant) speciation we may expect to find less morphological divergence and a greater degree of allopatry. A dated molecular phylogenetic hypothesis for Macowania elucidates species’ relationships and is used to address the potential impact of uplift on diversification. Morphological divergence of a small sample of reproductive and vegetative characters, used as a proxy for adaptive divergence, is measured against species’ range distributions to estimate mode of speciation across two subclades in the genus. Results The Macowania crown age is consistent with the hypothesis of post-uplift diversification, and we find evidence for both vicariant and adaptive speciation between the two subclades within Macowania. Both subclades exhibit strong signals of range allopatry, suggesting that geographic isolation was important in speciation. One subclade, associated with dry, rocky environments at high altitudes, shows very little morphological and ecological differentiation but high range allopatry. The other subclade occupies a greater variety of habitats and exhibits far greater morphological differentiation, but contains species with overlapping distribution ranges. Conclusions Species in Macowania are likely to have diversified in response to tectonic uplift, and we invoke uplift and uplift-mediated erosion as the main drivers of speciation. The greater relative morphological divergence in sympatric species of Macowania indicates that speciation in the non-sympatric taxa may not have required obvious adaptive differences, implying that simple geographic isolation was the driving force for speciation (‘neutral speciation’). PMID:24524661

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

PubMed

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 groups. To establish whether heliconiines are exceptional will require biogeographic comparative studies for a wider range of animal taxa including many more invertebrates.

Ancient papillomavirus-host co-speciation in Felidae

PubMed Central

Rector, Annabel; Lemey, Philippe; Tachezy, Ruth; Mostmans, Sara; Ghim, Shin-Je; Van Doorslaer, Koenraad; Roelke, Melody; Bush, Mitchell; Montali, Richard J; Joslin, Janis; Burk, Robert D; Jenson, Alfred B; Sundberg, John P; Shapiro, Beth; Van Ranst, Marc

2007-01-01

Background Estimating evolutionary rates for slowly evolving viruses such as papillomaviruses (PVs) is not possible using fossil calibrations directly or sequences sampled over a time-scale of decades. An ability to correlate their divergence with a host species, however, can provide a means to estimate evolutionary rates for these viruses accurately. To determine whether such an approach is feasible, we sequenced complete feline PV genomes, previously available only for the domestic cat (Felis domesticus, FdPV1), from four additional, globally distributed feline species: Lynx rufus PV type 1, Puma concolor PV type 1, Panthera leo persica PV type 1, and Uncia uncia PV type 1. Results The feline PVs all belong to the Lambdapapillomavirus genus, and contain an unusual second noncoding region between the early and late protein region, which is only present in members of this genus. Our maximum likelihood and Bayesian phylogenetic analyses demonstrate that the evolutionary relationships between feline PVs perfectly mirror those of their feline hosts, despite a complex and dynamic phylogeographic history. By applying host species divergence times, we provide the first precise estimates for the rate of evolution for each PV gene, with an overall evolutionary rate of 1.95 × 10-8 (95% confidence interval 1.32 × 10-8 to 2.47 × 10-8) nucleotide substitutions per site per year for the viral coding genome. Conclusion Our work provides evidence for long-term virus-host co-speciation of feline PVs, indicating that viral diversity in slowly evolving viruses can be used to investigate host species evolution. These findings, however, should not be extrapolated to other viral lineages without prior confirmation of virus-host co-divergence. PMID:17430578

The explosive radiation of Cheirolophus (Asteraceae, Cardueae) in Macaronesia

PubMed Central

2014-01-01

Background Considered a biodiversity hotspot, the Canary Islands have been the key subjects of numerous evolutionary studies concerning a large variety of organisms. The genus Cheirolophus (Asteraceae) represents one of the largest plant radiations in the Canarian archipelago. In contrast, only a few species occur in the Mediterranean region, the putative ancestral area of the genus. Here, our main aim was to reconstruct the phylogenetic and biogeographic history of Cheirolophus with special focus on explaining the origin of the large Canarian radiation. Results We found significant incongruence in phylogenetic relationships between nuclear and plastid markers. Each dataset provided resolution at different levels in Cheirolophus: the nuclear markers resolved the backbone of the phylogeny while the plastid data provided better resolution within the Canarian clade. The origin of Cheirolophus was dated in the Mid-Late Miocene, followed by rapid diversification into the three main Mediterranean lineages and the Macaronesian clade. A decrease in diversification rates was inferred at the end of the Miocene, with a new increase in the Late Pliocene concurrent with the onset of the Mediterranean climate. Diversification within the Macaronesian clade started in the Early-Mid Pleistocene, with unusually high speciation rates giving rise to the extant insular diversity. Conclusions Climate-driven diversification likely explains the early evolutionary history of Cheirolophus in the Mediterranean region. It appears that the exceptionally high diversification rate in the Canarian clade was mainly driven by allopatric speciation (including intra- and interisland diversification). Several intrinsic (e.g. breeding system, polyploid origin, seed dispersal syndrome) and extrinsic (e.g. fragmented landscape, isolated habitats, climatic and geological changes) factors probably contributed to the progressive differentiation of populations resulting in numerous microendemisms. Finally, hybridization events and emerging ecological adaptation may have also reinforced the diversification process. PMID:24888240

The explosive radiation of Cheirolophus (Asteraceae, Cardueae) in Macaronesia.

PubMed

Vitales, Daniel; Garnatje, Teresa; Pellicer, Jaume; Vallès, Joan; Santos-Guerra, Arnoldo; Sanmartín, Isabel

2014-06-02

Considered a biodiversity hotspot, the Canary Islands have been the key subjects of numerous evolutionary studies concerning a large variety of organisms. The genus Cheirolophus (Asteraceae) represents one of the largest plant radiations in the Canarian archipelago. In contrast, only a few species occur in the Mediterranean region, the putative ancestral area of the genus. Here, our main aim was to reconstruct the phylogenetic and biogeographic history of Cheirolophus with special focus on explaining the origin of the large Canarian radiation. We found significant incongruence in phylogenetic relationships between nuclear and plastid markers. Each dataset provided resolution at different levels in Cheirolophus: the nuclear markers resolved the backbone of the phylogeny while the plastid data provided better resolution within the Canarian clade. The origin of Cheirolophus was dated in the Mid-Late Miocene, followed by rapid diversification into the three main Mediterranean lineages and the Macaronesian clade. A decrease in diversification rates was inferred at the end of the Miocene, with a new increase in the Late Pliocene concurrent with the onset of the Mediterranean climate. Diversification within the Macaronesian clade started in the Early-Mid Pleistocene, with unusually high speciation rates giving rise to the extant insular diversity. Climate-driven diversification likely explains the early evolutionary history of Cheirolophus in the Mediterranean region. It appears that the exceptionally high diversification rate in the Canarian clade was mainly driven by allopatric speciation (including intra- and interisland diversification). Several intrinsic (e.g. breeding system, polyploid origin, seed dispersal syndrome) and extrinsic (e.g. fragmented landscape, isolated habitats, climatic and geological changes) factors probably contributed to the progressive differentiation of populations resulting in numerous microendemisms. Finally, hybridization events and emerging ecological adaptation may have also reinforced the diversification process.

Extraction of rare earth elements from a contaminated cropland soil using nitric acid, citric acid, and EDTA.

PubMed

Tang, Hailong; Shuai, Weitao; Wang, Xiaojing; Liu, Yangsheng

2017-08-01

Rare earth elements (REEs) contamination to the surrounding soil has increased the concerns of health risk to the local residents. Soil washing was first attempted in our study to remediate REEs-contaminated cropland soil using nitric acid, citric acid, and ethylene diamine tetraacetic acid (EDTA) for soil decontamination and possible recovery of REEs. The extraction time, washing agent concentration, and pH value of the washing solution were optimized. The sequential extraction analysis proposed by Tessier was adopted to study the speciation changes of the REEs before and after soil washing. The extract containing citric acid was dried to obtain solid for the X-ray fluorescence (XRF) analysis. The results revealed that the optimal extraction time was 72 h, and the REEs extraction efficiency increased as the agent concentration increased from 0.01 to 0.1 mol/L. EDTA was efficient to extract REEs over a wide range of pH values, while citric acid was around pH 6.0. Under optimized conditions, the average extraction efficiencies of the major REEs in the contaminated soil were 70.96%, 64.38%, and 62.12% by EDTA, nitric acid, and citric acid, respectively. The sequential extraction analyses revealed that most soil-bounded REEs were mobilized or extracted except for those in the residual fraction. Under a comprehensive consideration of the extraction efficiency and the environmental impact, citric acid was recommended as the most suitable agent for extraction of the REEs from the contaminated cropland soils. The XRF analysis revealed that Mn, Al, Si, Pb, Fe, and REEs were the major elements in the extract indicating a possibile recovery of the REEs.

Secondary sympatry caused by range expansion informs on the dynamics of microendemism in a biodiversity hotspot.

PubMed

Nattier, Romain; Grandcolas, Philippe; Elias, Marianne; Desutter-Grandcolas, Laure; Jourdan, Hervé; Couloux, Arnaud; Robillard, Tony

2012-01-01

Islands are bounded areas where high endemism is explained either by allopatric speciation through the fragmentation of the limited amount of space available, or by sympatric speciation and accumulation of daughter species. Most empirical evidence point out the dominant action of allopatric speciation. We evaluate this general view by looking at a case study where sympatric speciation is suspected. We analyse the mode, tempo and geography of speciation in Agnotecous, a cricket genus endemic to New Caledonia showing a generalized pattern of sympatry between species making sympatric speciation plausible. We obtained five mitochondrial and five nuclear markers (6.8 kb) from 37 taxa corresponding to 17 of the 21 known extant species of Agnotecous, and including several localities per species, and we conducted phylogenetic and dating analyses. Our results suggest that the diversification of Agnotecous occurred mostly through allopatric speciation in the last 10 Myr. Highly microendemic species are the most recent ones (<2 Myr) and current sympatry is due to secondary range expansion after allopatric speciation. Species distribution should then be viewed as a highly dynamic process and extreme microendemism only as a temporary situation. We discuss these results considering the influence of climatic changes combined with intricate soil diversity and mountain topography. A complex interplay between these factors could have permitted repeated speciation events and range expansion.

Selenium Metabolism in Cancer Cells: The Combined Application of XAS and XFM Techniques to the Problem of Selenium Speciation in Biological Systems

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Finney, Lydia; Vogt, Stefan; Witting, Paul K.; Harris, Hugh H.

2013-01-01

Determining the speciation of selenium in vivo is crucial to understanding the biological activity of this essential element, which is a popular dietary supplement due to its anti-cancer properties. Hyphenated techniques that combine separation and detection methods are traditionally and effectively used in selenium speciation analysis, but require extensive sample preparation that may affect speciation. Synchrotron-based X-ray absorption and fluorescence techniques offer an alternative approach to selenium speciation analysis that requires minimal sample preparation. We present a brief summary of some key HPLC-ICP-MS and ESI-MS/MS studies of the speciation of selenium in cells and rat tissues. We review the results of a top-down approach to selenium speciation in human lung cancer cells that aims to link the speciation and distribution of selenium to its biological activity using a combination of X-ray absorption spectroscopy (XAS) and X-ray fluorescence microscopy (XFM). The results of this approach highlight the distinct fates of selenomethionine, methylselenocysteine and selenite in terms of their speciation and distribution within cells: organic selenium metabolites were widely distributed throughout the cells, whereas inorganic selenium metabolites were compartmentalized and associated with copper. New data from the XFM mapping of electrophoretically-separated cell lysates show the distribution of selenium in the proteins of selenomethionine-treated cells. Future applications of this top-down approach are discussed. PMID:23698165

A comparative analysis of island floras challenges taxonomy-based biogeographical models of speciation.

PubMed

Igea, Javier; Bogarín, Diego; Papadopulos, Alexander S T; Savolainen, Vincent

2015-02-01

Speciation on islands, and particularly the divergence of species in situ, has long been debated. Here, we present one of the first, complete assessments of the geographic modes of speciation for the flora of a small oceanic island. Cocos Island (Costa Rica) is pristine; it is located 550 km off the Pacific coast of Central America. It harbors 189 native plant species, 33 of which are endemic. Using phylogenetic data from insular and mainland congeneric species, we show that all of the endemic species are derived from independent colonization events rather than in situ speciation. This is in sharp contrast to the results of a study carried out in a comparable system, Lord Howe Island (Australia), where as much as 8.2% of the plant species were the product of sympatric speciation. Differences in physiography and age between the islands may be responsible for the contrasting patterns of speciation observed. Importantly, comparing phylogenetic assessments of the modes of speciation with taxonomy-based measures shows that widely used island biogeography approaches overestimate rates of in situ speciation. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Self-consistent approach for neutral community models with speciation

NASA Astrophysics Data System (ADS)

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.

Arsenic Speciation and Extraction and the Significance of Biodegradable Acid on Arsenic Removal—An Approach for Remediation of Arsenic-Contaminated Soil

PubMed Central

Nguyen Van, Thinh; Osanai, Yasuhito; Do Nguyen, Hai; Kurosawa, Kiyoshi

2017-01-01

A series of arsenic remediation tests were conducted using a washing method with biodegradable organic acids, including oxalic, citric and ascorbic acids. Approximately 80% of the arsenic in one sample was removed under the effect of the ascorbic and oxalic acid combination, which was roughly twice higher than the effectiveness of the ascorbic and citric acid combination under the same conditions. The soils treated using biodegradable acids had low remaining concentrations of arsenic that are primarily contained in the crystalline iron oxides and organic matter fractions. The close correlation between extracted arsenic and extracted iron/aluminum suggested that arsenic was removed via the dissolution of Fe/Al oxides in soils. The fractionation of arsenic in four contaminated soils was investigated using a modified sequential extraction method. Regarding fractionation, we found that most of the soil contained high proportions of arsenic (As) in exchangeable fractions with phosphorus, amorphous oxides, and crystalline iron oxides, while a small amount of the arsenic fraction was organic matter-bound. This study indicated that biodegradable organic acids can be considered as a means for arsenic-contaminated soil remediation.

High performance preconcentration of inorganic Se species by dispersive micro-solid phase extraction with a nanosilica-ionic liquid hybrid material

NASA Astrophysics Data System (ADS)

Llaver, Mauricio; Coronado, Eduardo A.; Wuilloud, Rodolfo G.

2017-12-01

A highly sensitive and efficient dispersive micro-solid phase extraction (D-μ-SPE) method was developed for inorganic Se speciation analysis. A novel ionic liquid (IL)-nanomaterial hybrid consisting of 1-dodecyl-3-methylimidazolium bromide-functionalized nanosilica was used for the efficient retention of Se(IV) complexed with ammonium pyrrolidine dithiocarbamate, followed by elution with an ethyl acetate/Triton X-114 mixture and determination by electrothermal atomic absorption spectroscopy. The Se(VI) species was selectively determined by difference between total inorganic Se and Se(IV) after pre-reduction. The IL-nanomaterial hybrid was characterized by Fourier transform infrared spectroscopy and transmission electronic microscopy. Likewise, Se(IV) sorption capacity of the retention material and maximum amount of IL loaded on its surface were determined. Several factors concerning the functionalization, extraction and elution steps were optimized, yielding a 100% extraction efficiency for Se(IV) under optimal conditions. A limit of detection of 1.1 ng L- 1, a relative standard deviation of 5.7% and a 110-fold enhancement factor were obtained. The D-μ-SPE method was successfully applied to several water samples from different origins and compositions, including rain, tap, underground, river and sea.

Results of Hg speciation testing on MCU strip effluent hold tank (SEHT) and decontaminated salt solution hold tank (DSSHT) materials

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

Bannochie, C. J.

2015-09-17

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team.i,ii The tenth shipment of samples was designated to include Modular Caustic Side Solvent Extraction Unit (MCU) Strip Effluent Hold Tank (SEHT) and MCU Decontaminated Salt Solution Hold Tank (DSSHT) materials from processing Salt Batch 7b. The MCU SEHT (MCU-15-722) and DSSHT (MCU-15-709) samples were pulled on June 15, 2015. All MCU samples were received at SRNL on June 16, 2015. The DSSHT sample wasmore » moved the same day to refrigeration, while the SEHT sample was placed in the Shielded Cells. On July 9, 2015 it was opened and an aliquot diluted 1:100 with Eurofins deionized water and a portion of the diluted sample transferred to a Teflon® bottle prior to moving it to refrigeration that same day. All samples were kept in the dark and refrigerated until final dilutions were prepared for shipment to Eurofins.« less

Chemical speciation and potential mobility of heavy metals in the soil of former tin mining catchment.

PubMed

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

2012-01-01

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

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

PubMed Central

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

2012-01-01

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

Magnetic ferrite particles combined with electrothermal atomic absorption spectrometry for the speciation of low concentrations of arsenic.

PubMed

López-García, Ignacio; Marín-Hernández, Juan José; Hernández-Córdoba, Manuel

2018-05-01

Freshly in situ prepared ferrite particles were used for the micro-solid phase extraction of arsenic species. When the separation was carried out at pH 8, inorganic arsenic (As(III) + As(V)) and monomethylarsonic acid (MMA) were retained in the magnetic material. A second aliquot was treated with 2,3 dimercapto propanol, leading to the retention of As(V)+MMA, while a third aliquot was first treated with sodium thiosulphate, in which case only inorganic arsenic passed to the solid phase. In all cases, the solid residue collected by a magnet was suspended in a dilute nitric acid solution containing Triton X-100 and introduced into the electrothermal atomizer to obtain the analytical signal of arsenic. The use of palladium as a chemical modifier allowed calibration to be carried out with aqueous standards. The detection limit was 0.02µgL -1 arsenic for a 10mL sample volume. The procedure was applied to waters and herbal infusions, and its reliability was evaluated by analyzing eleven certified reference materials for which speciation data are provided. Copyright © 2017 Elsevier B.V. All rights reserved.

Adaptation to different host plant ages facilitates insect divergence without a host shift

PubMed Central

Zhang, Bin; Segraves, Kari A.; Xue, Huai-Jun; Nie, Rui-E; Li, Wen-Zhu; Yang, Xing-Ke

2015-01-01

Host shifts and subsequent adaption to novel host plants are important drivers of speciation among phytophagous insects. However, there is considerably less evidence for host plant-mediated speciation in the absence of a host shift. Here, we investigated divergence of two sympatric sister elm leaf beetles, Pyrrhalta maculicollis and P. aenescens, which feed on different age classes of the elm Ulmus pumila L. (seedling versus adult trees). Using a field survey coupled with preference and performance trials, we show that these beetle species are highly divergent in both feeding and oviposition preference and specialize on either seedling or adult stages of their host plant. An experiment using artificial leaf discs painted with leaf surface wax extracts showed that host plant chemistry is a critical element that shapes preference. Specialization appears to be driven by adaptive divergence as there was also evidence of divergent selection; beetles had significantly higher survival and fecundity when reared on their natal host plant age class. Together, the results identify the first probable example of divergence induced by host plant age, thus extending how phytophagous insects might diversify in the absence of host shifts. PMID:26378220

The reality and importance of founder speciation in evolution.

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

Inductively coupled plasma mass spectrometry study of the retention behavior of arsenic species on various solid phase extraction cartridges and its application in arsenic speciation

NASA Astrophysics Data System (ADS)

Yu, Chunhai; Cai, Qiantao; Guo, Zhong-Xian; Yang, Zhaoguang; Khoo, Soo Beng

2003-07-01

Inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate the retention behavior of arsenite, arsenate, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), arsenocholine (AsC), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TMAI) on various silica-based solid phase extraction (SPE) cartridges. A method for arsenic speciation is then developed on the basis of selective SPE separation of arsenic species and highly sensitive ICP-MS detection. Factors affecting the retention and elution of arsenic species were examined. Results showed that the retention of arsenic species depended on the chemical characteristics of arsenic species and the types of sorbent materials. Change of pH in the range of 2.0-9.0 did not show significant effects on the retention of DMA, AsB, AsC, TMAI and TMAO on an ethylbenzene sulfonic acid-based strong cation exchange (SCX-3) cartridge. pH also did not influence the retention of AsB, AsC, TMAI and TMAO on a mixed-mode (M-M) cartridge containing non-polar, strong cation exchange and strong anion exchange (SAX) functional groups. However, the retentions of As(V) and MMA on the SAX and the M-M cartridge changed with pH. As(V) and MMA were completely retained on the SAX cartridge and sequentially selectively eluted with 1.0 mol l -1 acetic acid (for MMA). DMA, AsB, AsC, TMAI and TMAO were completely retained on the SCX-3 cartridge and sequentially selectively eluted with 1.0 mol l -1 HNO 3 (for DMA). As(V), MMA, AsB, AsC, TMAI and TMAO were completely retained on the M-M cartridge. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently determined by ICP-MS. A detection limit of 8 ng l -1 arsenic in water sample was obtained. This method was successfully applied to arsenic speciation in various sources of water samples (drinking water, waste water, raw water, etc.) and US National Institute of Standards and Technology standard reference materials with good precision and accuracy.

An umbra-like virus of papaya discovered in Ecuador: detection, occurrence and phylogenetic relatedness

USDA-ARS?s Scientific Manuscript database

Double-stranded RNA (dsRNA) extractions from papaya leaves infected with Papaya ringspot virus (PRSV) revealed the presence of an unusual 4kb band, in addition to the presumed PRSV-associated 10kb band. Partial sequence of RT-PCR products from the 4kb dsRNA revealed homology to genomes of several me...

Results of initial analyses of the salt (macro) batch 9 tank 21H qualification samples

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

Peters, T. B.

2015-10-01

Savannah River National Laboratory (SRNL) analyzed samples from Tank 21H in support of qualification of Interim Salt Disposition Project (ISDP) Salt (Macro) Batch 9 for processing through the Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU). This document reports the initial results of the analyses of samples of Tank 21H. Analysis of the Tank 21H Salt (Macro) Batch 9 composite sample indicates that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amount of solids, or unusual colors. Further results on the chemistry and other tests willmore » be issued in the future.« less

FORTRAN Automated Code Evaluation System (faces) system documentation, version 2, mod 0. [error detection codes/user manuals (computer programs)

NASA Technical Reports Server (NTRS)

1975-01-01

A system is presented which processes FORTRAN based software systems to surface potential problems before they become execution malfunctions. The system complements the diagnostic capabilities of compilers, loaders, and execution monitors rather than duplicating these functions. Also, it emphasizes frequent sources of FORTRAN problems which require inordinate manual effort to identify. The principle value of the system is extracting small sections of unusual code from the bulk of normal sequences. Code structures likely to cause immediate or future problems are brought to the user's attention. These messages stimulate timely corrective action of solid errors and promote identification of 'tricky' code. Corrective action may require recoding or simply extending software documentation to explain the unusual technique.

Bunker Hill Sediment Characterization Study

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

Neal A. Yancey; Debby F. Bruhn

2009-12-01

The long history of mineral extraction in the Coeur d’Alene Basin has left a legacy of heavy metal laden mine tailings that have accumulated along the Coeur d’Alene River and its tributaries (U.S. Environmental Protection Agency, 2001; Barton, 2002). Silver, lead and zinc were the primary metals of economic interest in the area, but the ores contained other elements that have become environmental hazards including zinc, cadmium, lead, arsenic, nickel, and copper. The metals have contaminated the water and sediments of Lake Coeur d’Alene, and continue to be transported downstream to Spokane Washington via the Spokane River. In 1983, themore » EPA listed the Bunker Hill Mining and Metallurgical Complex on the National Priorities List. Since that time, many of the most contaminated areas have been stabilized or isolated, however metal contaminants continue to migrate through the basin. Designation as a Superfund site causes significant problems for the economically depressed communities in the area. Identification of primary sources of contamination can help set priorities for cleanup and cleanup options, which can include source removal, water treatment or no action depending on knowledge about the mobility of contaminants relative to water flow. The mobility of contaminant mobility under natural or engineered conditions depends on multiple factors including the physical and chemical state (or speciation) of metals and the range of processes, some of which can be seasonal, that cause mobilization of metals. As a result, it is particularly important to understand metal speciation (National Research Council, 2005) and the link between speciation and the rates of metal migration and the impact of natural or engineered variations in flow, biological activity or water chemistry.« less

Analysis of 1995 speciated volatile organic compound data in the south central U.S.

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

Sather, M.E.; Kemp, M.G.; Yarbrough, J.W.

1997-12-31

An analysis of 1995 speciated volatile organic compound (VOC) data from three areas in the south central US has been performed for Baton Rouge, Louisiana, Houston, Texas, and El Paso, Texas. All three areas are required by the Clean Air Act Amendments of 1990 to collect ambient monitoring data for over 50 VOC species, including ten Clean Air Act Title III toxic compounds, as per the Photochemical Assessment Monitoring Stations (PAMS) requirements. The PAMS program was initiated to provide more detailed VOC data for scientists, modelers, and managers working toward eliminating violations of the ozone National Ambient Air Quality Standardsmore » (NAAQS). This paper presents useful information from a preliminary analysis of the 1995 speciated VOC and related data from Baton Rouge, Houston, and El Paso. All data analyzed were extracted from the US Environmental Protection Agency (EPA) Aerometric Information Retrieval System (AIRS) data base after collection and validation by the states of Louisiana and Texas. Key observations from the analyses include: (1) the presence of propane peaks coincident with ozone peaks during all three ozone episode days at the El Paso site; (2) the dominance of mobile source VOC emissions in the El Paso emission inventory, in contrast to the Baton Rouge and Houston VOC emission inventories, after noting strong correlations between carbon monoxide and major exhaust VOC species of gasoline; and (3) the 1995 ozone episodes at the Houston site were influenced by both morning build-up of ambient VOC concentrations and afternoon puffs of VOC emissions, while the 1995 ozone episodes at the Baton Rouge site were influenced by high early and mid-morning VOC ambient concentrations.« less

Effects of biochars derived from chicken manure and rape straw on speciation and phytoavailability of Cd to maize in artificially contaminated loess soil.

PubMed

Zhao, Baowei; Xu, Renzhi; Ma, Fengfeng; Li, Yewei; Wang, Lu

2016-12-15

While biochar can reduce the bioavailability of heavy metals in acidic soils and reduce their risk of entering the food chain, conditions for alkaline soils such as loess soils with high pH values, high carbonate content and low organic matter content remain unclear. Pot experiments were conducted to assess the effects of four rates (1%, 5%, 10%, and 15% w/w) of biochars prepared at 600 °C from chicken manure and rape straw (CBC and RBC) on soil properties, Cd speciation and phytoavailability, and plant growth in Cd contaminated (20 mg kg -1 ) light sierozem using maize (Zea mays L.) as an indicator plant. Biochar additions significantly (P < 0.05) increased soil pH values, cation exchange capacity (CEC) and soil organic matter (OM). The results showed that Cd speciation turned somewhat into stable state as biochar application increased. When CBC and RBC was applied at the rate of 15%, the content of acid-extractable Cd decreased only by 16.3% and 11.64%, respectively. The uptake of Cd by maize shoots scarcely decreased with CBC and RBC amendment at the rate of 1% and 5%, respectively. Although it seemed that additions of more than 5% CBC or RBC significantly (P < 0.05) reduced Cd contents in maize shoots, maize growth was largely inhibited due to the high value of soil pH. These results could provide different implications for immobilization remediation of loess soils (e.g., light sierozem) contaminated with Cd. Copyright © 2016 Elsevier Ltd. All rights reserved.

Use of synchrotron radiation to characterize metals in plants: the case of Cd in the hyperacumulator Arabidopsis halleri

NASA Astrophysics Data System (ADS)

Isaure, M.; Sarret, G.; Verbruggen, N.

2010-12-01

Phytoremediation uses plants to extract (phytoextraction) or stabilize (phytostabilization) metals accumulated in soils, and can be an alternative to invasive physico-chemical remediation techniques. Its development requires the knowledge of the mechanisms involved in metal tolerance and accumulation in plants, and particularly the way that plants transfer and store metals. In that context, synchrotron radiation based techniques such as micro-focused X-Ray Fluorescence (µXRF), and micro-focused X-ray Absorption Spectroscopy, including Extended X-ray Absorption Fine Structure and X-ray Absorption Near Edge Structure, are particularly suited to determine the localization and the chemical forms of metals in the different tissues, cells and sub-cellular compartments. Arabidopsis halleri is a Zn, Cd hyperaccumulating plant, naturally growing on contaminated sites, and is a model plant to investigate metal hyperaccumulation. This work presents the application of µXRF and Cd µXANES to determine the distribution and speciation of Cd in this species. Results showed that Cd was mainly located in the mesophyll and veins of leaves. It is bound to S ligands in some leaves and to O/N ligands in other ones, and the observed variations may be related to the age of the leaves. Cd speciation seems to differ from other metals, and particularly Zn, generally encountered in hyperaccumulators. High local Cd concentrations were also detected at the base of trichomes, epidermal hairs of leaves, associated to O/N ligands, probably to the cell wall. This phenomenon was also observed on non-hyperaccumulators and is clearly not the major sink for Cd, but trichomes might play a role in the detoxification process. This study illustrates the suitability of synchrotron radiation based techniques to investigate metal distribution and speciation in plants.

Geochemical Weathering Increases Lead Bioaccessibility in Semi-Arid Mine Tailings

PubMed Central

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

2012-01-01

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

Effects of conversion of mangroves into gei wai ponds on accumulation, speciation and risk of heavy metals in intertidal sediments.

PubMed

Li, Rongyu; Qiu, Guo Yu; Chai, Minwei; Shen, Xiaoxue; Zan, Qijie

2018-06-23

Mangroves are often converted into gei wai ponds for aquaculture, but how such conversion affects the accumulation and behavior of heavy metals in sediments is not clear. The present study aims to quantify the concentration and speciation of heavy metals in sediments in different habitats, including gei wai pond, mangrove marsh dominated by Avicennia marina and bare mudflat, in a mangrove nature reserve in South China. The results showed that gei wai pond acidified the sediment and reduced its electronic conductivity and total organic carbon (TOC) when compared to A. marina marsh and mudflat. The concentrations of Cd, Cu, Zn and Pb at all sediment depths in gei wai pond were lower than the other habitats, indicating gei wai pond reduced the fertility and the ability to retain heavy metals in sediment. Gei wai pond sediment also had a lower heavy metal pollution problem according to multiple evaluation methods, including potential ecological risk coefficient, potential ecological risk index, geo-accumulation index, mean PEL quotients, pollution load index, mean ERM quotients and total toxic unit. Heavy metal speciation analysis showed that gei wai pond increased the transfer of the immobilized fraction of Cd and Cr to the mobilized one. According to the acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) analysis, the conversion of mangroves into gei wai pond reduced values of ([SEM] - [AVS])/f oc , and the role of TOC in alleviating heavy metal toxicity in sediment. This study demonstrated the conversion of mangrove marsh into gei wai pond not only reduced the ecological purification capacity on heavy metal contamination, but also enhanced the transfer of heavy metals from gei wai pond sediment to nearby habitats.

Evaluation of selenium in dietary supplements using elemental speciation.

PubMed

Kubachka, Kevin M; Hanley, Traci; Mantha, Madhavi; Wilson, Robert A; Falconer, Travis M; Kassa, Zena; Oliveira, Aline; Landero, Julio; Caruso, Joseph

2017-03-01

Selenium-enriched dietary supplements containing various selenium compounds are readily available to consumers. To ensure proper selenium intake and consumer confidence, these dietary supplements must be safe and have accurate label claims. Varying properties among selenium species requires information beyond total selenium concentration to fully evaluate health risk/benefits A LC-ICP-MS method was developed and multiple extraction methods were implemented for targeted analysis of common "seleno-amino acids" and related oxidation products, selenate, selenite, and other species relatable to the quality and/or accuracy of the labeled selenium ingredients. Ultimately, a heated water extraction was applied to recover selenium species from non-selenized yeast supplements in capsule, tablet, and liquid forms. For selenized yeast supplements, inorganic selenium was monitored as a means of assessing selenium yeast quality. A variety of commercially available selenium supplements were evaluated and discrepancies between labeled ingredients and detected species were noted. Published by Elsevier Ltd.

Evaluation of selenium in dietary supplements using elemental speciation

PubMed Central

Kubachka, Kevin M.; Hanley, Traci; Mantha, Madhavi; Wilson, Robert A.; Falconer, Travis M.; Kassa, Zena; Oliveira, Aline; Landero, Julio; Caruso, Joseph

2016-01-01

Selenium-enriched dietary supplements containing various selenium compounds are readily available to consumers. To ensure proper selenium intake and consumer confidence, these dietary supplements must be safe and have accurate label claims. Varying properties among selenium species requires information beyond total selenium concentration to fully evaluate health risk/benefits A LC-ICP-MS method was developed and multiple extraction methods were implemented for targeted analysis of common “seleno-amino acids” and related oxidation products, selenate, selenite, and other species relatable to the quality and/or accuracy of the labeled selenium ingredients. Ultimately, a heated water extraction was applied to recover selenium species from non-selenized yeast supplements in capsule, tablet, and liquid forms. For selenized yeast supplements, inorganic selenium was monitored as a means of assessing selenium yeast quality. A variety of commercially available selenium supplements were evaluated and discrepancies between labeled ingredients and detected species were noted. PMID:27719915

METHOD 544. DETERMINATION OF MICROCYSTINS AND ...

EPA Pesticide Factsheets

Method 544 is an accurate and precise analytical method to determine six microcystins (including MC-LR) and nodularin in drinking water using solid phase extraction and liquid chromatography tandem mass spectrometry (SPE-LC/MS/MS). The advantage of this SPE-LC/MS/MS is its sensitivity and ability to speciate the microcystins. This method development task establishes sample preservation techniques, sample concentration and analytical procedures, aqueous and extract holding time criteria and quality control procedures. Draft Method 544 undergone a multi-laboratory verification to ensure other laboratories can implement the method and achieve the quality control measures specified in the method. It is anticipated that Method 544 may be used in UCMR 4 to collect nationwide occurrence data for selected microcystins in drinking water. The purpose of this research project is to develop an accurate and precise analytical method to concentrate and determine selected MCs and nodularin in drinking water.

New data on the mobility of Pt emitted from catalytic converters.

PubMed

Fliegel, Daniel; Berner, Zsolt; Eckhardt, Detlef; Stüben, Doris

2004-05-01

The mobility and speciation of Pt was investigated in dust deposited in highway tunnels and in gully sediments. For this, a sequential extraction technique was used in combination with a microwave digestion procedure, followed by detection of Pt with high resolution ICP-MS. A digestion procedure using HNO(3)/HCl/H(2)O(2) was developed and its efficiency tested for environmental materials. Total Pt contents ranged from approximately 100 to 300 microg/kg. The high share of chemically mobile Pt in the tunnel dust (up to about 40%) indicates that Pt is predominantly emitted in a mobile form from the converter. The absence of a mobile fraction in the gully sediment is explained by the elution of Pt by run-off. Except for the mobile and easily mobilised fractions none of the other fractions of the sequential extraction contains Pt, neither in the dust samples nor in the gully sediment.

Speciation Methods Used to Assess Potential Health Effects of Toxic Metals in Environmental Materials

USGS Publications Warehouse

Wolf, Ruth E.; Morman, Suzette A.; Plumlee, Geoffrey S.

2008-01-01

Assessing potential exposures to toxic metals or metalloids such as arsenic and chromium in environmental materials is important in protecting public health. The chemical form of an element in, or released from, a material is also important, since some forms, such as Cr(VI), are more toxic than others, for example, Cr(III). We have used a variety of procedures to assess potential exposures to hexavalent chromium in ash and burned soils from October 2007 southern California wildfires. Synthetic lung-fluid and de-ionized water extractions simulate release in the lungs and potential environmental releases due to rainfall. Extracts were analyzed for specific chromium and arsenic species using HPLC-ICP-MS methodology. Results indicate that the highly oxidizing environment in wildfires promotes some chromium conversion to Cr(VI), and that the caustic alkalinity of ash enhances Cr(VI) release and stability in lung fluids and rainfall.

Speciation in birds: genes, geography, and sexual selection.

PubMed

Edwards, Scott V; Kingan, Sarah B; Calkins, Jennifer D; Balakrishnan, Christopher N; Jennings, W Bryan; Swanson, Willie J; Sorenson, Michael D

2005-05-03

Molecular studies of speciation in birds over the last three decades have been dominated by a focus on the geography, ecology, and timing of speciation, a tradition traceable to Mayr's Systematics and the Origin of Species. However, in the recent years, interest in the behavioral and molecular mechanisms of speciation in birds has increased, building in part on the older traditions and observations from domesticated species. The result is that many of the same mechanisms proffered for model lineages such as Drosophila--mechanisms such as genetic incompatibilities, reinforcement, and sexual selection--are now being seriously entertained for birds, albeit with much lower resolution. The recent completion of a draft sequence of the chicken genome, and an abundance of single-nucleotide polymorphisms on the autosomes and sex chromosomes, will dramatically accelerate research on the molecular mechanisms of avian speciation over the next few years. The challenge for ornithologists is now to inform well studied examples of speciation in nature with increased molecular resolution-to clone speciation genes if they exist--and thereby evaluate the relative roles of extrinsic, intrinsic, deterministic, and stochastic causes for avian diversification.

Rates of speciation in the fossil record

NASA Technical Reports Server (NTRS)

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

1998-01-01

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

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

PubMed

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.

Quantification of source impact to PM using three-dimensional weighted factor model analysis on multi-site data

NASA Astrophysics Data System (ADS)

Shi, Guoliang; Peng, Xing; Huangfu, Yanqi; Wang, Wei; Xu, Jiao; Tian, Yingze; Feng, Yinchang; Ivey, Cesunica E.; Russell, Armistead G.

2017-07-01

Source apportionment technologies are used to understand the impacts of important sources of particulate matter (PM) air quality, and are widely used for both scientific studies and air quality management. Generally, receptor models apportion speciated PM data from a single sampling site. With the development of large scale monitoring networks, PM speciation are observed at multiple sites in an urban area. For these situations, the models should account for three factors, or dimensions, of the PM, including the chemical species concentrations, sampling periods and sampling site information, suggesting the potential power of a three-dimensional source apportionment approach. However, the principle of three-dimensional Parallel Factor Analysis (Ordinary PARAFAC) model does not always work well in real environmental situations for multi-site receptor datasets. In this work, a new three-way receptor model, called "multi-site three way factor analysis" model is proposed to deal with the multi-site receptor datasets. Synthetic datasets were developed and introduced into the new model to test its performance. Average absolute error (AAE, between estimated and true contributions) for extracted sources were all less than 50%. Additionally, three-dimensional ambient datasets from a Chinese mega-city, Chengdu, were analyzed using this new model to assess the application. Four factors are extracted by the multi-site WFA3 model: secondary source have the highest contributions (64.73 and 56.24 μg/m3), followed by vehicular exhaust (30.13 and 33.60 μg/m3), crustal dust (26.12 and 29.99 μg/m3) and coal combustion (10.73 and 14.83 μg/m3). The model was also compared to PMF, with general agreement, though PMF suggested a lower crustal contribution.

Monitoring of electrokinetic removal of heavy metals in tailing-soils using sequential extraction analysis.

PubMed

Kim, S O; Kim, K W

2001-08-17

This research focused on the monitoring of the electrokinetic removal of heavy metals from tailing-soils, and emphasizes the dependency of removal efficiencies upon their physico-chemical states, as demonstrated by the different extraction methods adopted, which included aqua regia and sequential extraction. The tailing-soils examined contained high concentrations of target metal contaminants (Cd=179mgkg(-1), Cu=207mgkg(-1), Pb=5175mgkg(-1), and Zn=7600mgkg(-1)). The removal efficiencies of the different metals were significantly influenced by their speciations, mobilities and affinities (adsorption capacities) in the soil matrix. The removal efficiencies of mobile and weakly bound fractions, such as the exchangeable fraction were more than 90% by electrokinetic treatment, but strongly bound fractions, such as the organically bound species and residual fraction were not significantly removed (less than 30% removal efficiencies). In accordance with the general sequence of mobilities of heavy metals in soils, the removal efficiencies of more mobile heavy metals (Cd, Cu, and Zn) were higher than that of less mobile heavy metal (Pb).

Speciation of butyltin compounds in marine sediments with headspace solid phase microextraction and gas chromatography mass spectrometry.

PubMed

Cardellicchio, N; Giandomenico, S; Decataldo, A; Di Leo, A

2001-03-01

A method for the determination of organotin compounds (monobutyl = MBT, dibutyl = DBT, and tributyltin = TBT) in marine sediments by headspace Solid Phase Microextraction (SPME) has been developed. The analytical procedure involved 1) extraction of TBT, DBT and MBT from sediments with HCl and methanol mixture, 2) in situ derivatization with sodium tetraethylborate and 3) headspace SPME extraction using a fiber coated with poly(dimethylsiloxane). The derivatized organotin compounds were desorbed into the splitless injector and simultaneously analyzed by gas chromatography - mass spectrometry. The analytical method was optimized with respect to derivatization reaction and extraction conditions. The detection limits obtained for MBT, DBT and TBT ranged from 730 to 969 pg/g as Sn dry weight. Linear calibration curves were obtained for all analytes in the range of 30-1000 ng/L as Sn. Analysis of a standard reference sediment (CRM 462) demonstrates the suitability of this method for the determination of butyltin compounds in marine sediments. The application to the determination of TBT, DBT and MBT in a coastal marine sediment is shown.

Determination of arsenic species and arsenosugars in marine samples by HPLC-ICP-MS.

PubMed

Hirata, Shizuko; Toshimitsu, Hideki

2005-10-01

Arsenic-speciation analysis in marine samples was performed by high-pressure liquid chromatography (HPLC) with ICP-MS detection. Separation of eight arsenic species--As(III), MMA, DMA, As(V), AB, TMAO, AC and TeMAs(+)--was achieved on a C(18) column with isocratic elution (pH 3.0), under which conditions As(III) and MMA co-eluted. The entire separation was accomplished in 15 min. The HPLC-ICP-MS detection limits for the eight arsenic species were in the range 0.03-0.23 microg L(-1) based on 3 sigma for the blank response (n=5). The precision was calculated to be 2.4-8.0% (RSD) for the eight species. The method was successfully applied to several marine samples, e.g. oysters, fish, shrimps, and marine algae. Low-power microwave digestion was employed for extraction of arsenic from seafood products; ultrasonic extraction was employed for the extraction of arsenic from seaweeds. Separation of arsenosugars was achieved on an anion-exchange column. Concentrations of arsenosugars 2, 3, and 4 in marine algae were in the range 0.18-9.59 microg g(-1).

Sympatric speciation by sexual selection alone is unlikely.

PubMed

Arnegard, Matthew E; Kondrashov, Alexey S

2004-02-01

According to Darwin, sympatric speciation is driven by disruptive, frequency-dependent natural selection caused by competition for diverse resources. Recently, several authors have argued that disruptive sexual selection can also cause sympatric speciation. Here, we use hypergeometric phenotypic and individual-based genotypic models to explore sympatric speciation by sexual selection under a broad range of conditions. If variabilities of preference and display traits are each caused by more than one or two polymorphic loci, sympatric speciation requires rather strong sexual selection when females exert preferences for extreme male phenotypes. Under this kind of mate choice, speciation can occur only if initial distributions of preference and display are close to symmetric. Otherwise, the population rapidly loses variability. Thus, unless allele replacements at very few loci are enough for reproductive isolation, female preferences for extreme male displays are unlikely to drive sympatric speciation. By contrast, similarity-based female preferences that do not cause sexual selection are less destabilizing to the maintenance of genetic variability and may result in sympatric speciation across a broader range of initial conditions. Certain groups of African cichlids have served as the exclusive motivation for the hypothesis of sympatric speciation by sexual selection. Mate choice in these fishes appears to be driven by female preferences for extreme male phenotypes rather than similarity-based preferences, and the evolution of premating reproductive isolation commonly involves at least several genes. Therefore, differences in female preferences and male display in cichlids and other species of sympatric origin are more likely to have evolved as isolating mechanisms under disruptive natural selection.

Speciation in Drosophila: from phenotypes to molecules.

PubMed

Orr, H Allen; Masly, J P; Phadnis, Nitin

2007-01-01

Study of the genetics of speciation--and especially of the genetics of intrinsic postzygotic isolation-has enjoyed remarkable progress over the last 2 decades. Indeed progress has been so rapid that one might be tempted to ask if the genetics of postzygotic isolation is now wrapped up. Here we argue that the genetics of speciation is far from complete. In particular, we review 2 topics where recent work has revealed major surprises: 1) the role of meiotic drive in hybrid sterility and 2) the role of gene transposition in speciation. These surprises, and others like them, suggest that evolutionary biologists may understand less about the genetic basis of speciation than seemed likely a few years ago.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

How humans drive speciation as well as extinction

PubMed Central

Maron, M.

2016-01-01

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

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

PubMed

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.

How humans drive speciation as well as extinction.

PubMed

Bull, J W; Maron, M

2016-06-29

A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation-and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon 'no net loss' conservation literature-considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. © 2016 The Author(s).

Speciation in fungal and oomycete plant pathogens

USDA-ARS?s Scientific Manuscript database

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

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

EPA Science Inventory

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

Ruminant-specific multiple duplication events of PRDM9 before speciation

USDA-ARS?s Scientific Manuscript database

Understanding the genetic and evolutionary mechanisms of speciation genes in sexually reproducing organisms would provide important insights into mammalian reproduction and fitness. PRDM9, a widely known speciation gene, has recently gained attention for its important role in meiotic recombination a...

The Development and Uses of EPA's SPECIATE Database

EPA Science Inventory

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

Distribution and enantiomeric composition of amino acids in the Murchison meteorite

NASA Technical Reports Server (NTRS)

Engel, M. H.; Nagy, B.

1982-01-01

Studies of the amino acid contents and enantiomeric compositions of a single stone from the Murchison meteorite are reported. Water-extracted and 6M HCl-extracted samples from the meteorite interior of meteorite fragments were analyzed by gas chromatography and combined gas chromatography-chemical ionization mass spectrometry. Examination of the D/L ratios of glutamic acid, aspartic acid, proline, leucine and alanine reveals those amino acids extractable by water to be partially racemized, whereas the acid-extracted amino acids were less racemized. The amino acid composition of the stone is similar to those previously reported, including the absence of serine, threonine, tyrosine phenylalanine and methionine and the presence of unusual amino acids including such as isovaline, alpha-aminoisobutyric acid and pseudoleucine. It is concluded that the most likely mechanism accounting for the occurrence of nonracemic amino acid mixtures in the Murchison meteorite is by extraterrestrial stereoselective synthesis or decomposition reactions.

Results of initial analyses of the salt (macro) batch 10 tank 21H qualification samples

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

Peters, T. B.

2017-01-01

Savannah River National Laboratory (SRNL) analyzed samples from Tank 21H in support of qualification of Interim Salt Disposition Project (ISDP) Salt (Macro) Batch 10 for processing through the Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU). This document reports the initial results of the analyses of samples of Tank 21H. Analysis of the Tank 21H Salt (Macro) Batch 10 composite sample indicates that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amount of solids, or unusual colors. Further sample results will be reported in a futuremore » document. This memo satisfies part of Deliverable 3 of the Technical Task Request (TTR).« less

Antimicrobial phenolics and unusual glycerides from Helichrysum italicum subsp. microphyllum.

PubMed

Taglialatela-Scafati, Orazio; Pollastro, Federica; Chianese, Giuseppina; Minassi, Alberto; Gibbons, Simon; Arunotayanun, Warunya; Mabebie, Blessing; Ballero, Mauro; Appendino, Giovanni

2013-03-22

During a large-scale isolation campaign for the heterodimeric phloroglucinyl pyrone arzanol (1a) from Helichrysum italicum subsp. microphyllum, several new phenolics as well as an unusual class of lipids named santinols (5a-c, 6-8) have been characterized. Santinols are angeloylated glycerides characterized by the presence of branched acyl- or keto-acyl chains and represent a hitherto unreported class of plant lipids. The antibacterial activity of arzanol and of a selection of Helichrysum phenolics that includes coumarates, benzofurans, pyrones, and heterodimeric phloroglucinols was evaluated, showing that only the heterodimers showed potent antibacterial action against multidrug-resistant Staphylococcus aureus isolates. These observations validate the topical use of Helichrysum extracts to prevent wound infections, a practice firmly established in the traditional medicine of the Mediterranean area.

Results of initial analyses of the salt (macro) batch 11 Tank 21H qualification samples

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

Peters, T. B.

Savannah River National Laboratory (SRNL) analyzed samples from Tank 21H in support of qualification of Interim Salt Disposition Project (ISDP) Salt (Macro) Batch 11 for processing through the Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU). This document reports the initial results of the analyses of samples of Tank 21H. Analysis of the Tank 21H Salt (Macro) Batch 11 composite sample indicates that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amounts of solids, or unusual colors. Further sample results will be reported in a futuremore » document. This memo satisfies part of Deliverable 3 of the Technical Task Request (TTR).« less

A Survey of PWNe around Narrow-Pulse Gamma-ray Pulsars

NASA Astrophysics Data System (ADS)

Romani, Roger

2010-09-01

We propose here, on behalf of the Fermi LAT team, ACIS observations of the X-ray counterparts of six unusual gamma-ray pulsars discovered by the LAT. The targets, four seen only in the gamma-rays, two also radio-detected, have unusual single or narrow double pulse profiles, which require particular emission geometries for different pulsar models. By measuring the arcsecond-scale structure of the wind nebula termination shocks of these young (<100kyr) objects, CXO can pin down the viewing angle and test the pulsar physics. All have known X-ray fluxes and we can also extract spectral and distance estimates needed to interpret the GeV gamma-rays. The survey sample covers a range of ages, spindown powers and expected inclinations, making it a powerful test of pulsar emission models.

EPA’s SPECIATE 4.4 Database - Development and Uses

EPA Science Inventory

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...

Cold Temperature Effects on Speciated VOC Emissions from modern GDI Light Duty Truck

EPA Science Inventory

Although gasoline direct injection (GDI) vehicles represent nearly half of the light-duty vehicle market share, few studies have reported speciated volatile organic compounds (VOCs) in GDI vehicle exhaust emissions. In this study, speciated VOC emissions were characterized from t...

The development of exhaust speciation profiles for commercial jet engines.

DOT National Transportation Integrated Search

2007-10-01

This study reports the emissions of CO, CO2, NOx, Particulate Matter (PM) mass, : speciated PM and speciated hydrocarbons at six thrust settings: 4%, 7%, 30%, 40%, 65% : and 85%, measured from both engines on four parked 737 aircraft at the Oakland :...

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

PubMed

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.

Sympatric speciation as a consequence of male pregnancy in seahorses

PubMed Central

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

2003-01-01

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

Ephemeral ecological speciation and the latitudinal biodiversity gradient.

PubMed

Cutter, Asher D; Gray, Jeremy C

2016-10-01

The richness of biodiversity in the tropics compared to high-latitude parts of the world forms one of the most globally conspicuous patterns in biology, and yet few hypotheses aim to explain this phenomenon in terms of explicit microevolutionary mechanisms of speciation and extinction. We link population genetic processes of selection and adaptation to speciation and extinction by way of their interaction with environmental factors to drive global scale macroecological patterns. High-latitude regions are both cradle and grave with respect to species diversification. In particular, we point to a conceptual equivalence of "environmental harshness" and "hard selection" as eco-evolutionary drivers of local adaptation and ecological speciation. By describing how ecological speciation likely occurs more readily at high latitudes, with such nascent species especially prone to extinction by fusion, we derive the ephemeral ecological speciation hypothesis as an integrative mechanistic explanation for latitudinal gradients in species turnover and the net accumulation of biodiversity. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Minimal effects of latitude on present-day speciation rates in New World birds

PubMed Central

Rabosky, Daniel L.; Title, Pascal O.; Huang, Huateng

2015-01-01

The tropics contain far greater numbers of species than temperate regions, suggesting that rates of species formation might differ systematically between tropical and non-tropical areas. We tested this hypothesis by reconstructing the history of speciation in New World (NW) land birds using BAMM, a Bayesian framework for modelling complex evolutionary dynamics on phylogenetic trees. We estimated marginal distributions of present-day speciation rates for each of 2571 species of birds. The present-day rate of speciation varies approximately 30-fold across NW birds, but there is no difference in the rate distributions for tropical and temperate taxa. Using macroevolutionary cohort analysis, we demonstrate that clades with high tropical membership do not produce species more rapidly than temperate clades. For nearly any value of present-day speciation rate, there are far more species in the tropics than the temperate zone. Any effects of latitude on speciation rate are marginal in comparison to the dramatic variation in rates among clades. PMID:26019156

Speciation by Symbiosis: the Microbiome and Behavior

PubMed Central

Shropshire, J. Dylan

2016-01-01

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

Speciation by Symbiosis: the Microbiome and Behavior.

PubMed

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.

A method for investigating relative timing information on phylogenetic trees.

PubMed

Ford, Daniel; Matsen, Frederick A; Stadler, Tanja

2009-04-01

In this paper, we present a new way to describe the timing of branching events in phylogenetic trees. Our description is in terms of the relative timing of diversification events between sister clades; as such it is complementary to existing methods using lineages-through-time plots which consider diversification in aggregate. The method can be applied to look for evidence of diversification happening in lineage-specific "bursts", or the opposite, where diversification between 2 clades happens in an unusually regular fashion. In order to be able to distinguish interesting events from stochasticity, we discuss 2 classes of neutral models on trees with relative timing information and develop a statistical framework for testing these models. These model classes include both the coalescent with ancestral population size variation and global rate speciation-extinction models. We end the paper with 2 example applications: first, we show that the evolution of the hepatitis C virus deviates from the coalescent with arbitrary population size. Second, we analyze a large tree of ants, demonstrating that a period of elevated diversification rates does not appear to have occurred in a bursting manner.

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

PubMed

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

2011-09-01

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

Development of new natural extracts.

PubMed

Lavoine-Hanneguelle, Sophie; Périchet, Christine; Schnaebele, Nicolas; Humbert, Marina

2014-11-01

For over the past 20 years, a remarkable development in the study and search of natural products has been observed. This is linked to a new market trend towards ecology and also due to new regulations. This could be a rupture, but also a real booster for creativity. Usually, in the flavor and fragrance field, creativity was boosted by the arrival of new synthetic molecules. Naturals remained the traditional, century-old products, protected by secrecy and specific know-how from each company. Regulatory restrictions or eco-friendly certification constraints like hexane-free processes triggered an important brainstorming in the industry. As a result, we developed new eco-friendly processes including supercritical CO2 extraction, allowing fresh plants to be used to obtain industrial flower extracts (Jasmine Grandiflorum, Jasmine Sambac, Orange blossom). These extracts are analyzed by GC, GC/MS, GCO, and HPTLC techniques. New or unusual raw materials can also be explored, but the resulting extracts have to be tested for safety reasons. Some examples are described. Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich.

Speciation of chromium in environmental samples by dual electromembrane extraction system followed by high performance liquid chromatography.

PubMed

Safari, Meysam; Nojavan, Saeed; Davarani, Saied Saeed Hosseiny; Morteza-Najarian, Amin

2013-07-30

This study proposes the dual electromembrane extraction followed by high performance liquid chromatography for selective separation-preconcentration of Cr(VI) and Cr(III) in different environmental samples. The method was based on the electrokinetic migration of chromium species toward the electrodes with opposite charge into the two different hollow fibers. The extractant was then complexed with ammonium pyrrolidinedithiocarbamate for HPLC analysis. The effects of analytical parameters including pH, type of organic solvent, sample volume, stirring rate, time of extraction and applied voltage were investigated. The results showed that Cr(III) and Cr(VI) could be simultaneously extracted into the two different hollow fibers. Under optimized conditions, the analytes were quantified by HPLC instrument, with acceptable linearity ranging from 20 to 500 μg L(-1) (R(2) values≥0.9979), and repeatability (RSD) ranging between 9.8% and 13.7% (n=5). Also, preconcentration factors of 21.8-33 that corresponded to recoveries ranging from 31.1% to 47.2% were achieved for Cr(III) and Cr(VI), respectively. The estimated detection limits (S/N ratio of 3:1) were less than 5.4 μg L(-1). Finally, the proposed method was successfully applied to determine Cr(III) and Cr(VI) species in some real water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

SPECIATION OF ORGANICS IN WATER WITH RAMAN SPECTROSCOPY: UTILITY OF IONIC STRENGTH VARIATION

EPA Science Inventory

We have developed and are applying an experimental and mathematical method for describing the micro-speciation of complex organic contaminants in aqueous media. For our case, micro-speciation can be defined as qualitative and quantitative identification of all discrete forms of ...

Speciation of organotin compounds in urine by GC-MIP-AED and GC-MS after ethylation and liquid-liquid extraction.

PubMed

Zachariadis, G A; Rosenberg, E

2009-04-15

A method for the determination of organotin compounds in urine samples based on liquid-liquid extraction (LLE) in hexane and gas chromatographic separation was developed and optimized. Seven organotin species, namely monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TeBT), monophenyltin (MPhT), diphenyltin (DPhT) and triphenyltin (TPhT), were in situ derivatized by sodium tetraethylborate (NaBEt(4)) to form ethylated less polar derivatives directly in the urine matrix. The critical parameters which have a significant effect on the yield of the successive liquid-liquid extraction procedure were examined, by using standard solutions of tetrabutyltin in hexane. The method was optimized for use in direct analysis of undiluted human urine samples and ways to overcome practical problems such as foam formation during extraction, due to various constituents of urine are discussed. After thorough optimization of the extraction procedure, all examined species could be determined after 3 min of simultaneous derivatization and extraction at room temperature and 5 min phase separation by centrifugation. Gas chromatography with a microwave-induced plasma atomic emission detector (MIP-AED) as element specific detector was employed for quantitative measurements, while a quadrupole mass spectrometric detector (MS) was used as molecular specific detector. The detection limits were between 0.42 and 0.67 microg L(-1) (as Sn) for the quantitative LLE-GC-MIP-AED method and the precision between 4.2% and 11.7%, respectively.

Automated dynamic hollow fiber liquid-liquid-liquid microextraction combined with capillary electrophoresis for speciation of mercury in biological and environmental samples.

PubMed

Li, Pingjing; He, Man; Chen, Beibei; Hu, Bin

2015-10-09

A simple home-made automatic dynamic hollow fiber based liquid-liquid-liquid microextraction (AD-HF-LLLME) device was designed and constructed for the simultaneous extraction of organomercury and inorganic mercury species with the assistant of a programmable flow injection analyzer. With 18-crown-6 as the complexing reagent, mercury species including methyl-, ethyl-, phenyl- and inorganic mercury were extracted into the organic phase (chlorobenzene), and then back-extracted into the acceptor phase of 0.1% (m/v) 3-mercapto-1-propanesulfonic acid (MPS) aqueous solution. Compared with automatic static (AS)-HF-LLLME system, the extraction equilibrium of target mercury species was obtained in shorter time with higher extraction efficiency in AD-HF-LLLME system. Based on it, a new method of AD-HF-LLLME coupled with large volume sample stacking (LVSS)-capillary electrophoresis (CE)/UV detection was developed for the simultaneous analysis of methyl-, phenyl- and inorganic mercury species in biological samples and environmental water. Under the optimized conditions, AD-HF-LLLME provided high enrichment factors (EFs) of 149-253-fold within relatively short extraction equilibrium time (25min) and good precision with RSD between 3.8 and 8.1%. By combining AD-HF-LLLME with LVSS-CE/UV, EFs were magnified up to 2195-fold and the limits of detection (at S/N=3) for target mercury species were improved to be sub ppb level. Copyright © 2015 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2006-05-01

Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S, S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si 4(Mg 1.65Zn 1.35)O 10(OH) 2 · nH 2O), willemite (Zn 2SiO 4), and gahnite (ZnAl 2O 4), in proportions of ˜30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting that one of the three predominant Zn species was highly soluble under the extraction conditions. Comparison of EXAFS data before and after chemical treatment revealed that the Zn phosphate component was entirely and selectively dissolved in the first 24 h of contact time. Preferential dissolution of the Zn phosphate component is supported by thermodynamic calculations. Despite the long-term contamination of this soil, about 79% of Zn, 91% of Pb, and 100% of Cu can be solubilized in the laboratory on a time scale of a few days by chemical complexants. According to metal speciation results and thermodynamic calculations, the lower extraction level measured for Zn is due to the Zn phyllosilicate component, which is less soluble than Zn phosphate and Zn ferrihydrite.

Distribution and speciation of ambient selenium in contrasted soils, from mineral to organic rich.

PubMed

Tolu, Julie; Thiry, Yves; Bueno, Maïté; Jolivet, Claudy; Potin-Gautier, Martine; Le Hécho, Isabelle

2014-05-01

Selenium adsorption onto oxy-hydroxides mainly controls its mobility in volcanic soils, red earths and soils poor in organic matter (OM) while the influence of OM was emphasized in podzol and peat soils. This work aims at deciphering how those solid phases influence ambient Se mobility and speciation under less contrasted conditions in 26 soils spanning extensive ranges of OM (1-32%), Fe/Al oxy-hydroxides (0.3-6.1%) contents and pH (4.0-8.3). The soil collection included agriculture, meadow and forest soils to assess the influence of OM quality as well. Trace concentrations of six ambient Se species (Se(IV), Se(VI) and 4 organo-Se compounds) were analyzed by HPLC-ICP-MS in three extractants (ultrapure water, phosphate and sodium hydroxide) targeting Se associated to different soil phases. The Kd values determined from ultrapure water extraction were higher than those reported in commonly used short-term experiments after Se-spiking. Correlations of ambient Se content and distribution with soil parameters explained this difference by an involvement of slow processes in Se retention in soils. The 26 Kd values determined here for a wide variety of soils thus represent a relevant database for long-term prediction of Se mobility. For soils containing less than 20% OM, ambient Se solubility is primarily controlled by its adsorption onto crystalline oxy-hydroxides. However, OM plays an important role in Se mobility by forming organo-mineral associations that may protect adsorbed Se from leaching and/or create anoxic zones (aggregates) where Se is immobilized after its reduction. Although for the first time, inorganic Se(IV), Se(VI) and organo-Se compounds were simultaneously investigated in a large soil collection, high Se proportions remain unidentified in each soil extract, most probably due to Se incorporation and/or binding to colloidal-sized OM. Variations of environmental factors regulating the extent of OM-mineral associations/aggregation may thus lead to changes in Se mobility and bio-availability. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of temperature on the protonation of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid in aqueous solutions: Potentiometric and calorimetric studies

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

Li, Xingliang; Zhang, Zhicheng; Endrizzi, Francesco

2015-06-01

The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) has been demonstrated in several pilot-scale operations to be effective at separating trivalent actinides (An 3+) from trivalent lanthanides (Ln 3+). However, fundamental studies have revealed undesired aspects of TALSPEAK, such as the significant partitioning of Na +, lactic acid, and water into the organic phase, thermodynamically unpredictable pH dependence, and the slow extraction kinetics. In the modified TALSPEAK process, the combination of the aqueous holdback complexant HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid) with the extractant HEH[EHP] (2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester) in the organic phase has been found tomore » exhibit a nearly flat pH dependence between 2.5 and 4.5 and more rapid phase transfer kinetics for the heavier lanthanides. To help understand the speciation of Ln 3+ and An 3+ in the modified TALSPEAK, systematic studies are underway on the thermodynamics of major reactions in the HEDTA system under conditions relevant to the process (e.g., higher temperatures). Thermodynamics of the protonation and complexation of HEDTA with Ln 3+ were studied at variable temperatures. Equilibrium constants and enthalpies were determined by a combination of techniques including potentiometry and calorimetry. This paper presents the protonation constants of HEDTA at T = (25 to 70) °C. The potentiometric titrations have demonstrated that, stepwise, the first two protonation constants decrease and the third one slightly increases with the increase of temperature. This trend is in good agreement with the enthalpy of protonation directly determined by calorimetry. The results of NMR analysis further confirm that the first two protonation reactions occur on the diamine nitrogen atoms, while the third protonation reaction occurs on the oxygen of a carboxylate group. These data, in conjunction with the thermodynamic parameters of Ln 3+/An 3+ complexes with HEDTA at different temperatures, will help to predict the speciation and temperature-dependent behavior of Ln 3+/An 3+ in the modified TALSPEAK process.« less

The flotation tailings of the former Pb-Zn mine of Touiref (NW Tunisia): mineralogy, mine drainage prediction, base-metal speciation assessment and geochemical modeling.

PubMed

Othmani, Mohamed Ali; Souissi, Fouad; Bouzahzah, Hassan; Bussière, Bruno; da Silva, Eduardo Ferreira; Benzaazoua, Mostafa

2015-02-01

The underground extraction of Pb-Zn mineralization in the Touiref area stopped in 1958. A large volume of flotation tailings (more than 500 Mt) containing sulfides were deposited in a tailings impoundment. The goals of this study are to evaluate the neutralization capacity of the unoxidized and oxidized tailings, to assess the speciation of metals between the different components of the tailings material, and to assess the mobility of metals and the secondary minerals' precipitation in pore waters using geochemical modeling. To accomplish these objectives, representative samples from both fresh and oxidized zones were collected along a vertical profile through the tailings pile. Physical, chemical (ICP-MS), and mineralogical characterization (X-ray diffraction (XRD), reflected light microscopy, scanning electron microscope (SEM)) of these samples was performed. Grain size analysis shows that the tailings are dominated by silt- to sand-sized fractions. The microscopic observation highlights the presence of pyrite, marcasite, galena, and sphalerite as primary minerals in a carbonated matrix. The study reveals also the presence of secondary minerals represented by cerussite, smithsonite, anglesite, and Fe oxi-hydroxides as important scavengers for trace elements. The static tests show that the presence of calcite in the tailing samples ensures acid-neutralizing capacity (ANC), which is significantly greater than the acidity potential (PA). The geochemical characterization of the unoxidized samples shows higher Cd, Pb, and Zn concentrations than the oxidized samples containing the highest values for Fe and SO4. Sequential extraction tests show that significant percentages of metals are distributed between the acid-soluble fractions (Cd, Pb, and Zn) and the reducible one (Zn). Pore water analysis indicates that Ca is the dominant cation (8,170 and 6,200 mg L(-1), respectively), whereas sulfate is the principal anion (6,900 and 5,100 mg L(-1), respectively). Saturation index (SI) calculations of minerals in pore water extracted from both the oxidized and unoxidized samples are indicative of gypsum (SI >0) and Fe(III) oxides (SI ≫0) precipitation. The latter controls the Fe concentration in solution.

Antioxidant potential of Aesculus hippocastanum extract and escin against reactive oxygen and nitrogen species.

PubMed

Vašková, J; Fejerčáková, A; Mojžišová, G; Vaško, L; Patlevič, P

2015-01-01

Antioxidant, anti-inflammatory and venoconstrictor properties have been attributed to extracts from Aesculus hippocastanum. These unusual and diverse properties may be possibly basically linked with ability to scavenge free radicals. The scavenging capacity of dry horse chestnut extract of and escin have been investigated in vitro against superoxide anion radicals, hydroxyl radicals, nitrites and peroxynitrite. In general, the activity of the whole extract against superoxide radicals did not exceed 15% at pH 7.4, but the highest inhibition (46.11%) was recorded against hydroxyl radicals at a concentration of 100 µg.ml-1; however, the activity against other radicals was lower. Escin demonstrated a better ability to counteract nitric oxide oxidation products, nitrites. However, the efficiency of the whole extract completely disappeared as the concentration increased. Both extracts showed very low activity towards peroxynitrite. Escin was even able to induce peroxynitrite formation at the lower concentrations used. Whole extract showed better antiradical properties compared to its main active ingredient, escin, probably due to potential synergistic interaction with a mixture of compounds present in the plant extract. These findings can be the basis of both the presentation of side-effects and the persistence of disease in spite of ongoing treatment.

Field Evaluation Of Arsenic Speciation In Sediments At The Ground Water/Surface Water Interface

EPA Science Inventory

The speciation and mineralogy of sediments contaminated with arsenic at the ground water/surface water interface of the Ft. Devens Super Fund Site in Ft. Devens, MA were determined using X-ray absorption fine structure and X-ray diffraction spectroscopy. Speciation and mineralog...

Gas and liquid chromatography with inductively coupled plasma mass spectrometry detection for environmental speciation analysis — advances and limitations

NASA Astrophysics Data System (ADS)

Szpunar, Joanna; McSheehy, Shona; Połeć, Kasia; Vacchina, Véronique; Mounicou, Sandra; Rodriguez, Isaac; Łobiński, Ryszard

2000-07-01

Recent advances in the coupling of gas chromatography (GC) and high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP MS) and their role in trace element speciation analysis of environmental materials are presented. The discussion is illustrated with three research examples concerning the following topics: (i) development and coupling of multicapillary microcolumn GC with ICP MS for speciation of organotin in sediment and biological tissue samples; (ii) speciation of arsenic in marine algae by size-exclusion-anion-exchange HPLC-ICP MS; and (iii) speciation of cadmium in plant cell cultures by size-exclusion HPLC-ICP MS. Particular attention is paid to the problem of signal identification in ICP MS chromatograms; the potential of electrospray MS/MS for this purpose is highlighted.

Chromosomes, conflict, and epigenetics: chromosomal speciation revisited.

PubMed

Brown, Judith D; O'Neill, Rachel J

2010-01-01

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

Living organisms as an alternative to hyphenated techniques for metal speciation. Evaluation of baker's yeast immobilized on silica gel for Hg speciation*1

NASA Astrophysics Data System (ADS)

Pérez-Corona, Teresa; Madrid-Albarrán, Yolanda; Cámara, Carmen; Beceiro, Elisa

1998-02-01

The use of living organisms for metal preconcentration and speciation is discussed. Among substrates, Saccharomyces cerevisiae baker's yeast has been successfully used for the speciation of mercury [Hg(II) and CH 3Hg +], selenium [Se(IV) and Se(VI)] and antimony [Sb(III) and Sb(V)]. To illustrate the capabilities of these organisms, the analytical performance of baker's yeast immobilized on silica gel for on-line preconcentration and speciation of Hg(II) and methylmercury is reported. The immobilized cells were packed in a PTFE microcolumn, through which mixtures of organic and inorganic mercury solutions were passed. Retention of inorganic and organic mercury solutions took place simultaneously, with the former retained in the silica and the latter on the yeast. The efficiency uptake for both species was higher than 95% over a wide pH range. The speciation was carried out by selective and sequential elution with 0.02 mol L -1 HCl for methylmercury and 0.8 mol L -1 CN - for Hg(II). This method allows both preconcentration and speciation of mercury. The preconcentration factors were around 15 and 100 for methylmercury and mercury(II), respectively. The method has been successfully applied to spiked sea water samples.

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

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

2014-01-01

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

Automobile shredded residue valorisation by hydrometallurgical metal recovery.

PubMed

Granata, Giuseppe; Moscardini, Emanuela; Furlani, Giuliana; Pagnanelli, Francesca; Toro, Luigi

2011-01-15

The aim of this work was developing a hydrometallurgical process to recover metals from automobile shredded residue (or car fluff). Automobile shredded residue (ASR) was characterised by particle size distribution, total metal content and metal speciation in order to guide the choice of target metals and the operating conditions of leaching. Characterisation results showed that Fe is the most abundant metal in the waste, while Zn was the second abundant metal in the fraction with diameter lower than 500 μm. Sequential extractions denoted that Zn was easily extractable by weak acid attack, while Fe and Al required a strong acid attack to be removed. In order to recover zinc from <500 μm fraction leaching tests were operated using acetic acid, sulphuric acid and sodium hydroxide at different concentrations. Sulphuric acid determined the highest zinc extraction yield, while acetic acid determined the highest zinc extractive selectivity. Sodium hydroxide promoted an intermediate situation between sulphuric and acetic acid. Zn recovery by electro winning using acetic leach liquor determined 95% of Zn electro deposition yield in 1h, while using sulphuric leach liquor 40% yield in 1h and 50% yield in 2h were obtained. Simulation results showed that the sulphuric leaching process was more attractive than acetic leaching process. Copyright © 2010 Elsevier B.V. All rights reserved.

Selenium speciation methods and application to soil saturation extracts from San Joaquin Valley, California

USGS Publications Warehouse

Fio, John L.; Fujii, Roger

1990-01-01

Methods to determine soluble concentrations of selenite, selenate, and organic Se were evaluated on saturation extracts of soil samples collected from three sites on the Panoche Creek alluvial fan in the western San Joaquin Valley, California. The methods were used in combination with hydride-generation atomic-absorption spectrometry for detection of Se, and included a selective chemical-digestion method and three chromatographic methods using XAD-8 resin, Sep-Pak C18 cartridge, and a combination of XAD-8 resin and activated charcoal. The chromatography methods isolate dissolved organic matter that can inhibit Se detection by hydride-generation atomic-absorption spectrometry. Isolation of hydrophobic organic matter with XAD-8 did not affect concentrations of selenite and selenate, and the isolated organic matter represents a minimal estimation of organic Se. Ninety-eight percent of the Se in the extracts was selenate and about 100% of the isolated organic Se was associated with the humic acid fraction of dissolved organic matter. The depth distribution of Se species in the soil saturation extracts support a hypothesis that the distribution of soluble Se and salinity in these soils is the result of evaporation from a shallow water table and leaching by irrigation water low in Se and salinity.

Biogeochemical and hydrological controls in mobilizing Se in a saline wetland environment

NASA Astrophysics Data System (ADS)

Datta, S.; Hettiarachchi, G. M.; Crawford, M.; Karna, R.; Allmendinger, N. E.; Khatiwada, R.

2010-12-01

Selenium (Se) contamination in watersheds remains a challenge to water and land and wildlife managers throughout the west and mid west of US. In that sense, understanding the fundamentals of Se mobilization, fixation and bioconcentration is the current research endeavor. The challenge for Se research is developing watershed-geochemical models that are well founded in Se geochemical/biologcial principles that can be applied in a wide range of situations to inform decisions. Pariette Wetlands, a 9000 acre Bureau of Land Management controlled wetland system composed of 20 ponds located at the confluence of Pariette Draw and the Green River is the present location of this study. The agricultural and irrigation practices and the water-rock interactions leading to salinization can be associated with changes in Se chemistry in the rivers. Since its inception Pariette Wetlands has been home to a rich and diverse wetland ecosystem located in the arid Uintah Basin of Northeastern Utah. Detailed sampling of surficial sediments (0-1 m) from stream banks, channel beds and for water sampling have been undergone in 2 separate field trips throughout the entire reach of the wetland. To establish Pariette Draw’s contribution of Se to the Green river, water and sediments were also sampled from the Green River up and downstream of its confluence with Pariette Draw. In situ measurements of water parameters within the wetland suggest a clear trend of increased pH from upstream, 8, to downstream, 9.2 and combined with TDS suggest a pH controlled saline environment system. The headwaters near Flood Control Dam have an added input of Se from a possible irrigation source upstream in Pleasant Valley area while Se drastically decreases downstream towards the Red Head Pond. Se fractionation in sediments is being analyzed via a sequential extraction procedure to locate the labile fractions of mostly inorganic bound Se. Solid state speciation of Se via μ-XRF aided μ-XANES is being combined with HPLC-MS measured speciation of Se in the water samples. The μ-XRF mapping of Se indicated that Se was highly localized in these surficial sediment samples and therefore, spatially resolved µ-XANES was essential for Se speciation. The µ-XANES speciation of these surficial sediments showed that Se speciation to significantly vary among the 2 sets of seasonal samples (saturated year long versus saturated only seasonally) hence suggesting that continuous drying and wetting cycles or continuous saturation in this environment did have significant impact on sequestration and bioavailability of Se. This work focuses on using this watershed as 'field laboratories' to expand on predicting selenium concentrations from general/fundamental understanding of first-order principles

Speciation and bioaccessibility of mercury in adobe bricks and dirt floors in Huancavelica, Peru.

PubMed

Hagan, Nicole; Robins, Nicholas; Gonzales, Ruben Dario Espinoza; Hsu-Kim, Heileen

2015-04-01

Huancavelica, Peru, a historic cinnabar refining site, is one of the most mercury (Hg)-contaminated urban areas in the world. Exposure is amplified because residents build their adobe brick homes from contaminated soil. The objectives of this study were to compare two Hg-leaching procedures, and their application as risk-assessment screening tools in Hg-contaminated adobe brick homes in Huancavelica. The purpose was to evaluate potential health implications, particularly for children, after ingestion of Hg-contaminated particles. Hg was measured in adobe brick and dirt floor samples from 60 households by total Hg extraction, simulated gastric fluid (GF) extraction, and sequential selective extraction (SSE), which provides more detailed data but is resource-intensive. Most of the Hg present in samples was relatively insoluble, although in some households soluble Hg species were present at concentrations that may be of concern after ingestion. A strong correlation was identified between results from simulated GF extraction of adobe bricks and dirt floors and the more soluble fractions of Hg from SSE. Simulated GF extraction data were combined with ingestion and body mass characteristics for small children to compare potential risk of ingestion of Hg-contaminated soil with current health standards. Simulated GF extraction can be used as a risk assessment screening tool for effective allocation of time and resources to households that have measurable concentrations of bioaccessible Hg. Combining simulated GF extraction data with health standards enables intervention strategies targeted at households with the greatest potential health threat from ingestion of Hg-contaminated particles.

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste

USGS Publications Warehouse

Al-Abed, S. R.; Hageman, P.L.; Jegadeesan, G.; Madhavan, N.; Allen, D.

2006-01-01

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (Eh), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the Eh-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Abnormal pelvic morphology and high cervical length are responsible for high-risk pregnancies in women displaying achondroplasia.

PubMed

Vivanti, Alexandre J; Cordier, Anne-Gael; Baujat, Geneviève; Benachi, Alexandra

2016-12-05

Pregnancies of women displaying achondroplasia are at high risk of adverse events. Early sonographic assessment of affected women can indicate an unusually long cervical length. It is the consequence of pathological anatomy of the pelvis. Thus, there is a foreseeable dystocia owing to cephalopelvic disproportion. Furthermore, this situation could also complicate cervical ripening prior to fetal extraction.

Pollinator-driven ecological speciation in plants: new evidence and future perspectives

PubMed Central

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 further illustrate innovative experimental approaches, and they employ modern tools in genetics and floral trait quantification. Future advances to the field require better quantification of selection through male fitness and pollinator isolation, for instance by exploiting next-generation sequencing technologies. By combining these new tools with strategically chosen study systems, and smart experimental design, we predict that examples of pollinator-driven speciation will be among the most widespread and compelling of all cases of ecological speciation. PMID:24418954

pH-Specific structural speciation of the ternary V(V)-peroxido-betaine system: a chemical reactivity-structure correlation.

PubMed

Gabriel, C; Kioseoglou, E; Venetis, J; Psycharis, V; Raptopoulou, C P; Terzis, A; Voyiatzis, G; Bertmer, M; Mateescu, C; Salifoglou, A

2012-06-04

Vanadium involvement in cellular processes requires deep understanding of the nature and properties of its soluble and bioavailable forms arising in aqueous speciations of binary and ternary systems. In an effort to understand the ternary vanadium-H(2)O(2)-ligand interactions relevant to that metal ion's biological role, synthetic efforts were launched involving the physiological ligands betaine (Me(3)N(+)CH(2)CO(2)(-)) and H(2)O(2). In a pH-specific fashion, V(2)O(5), betaine, and H(2)O(2) reacted and afforded three new, unusual, and unique compounds, consistent with the molecular formulation K(2)[V(2)O(2)(O(2))(4){(CH(3))(3)NCH(2)CO(2))}]·H(2)O (1), (NH(4))(2)[V(2)O(2)(O(2))(4){(CH(3))(3)NCH(2)CO(2))}]·0.75H(2)O (2), and {Na(2)[V(2)O(2)(O(2))(4){(CH(3))(3)NCH(2)CO(2))}(2)]}(n)·4nH(2)O (3). All complexes 1-3 were characterized by elemental analysis; UV/visible, FT-IR, Raman, and NMR spectroscopy in solution and the solid state; cyclic voltammetry; TGA-DTG; and X-ray crystallography. The structures of 1 and 2 reveal the presence of unusual ternary dinuclear vanadium-tetraperoxido-betaine complexes containing [(V(V)═O)(O(2))(2)] units interacting through long V-O bonds. The two V(V) ions are bridged through the oxygen terminal of one of the peroxide groups bound to the vanadium centers. The betaine ligand binds only one of the two V(V) ions. In the case of the third complex 3, the two vanadium centers are not immediate neighbors, with Na(+) ions (a) acting as efficient oxygen anchors and through Na-O bonds holding the two vanadium ions in place and (b) providing for oxygen-containing ligand binding leading to a polymeric lattice. In 1 and 3, interesting 2D (honeycomb) and 1D (zigzag chains) topologies of potassium nine-coordinate polyhedra (1) and sodium octahedra (3), respectively, form. The collective physicochemical properties of the three ternary species 1-3 project the chemical role of the low molecular mass biosubstrate betaine in binding V(V)-diperoxido units, thereby stabilizing a dinuclear V(V)-tetraperoxido dianion. Structural comparisons of the anions in 1-3 with other known dinuclear V(V)-tetraperoxido binary anionic species provide insight into the chemical reactivity of V(V)-diperoxido systems and their potential link to cellular events such as insulin mimesis and anitumorigenicity modulated by the presence of betaine.

Demographic modelling with whole-genome data reveals parallel origin of similar Pundamilia cichlid species after hybridization.

PubMed

Meier, Joana I; Sousa, Vitor C; Marques, David A; Selz, Oliver M; Wagner, Catherine E; Excoffier, Laurent; Seehausen, Ole

2017-01-01

Modes and mechanisms of speciation are best studied in young species pairs. In older taxa, it is increasingly difficult to distinguish what happened during speciation from what happened after speciation. Lake Victoria cichlids in the genus Pundamilia encompass a complex of young species and polymorphic populations. One Pundamilia species pair, P. pundamilia and P. nyererei, is particularly well suited to study speciation because sympatric population pairs occur with different levels of phenotypic differentiation and reproductive isolation at different rocky islands within the lake. Genetic distances between allopatric island populations of the same nominal species often exceed those between the sympatric species. It thus remained unresolved whether speciation into P. nyererei and P. pundamilia occurred once, followed by geographical range expansion and interspecific gene flow in local sympatry, or if the species pair arose repeatedly by parallel speciation. Here, we use genomic data and demographic modelling to test these alternative evolutionary scenarios. We demonstrate that gene flow plays a strong role in shaping the observed patterns of genetic similarity, including both gene flow between sympatric species and gene flow between allopatric populations, as well as recent and early gene flow. The best supported model for the origin of P. pundamilia and P. nyererei population pairs at two different islands is one where speciation happened twice, whereby the second speciation event follows shortly after introgression from an allopatric P. nyererei population that arose earlier. Our findings support the hypothesis that very similar species may arise repeatedly, potentially facilitated by introgressed genetic variation. © 2016 John Wiley & Sons Ltd.

Ecological speciation in the tropics: insights from comparative genetic studies in Amazonia

PubMed Central

Beheregaray, Luciano B.; Cooke, Georgina M.; Chao, Ning L.; Landguth, Erin L.

2015-01-01

Evolution creates and sustains biodiversity via adaptive changes in ecologically relevant traits. Ecologically mediated selection contributes to genetic divergence both in the presence or absence of geographic isolation between populations, and is considered an important driver of speciation. Indeed, the genetics of ecological speciation is becoming increasingly studied across a variety of taxa and environments. In this paper we review the literature of ecological speciation in the tropics. We report on low research productivity in tropical ecosystems and discuss reasons accounting for the rarity of studies. We argue for research programs that simultaneously address biogeographical and taxonomic questions in the tropics, while effectively assessing relationships between reproductive isolation and ecological divergence. To contribute toward this goal, we propose a new framework for ecological speciation that integrates information from phylogenetics, phylogeography, population genomics, and simulations in evolutionary landscape genetics (ELG). We introduce components of the framework, describe ELG simulations (a largely unexplored approach in ecological speciation), and discuss design and experimental feasibility within the context of tropical research. We then use published genetic datasets from populations of five codistributed Amazonian fish species to assess the performance of the framework in studies of tropical speciation. We suggest that these approaches can assist in distinguishing the relative contribution of natural selection from biogeographic history in the origin of biodiversity, even in complex ecosystems such as Amazonia. We also discuss on how to assess ecological speciation using ELG simulations that include selection. These integrative frameworks have considerable potential to enhance conservation management in biodiversity rich ecosystems and to complement historical biogeographic and evolutionary studies of tropical biotas. PMID:25653668

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

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2009-12-01

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

Speciation and reactivity of uranium products formed during in situ bioremediation in a shallow alluvial aquifer.

PubMed

Alessi, Daniel S; Lezama-Pacheco, Juan S; Janot, Noémie; Suvorova, Elena I; Cerrato, José M; Giammar, Daniel E; Davis, James A; Fox, Patricia M; Williams, Kenneth H; Long, Philip E; Handley, Kim M; Bernier-Latmani, Rizlan; Bargar, John R

2014-11-04

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

Speciation and Reactivity of Uranium Products Formed during in Situ Bioremediation in a Shallow Alluvial Aquifer

PubMed Central

2015-01-01

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans. PMID:25265543

Influence of Calcium Carbonate on Cobalt Phytoavailability in Fluvo-aquic Soil

NASA Astrophysics Data System (ADS)

Wang, Mengyuan; Liu, Borui; Ma, Yufei; Xue, Qianhui; Huang, Qing

2017-12-01

In order to study the efficacy of calcium carbonate for cobalt (Co) fixation, as well as its influence on chemical speciation of Co in fluvo-aquic soil, pakchoies were planted in the soil with different quantities of exogenous Co and calcium carbonate. Co concentrations in the mature plant shoots were analyzed, and the chemical speciation of Co were detected with the Tessier five-step sequential extraction. The results showed that the Co concentration in plants tended to decrease first and then get higher with the concentration of calcium carbonate increasing (0-12g/kg) in soil (P < 0.05). The proportion of Co in the exchangeable form in the soil followed the similar tendency (P < 0.05), which might transform from the exchangeable form into the carbonate-associated and organic-associated forms. A regression analysis showed that when the concentrations of calcium carbonate were in the range of 5.0 to 7.5 g/kg, Co concentration in the plant reached to the lowest point, while the proportion of Co in the exchangeable form reached the minimum. In conclusion, to get the optimum effect, the dosage of calcium carbonate should be kept in the range of 5.0 to 7.5 g/kg when it is applied to Co fixation.

Relation between different metal pollution criteria in sediments and its contribution on assessing toxicity.

PubMed

Alves, Cristina M; Ferreira, Carlos M H; Soares, Helena M V M

2018-05-14

Several tools have been developed and applied to evaluate the metal pollution status of sediments and predict their potential ecological risk assessment. To date, a comprehensive relationship between the information given by these sediment tools for predicting metal bioavailability and the effective toxicity observed is lacking. In this work, the possible inter-correlations between the data outcoming from using several qualitative evaluation tools of the sediment contamination (contamination factor, CF, the enrichment factor, EF, or the geoaccumulation index, Igeo), metal speciation on sediments (evaluated by the modified BCR sequential extraction procedure) and free metal concentrations in pore waters were studied. It was also our aim to evaluate if these assessment tools could be used for predicting the pore waters toxicity data as toxicity proxy. Principal component analysis and cluster analysis revealed that two quality indices used (CF and EF) were highly correlatable with the more labile fractions from BCR sediment speciation. However, neither of these parameters did correlate with the toxicity of pore waters measured by the chronic toxicity (72 h) in Pseudokirchneriella subcapitata. In contrast, the toxic effects of the given total metal load in sediments were better evaluated by using an additive metal approach using pore water free metal concentrations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Competitive adsorption of heavy metals in soil underlying an infiltration facility installed in an urban area.

PubMed

Hossain, M A; Furumai, H; Nakajima, F

2009-01-01

Accumulation of heavy metals at elevated concentration and potential of considerable amount of the accumulated heavy metals to reach the soil system was observed from earlier studies in soakaways sediments within an infiltration facility in Tokyo, Japan. In order to understand the competitive adsorption behaviour of heavy metals Zn, Ni and Cu in soil, competitive batch adsorption experiments were carried out using single metal and binary metal combinations on soil samples representative of underlying soil and surface soil at the site. Speciation analysis of the adsorbed metals was carried out through BCR sequential extraction method. Among the metals, Cu was not affected by competition while Zn and Ni were affected by competition of coexisting metals. The parameters of fitted 'Freundlich' and 'Langmuir' isotherms indicated more intense competition in underlying soil compared to surface soil for adsorption of Zn and Ni. The speciation of adsorbed metals revealed less selectivity of Zn and Ni to soil organic matter, while dominance of organic bound fraction was observed for Cu, especially in organic rich surface soil. Compared to underlying soil, the surface soil is expected to provide greater adsorption to heavy metals as well as provide greater stability to adsorbed metals, especially for Cu.

Speciation and Toxic Emissions from On road Vehicles, and Particulate Matter Emissions from Light-Duty Gasoline Vehicles in MOVES201X

EPA Science Inventory

Updated methane, non-methane organic gas, and volatile organic compound calculations based on speciation data. Updated speciation and toxic emission rates for new model year 2010 and later heavy-duty diesel engines. Updated particulate matter emission rates for 2004 and later mod...

Sexual selection drives speciation in an Amazonian frog

USGS Publications Warehouse

Boul, K.E.; Funk, W.C.; Darst, C.R.; Cannatella, D.C.; Ryan, M.J.

2007-01-01

One proposed mechanism of speciation is divergent sexual selection, whereby divergence in female preferences and male signals results in behavioural isolation. Despite the appeal of this hypothesis, evidence for it remains inconclusive. Here, we present several lines of evidence that sexual selection is driving behavioural isolation and speciation among populations of an Amazonian frog (Physalaemus petersi). First, sexual selection has promoted divergence in male mating calls and female preferences for calls between neighbouring populations, resulting in strong behavioural isolation. Second, phylogenetic analysis indicates that populations have become fixed for alternative call types several times throughout the species' range, and coalescent analysis rejects genetic drift as a cause for this pattern, suggesting that this divergence is due to selection. Finally, gene flow estimated with microsatellite loci is an average of 30 times lower between populations with different call types than between populations separated by a similar geographical distance with the same call type, demonstrating genetic divergence and incipient speciation. Taken together, these data provide strong evidence that sexual selection is driving behavioural isolation and speciation, supporting sexual selection as a cause for speciation in the wild. ?? 2006 The Royal Society.

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

PubMed Central

Williams, David R.

2004-01-01

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

Impact of arsenic in foodstuffs on the people living in the arsenic-affected areas of West Bengal, India.

PubMed

Mandal, Badal K; Suzuki, Kazuo T; Anzai, Kazunori

2007-10-01

Although the accumulation of arsenic (As) in human blood is linked with some diseases and with occupational exposure, there are few reports on speciation of As in blood. On the basis of our earlier article, elevated level of arsenicals in human urine and blood were found in the ex-exposed population via As-containing drinking water. The aim of the present study was to get an insight on impact of As in foodstuffs on the people living in the As-affected areas. Moreover, speciation of arsenicals in urine, and water-samples found in arsenobetaine (AsB). Since sampling population (n=25) was not taking any seafood, As in foodstuffs was thought to be the prime source for this discrepancy. So, speciation of methanol extract of freeze-dried red blood cells (RBCs) and foodstuffs, and trichloro acetic acid (TCA) treated plasma by high performance liquid chromatography-inductively coupled argon plasma mass spectrometer (HPLC-ICP MS) collected from the study population (n=33) was carried out to support our hypothesis. Results showed that urine contained AsB (1.7%), arsenite (iAs(III)) (14.3), arsenate (iAs(V)) (4.9), monomethylarsonous acid (MMA(III)) (0.64), monomethylarsonic acid (MMA(V)) (13.6), dimethylarsinous acid (DMA(III)) (7.7), and dimethylarsinic acid (DMA(V)) (65.4). Blood contained 21.3 microg L(- 1) (mean) As and of which 27.3% was in plasma and 72.7% in RBCs. RBCs contained AsB (21.6%) and DMA(V) (78.4) and blood plasma contained AsB (12.4%), iAs(III) (25.9), MMA(V) (30.3), and DMA(V) (31.4). Furthermore, speciation of As in foodstuffs showed that most of them contained AsB (3.54-25.81 microg kg(- 1)) (25.81-312.44 microg kg(- 1)) along with iAs(III) (9.62-194.93), iAs(V) (17.63-78.33), MMA(V) (9.47-73.22) and DMA(V) (13.43-101.15) that supported the presence of AsB and elevated As in urine and blood samples of the present study group. Inorganic As (iAs) predominates in rice (67.17-86.62%) and in spices (40-90.35%), respectively over organic As. So, As in the food chain is a real threat to human health.

New analytic results for speciation times in neutral models.

PubMed

Gernhard, Tanja

2008-05-01

In this paper, we investigate the standard Yule model, and a recently studied model of speciation and extinction, the "critical branching process." We develop an analytic way-as opposed to the common simulation approach-for calculating the speciation times in a reconstructed phylogenetic tree. Simple expressions for the density and the moments of the speciation times are obtained. Methods for dating a speciation event become valuable, if for the reconstructed phylogenetic trees, no time scale is available. A missing time scale could be due to supertree methods, morphological data, or molecular data which violates the molecular clock. Our analytic approach is, in particular, useful for the model with extinction, since simulations of birth-death processes which are conditioned on obtaining n extant species today are quite delicate. Further, simulations are very time consuming for big n under both models.

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

PubMed

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 diversification and offers a very different perspective on the phylogenetic patterns expected in the absence of ecology.

Biological signatures of dynamic river networks from a coupled landscape evolution and neutral community model

NASA Astrophysics Data System (ADS)

Stokes, M.; Perron, J. T.

2017-12-01

Freshwater systems host exceptionally species-rich communities whose spatial structure is dictated by the topology of the river networks they inhabit. Over geologic time, river networks are dynamic; drainage basins shrink and grow, and river capture establishes new connections between previously separated regions. It has been hypothesized that these changes in river network structure influence the evolution of life by exchanging and isolating species, perhaps boosting biodiversity in the process. However, no general model exists to predict the evolutionary consequences of landscape change. We couple a neutral community model of freshwater organisms to a landscape evolution model in which the river network undergoes drainage divide migration and repeated river capture. Neutral community models are macro-ecological models that include stochastic speciation and dispersal to produce realistic patterns of biodiversity. We explore the consequences of three modes of speciation - point mutation, time-protracted, and vicariant (geographic) speciation - by tracking patterns of diversity in time and comparing the final result to an equilibrium solution of the neutral model on the final landscape. Under point mutation, a simple model of stochastic and instantaneous speciation, the results are identical to the equilibrium solution and indicate the dominance of the species-area relationship in forming patterns of diversity. The number of species in a basin is proportional to its area, and regional species richness reaches its maximum when drainage area is evenly distributed among sub-basins. Time-protracted speciation is also modeled as a stochastic process, but in order to produce more realistic rates of diversification, speciation is not assumed to be instantaneous. Rather, each new species must persist for a certain amount of time before it is considered to be established. When vicariance (geographic speciation) is included, there is a transient signature of increased regional diversity after river capture. The results indicate that the mode of speciation and the rate of speciation relative to the rate of divide migration determine the evolutionary signature of river capture.

Speciation gradients and the distribution of biodiversity.

PubMed

Schluter, Dolph; Pennell, Matthew W

2017-05-31

Global patterns of biodiversity are influenced by spatial and environmental variations in the rate at which new species form. We relate variations in speciation rates to six key patterns of biodiversity worldwide, including the species-area relationship, latitudinal gradients in species and genetic diversity, and between-habitat differences in species richness. Although they sometimes mirror biodiversity patterns, recent rates of speciation, at the tip of the tree of life, are often highest where species richness is low. Speciation gradients therefore shape, but are also shaped by, biodiversity gradients and are often more useful for predicting future patterns of biodiversity than for interpreting the past.

Enzyme-assisted extraction and liquid chromatography mass spectrometry for the determination of arsenic species in chicken meat.

PubMed

Liu, Qingqing; Peng, Hanyong; Lu, Xiufen; Le, X Chris

2015-08-12

Chicken is the most consumed meat in North America. Concentrations of arsenic in chicken range from μg kg(-1) to mg kg(-1). However, little is known about the speciation of arsenic in chicken meat. The objective of this research was to develop a method enabling determination of arsenic species in chicken breast muscle. We report here enzyme-enhanced extraction of arsenic species from chicken meat, separation using anion exchange chromatography (HPLC), and simultaneous detection with both inductively coupled plasma mass spectrometry (ICPMS) and electrospray ionization tandem mass spectrometry (ESIMS). We compared the extraction of arsenic species using several proteolytic enzymes: bromelain, papain, pepsin, proteinase K, and trypsin. With the use of papain-assisted extraction, 10 arsenic species were extracted and detected, as compared to 8 detectable arsenic species in the water/methanol extract. The overall extraction efficiency was also improved using a combination of ultrasonication and papain digestion, as compared to the conventional water/methanol extraction. Detection limits were in the range of 1.0-1.8 μg arsenic per kg chicken breast meat (dry weight) for seven arsenic species: arsenobetaine (AsB), inorganic arsenite (As(III)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), inorganic arsenate (As(V)), 3-nitro-4-hydroxyphenylarsonic acid (Roxarsone), and N-acetyl-4-hydroxy-m-arsanilic acid (NAHAA). Analysis of breast meat samples from six chickens receiving feed containing Roxarsone showed the presence of (mean±standard deviation μg kg(-1)) AsB (107±4), As(III) (113±7), As(V) (7±2), MMA (51±5), DMA (64±6), Roxarsone (18±1), and four unidentified arsenic species (approximate concentration 1-10 μg kg(-1)). Copyright © 2015 Elsevier B.V. All rights reserved.

Speciation analysis of mercury by dispersive solid-phase extraction coupled with capillary electrophoresis.

PubMed

Li, Jinhua; Liu, Junying; Lu, Wenhui; Gao, Fangfang; Wang, Liyan; Ma, Jiping; Liu, Huitao; Liao, Chunyang; Chen, Lingxin

2018-04-23

A pretreatment method of dispersive solid-phase extraction (DSPE) along with back-extraction followed by CE-UV detector was developed for the determination of mercury species in water samples. Sulfhydryl-functionalized SiO 2 microspheres (SiO 2 -SH) were synthesized and used as DSPE adsorbents for selective extraction and enrichment of three organic mercury species namely ethylmercury (EtHg), methylmercury (MeHg), and phenylmercury (PhHg), along with L-cysteine (L-cys) containing hydrochloric acid as back-extraction solvent. Several main extraction parameters were systematically investigated including sample pH, amount of adsorbent, extraction and back-extraction time, volume of eluent, and concentration of hydrochloric acid. Under optimal conditions, good linearity was achieved with correlation coefficients over 0.9990, in the range of 4-200 μg/L for EtHg, and 2-200 μg/L for MeHg and PhHg. The LODs were obtained of 1.07, 0.34, and 0.24 μg/L for EtHg, MeHg, and PhHg, respectively, as well as the LOQs were 3.57, 1.13, and 0.79 μg/L, respectively, with enrichment factors ranging from 109 to 184. Recoveries were attained with tap and lake water samples in a range of 62.3-107.2%, with relative standard deviations of 3.5-10.1%. The results proved that the method of SiO 2 -SH based DSPE coupled with CE-UV was a simple, rapid, cost-effective, and eco-friendly alternative for the determination of mercury species in water samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New mitochondrial DNA data affirm the importance of Pleistocene speciation in North American birds.

PubMed

Johnson, Ned K; Cicero, Carla

2004-05-01

The timing of origin of modern North American bird species in relation to Pleistocene glaciations has long been the topic of significant discussion and disagreement. Recently, Klicka and Zink (1997) and Avise and Walker (1998) enlivened this debate by using calibrated molecular distance values to estimate timing of speciations. Here we use new molecular studies to test their conclusions. Molecular distance values for 39 pairs of proven sister species, 27 of which are based on new data, alter the currently perceived pattern that avian species splits occurred mainly in the Pliocene and early-mid-Pleistocene. Mitochondrial DNA divergence values for this set of taxa showed a skewed distribution pointing toward relatively young speciation times, in contrast to the pattern presented by Klicka and Zink (1997) for 35 sister plus non-sister species pairs. Our pattern was not significantly different from that of Avise and Walker (1998) for "intraspecific phylogroups," some of which are species. We conclude that the entire Pleistocene, including the last two glacial cycles (<250,000 years ago), was important in speciations of modern North American birds. A substantial number of speciations were both initiated and completed in the last 250,000 years. Simultaneously, many taxa began to diverge in the Pleistocene but their speciations are not yet complete (per Avise and Walker 1998). The suggestion that durations of speciations average two million years is probably a substantial overestimate.

Ecological Impacts of Reverse Speciation in Threespine Stickleback.

PubMed

Rudman, Seth M; Schluter, Dolph

2016-02-22

Young species are highly prone to extinction via increased gene flow after human-caused environmental changes. This mechanism of biodiversity loss, often termed reverse speciation or introgressive extinction, is of exceptional interest because the parent species are typically highly differentiated ecologically. Reverse speciation events are potentially powerful case studies for the role of evolution in driving ecological changes, as the phenotypic shifts associated with introgressive extinction can be large and they occur over particularly short timescales. Furthermore, reverse speciation can lead to novel phenotypes, which may in turn produce novel ecological effects. Here we investigate the ecological shift associated with reverse speciation in threespine stickleback fish using a field study and a replicated experiment. We find that an instance of introgressive extinction had cascading ecological consequences that altered the abundance of both aquatic prey and the pupating aquatic insects that emerged into the terrestrial ecosystem. The community and ecosystem impacts of reverse speciation were novel, and yet they were also predictable based on ecological and morphological considerations. The study suggests that knowledge about the community ecology and changes in functional morphology of a dominant species may lead to some predictive power for the ecological effects of evolutionary change. Moreover, the rapid nature and resultant ecological impacts associated with reverse speciation demonstrates the interplay between biodiversity, evolutionary change, and ecosystem function. Copyright © 2016 Elsevier Ltd. All rights reserved.

Refining the conditions for sympatric ecological speciation.

PubMed

Débarre, F

2012-12-01

Can speciation occur in a single population when different types of resources are available, in the absence of any geographical isolation, or any spatial or temporal variation in selection? The controversial topics of sympatric speciation and ecological speciation have already stimulated many theoretical studies, most of them agreeing on the fact that mechanisms generating disruptive selection, some level of assortment, and enough heterogeneity in the available resources, are critical for sympatric speciation to occur. Few studies, however, have combined the three factors and investigated their interactions. In this article, I analytically derive conditions for sympatric speciation in a general model where the distribution of resources can be uni- or bimodal, and where a parameter controls the range of resources that an individual can exploit. This approach bridges the gap between models of a unimodal continuum of resources and Levene-type models with discrete resources. I then test these conditions against simulation results from a recently published article (Thibert-Plante & Hendry, 2011, J. Evol. Biol. 24: 2186-2196) and confirm that sympatric ecological speciation is favoured when (i) selection is disruptive (i.e. individuals with an intermediate trait are at a local fitness minimum), (ii) resources are differentiated enough and (iii) mating is assortative. I also discuss the role of mating preference functions and the need (or lack thereof) for bimodality in resource distributions for diversification. © 2012 The Author. Journal of Evolutionary Biology © 2012 European Society For Evolutionary Biology.

An unusual presentation of pseudocowpox associated with an outbreak of pustular ulcerative vulvovaginitis in a Swedish dairy herd.

PubMed

Blomqvist, Gunilla; Ullman, Karin; Segall, Thomas; Hauzenberger, Elenor; Renström, Lena; Persson-Waller, Karin; Leijon, Mikael; Valarcher, Jean-Francois

2018-03-01

Species Pseudocowpox virus (PCPV; family Poxviridae) is known to cause pustular cutaneous disease in cattle. We describe an outbreak of pseudocowpox with an unusual clinical picture in a free-stall dairy herd of ~80 cows. Approximately 90% of the cows had vesicles, erosions, papules, and scabs on the vulva and vaginal mucosa. Histologic analysis of biopsy tissues indicated a primary, although not specified, viral infection. Transmission electron microscopy revealed parapoxvirus particles in both tissue and vesicular materials. Deep sequencing analysis of extracted DNA from swabbed vesicle areas gave a contig of nearly 120,000 nucleotides, matching the PCPV strain VR 634 with 100% identity. Analyses confirmed the absence of other potential causes of pustular vulvovaginitis such as bovine herpesvirus 1 and Ureaplasma diversum. A rolling cow brush was suspected to be the fomite.

Anagenesis, Cladogenesis, and Speciation on Islands.

PubMed

Emerson, Brent C; Patiño, Jairo

2018-05-03

Anagenesis and cladogenesis are fundamental evolutionary concepts, but are increasingly being adopted as speciation models in the field of island biogeography. Here, we review the origin of the terms 'anagenetic' and 'cladogenetic' speciation, critique their utility, and finally suggest alternative terminology that better describes the geographical relationships of insular sister species. Copyright © 2018 Elsevier Ltd. All rights reserved.

Speciation and amphotericin B sensitivity studies on blood isolates of Candida from burned patients

PubMed Central

Stieritz, Donald D.; Law, Edward J.; Holder, Ian Alan

1973-01-01

Methods of speciating Candida isolates from clinical specimens are described and the necessity of speciation is emphasized. Differences in susceptibility of C. albicans and C. tropicalis to amphotericin B were observed and the implications of this in relation to treatment with amphotericin B and the development of resistance are discussed. PMID:4578160

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

PubMed Central

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

2014-01-01

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

Ecological speciation in an island snail: evidence for the parallel evolution of a novel ecotype and maintenance by ecologically dependent postzygotic isolation.

PubMed

Stankowski, Sean

2013-05-01

Speciation is the process by which reproductive isolation evolves between populations. Two general models of speciation have been proposed: ecological speciation, where reproductive barriers evolve due to ecologically based divergent selection, and mutation-order speciation, where populations fix different mutations as they adapt to similar selection pressures. I evaluate these alternative models and determine the progress of speciation in a diverse group of land snails, genus Rhagada, inhabiting Rosemary Island. A recently derived keeled-flat morphotype occupies two isolated rocky hills, while globose-shelled snails inhabit the surrounding plains. The study of one hill reveals that they are separated by a narrow hybrid zone. As predicted by ecological speciation theory, there are local and landscape level associations between shell shape and habitat, and the morphological transition coincides with a narrow ecotone between the two distinct environments. Microsatellite DNA revealed a cline of hybrid index scores much wider than the morphological cline, further supporting the ecological maintenance of the morphotypes. The hybrid zone does not run through an area of low population density, as is expected for mutation-order hybrid zones, and there is a unimodal distribution of phenotypes at the centre, suggesting that there is little or no prezygotic isolation. Instead, these data suggest that the ecotypes are maintained by ecologically dependent postzygotic isolation (i.e. ecological selection against hybrids). Mitochondrial and Microsatellite DNA indicate that the keeled-flat form evolved recently, and without major historical disruptions to gene flow. The data also suggest that the two keeled-flat populations, inhabiting similar rocky hills, have evolved in parallel. These snails provide a complex example of ecological speciation in its early stages. © 2013 Blackwell Publishing Ltd.

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

PubMed Central

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 evolutionary dynamics and speciation rates in the dramatically changing environments of Northern Europe. PMID:23589633

Extinction Risk and Diversification Are Linked in a Plant Biodiversity Hotspot

PubMed Central

Davies, T. Jonathan; Smith, Gideon F.; Bellstedt, Dirk U.; Boatwright, James S.; Bytebier, Benny; Cowling, Richard M.; Forest, Félix; Harmon, Luke J.; Muasya, A. Muthama; Schrire, Brian D.; Steenkamp, Yolande; van der Bank, Michelle; Savolainen, Vincent

2011-01-01

It is widely recognized that we are entering an extinction event on a scale approaching the mass extinctions seen in the fossil record. Present-day rates of extinction are estimated to be several orders of magnitude greater than background rates and are projected to increase further if current trends continue. In vertebrates, species traits, such as body size, fecundity, and geographic range, are important predictors of vulnerability. Although plants are the basis for life on Earth, our knowledge of plant extinctions and vulnerabilities is lagging. Here, we disentangle the underlying drivers of extinction risk in plants, focusing on the Cape of South Africa, a global biodiversity hotspot. By comparing Red List data for the British and South African floras, we demonstrate that the taxonomic distribution of extinction risk differs significantly between regions, inconsistent with a simple, trait-based model of extinction. Using a comprehensive phylogenetic tree for the Cape, we reveal a phylogenetic signal in the distribution of plant extinction risks but show that the most threatened species cluster within short branches at the tips of the phylogeny—opposite to trends in mammals. From analyzing the distribution of threatened species across 11 exemplar clades, we suggest that mode of speciation best explains the unusual phylogenetic structure of extinction risks in plants of the Cape. Our results demonstrate that explanations for elevated extinction risk in plants of the Cape flora differ dramatically from those recognized for vertebrates. In the Cape, extinction risk is higher for young and fast-evolving plant lineages and cannot be explained by correlations with simple biological traits. Critically, we find that the most vulnerable plant species are nonetheless marching towards extinction at a more rapid pace but, surprisingly, independently from anthropogenic effects. Our results have important implications for conservation priorities and cast doubts on the utility of current Red List criteria for plants in regions such as the Cape, where speciation has been rapid, if our aim is to maximize the preservation of the tree-of-life. PMID:21629678

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

NASA Astrophysics Data System (ADS)

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

2009-08-01

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

Determination of sixteen elements and arsenic species in brown, polished and milled rice.

PubMed

Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

2014-01-01

The concentrations of 16 elements in 10 rice flour samples and the distribution of the elements in the rice grains from which the flour were made were determined by ICP-MS and ICP-OES after microwave-assisted digestion of the samples. Arsenic speciation analysis was carried out by HPLC-ICP-MS following heat-assisted extraction of the sample. The concentrations of inorganic As (As(III) and As(V)), monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) and their distribution in the rice grains were determined. Portions of the brown rice were polished/milled to different degrees to yield milled off samples and polished rice samples. All samples were powdered and analyzed for 16 elements and for As species. The recoveries and mass balances for all elements in all samples showed good agreements with the starting materials. As(III), As(V), MMAA and DMAA were detected, and the sums of the concentrations of all species in the extract were 86-105% of the total As concentration in each case.

Speciation and monitoring test for inorganic arsenic in white rice flour.

PubMed

Narukawa, Tomohiro; Hioki, Akiharu; Chiba, Koichi

2012-02-01

A monitoring test for arsenic species in white rice flour was developed and applied to flours made from 20 samples of polished rice collected from locations all over Japan. The arsenic species in white rice flour made from five samples each of four types of rice were analyzed by HPLC-ICP-MS after a heat-assisted aqueous extraction. The total arsenic and major and minor element concentrations in the white rice flours were measured by ICP-MS and ICP-OES after microwave-assisted digestion. 91 ± 1% of the arsenic in the flours was extractable. Concentrations of arsenite [As(III)], arsenate [As(V)], and dimethylarsinic acid (DMAA) were closely positively correlated with the total arsenic concentrations. The total arsenic concentration in flours made from rice collected around Japan was 0.15 ± 0.07 mg kg(-1) (highest, 0.32 mg kg(-1)), which is very low. It was thus confirmed that the white rice flour samples collected in this experiment were not suffered from noticeable As contamination.

Chromium fate in constructed wetlands treating tannery wastewaters.

PubMed

Dotro, Gabriela; Palazolo, Paul; Larsen, Daniel

2009-06-01

Nine experimental wetlands were built to determine chromium partitioning inside systems treating tannery wastewaters. Results showed 5-day biochemical oxygen demand and chromium removals of 95 to 99% and 90 to 99%, respectively. The majority of chromium was found in association with media (96 to 98%), followed by effluents (2.9 to 3.9%), and the least was found in plant parts (0.1%). Chemical speciation modeling of solutions and scanning electron microscope analysis suggest two potential chromium removal mechanisms--sorption/coprecipitation with iron hydroxides or oxyhydroxides and biomass sorption. The release of the majority of chromium in the iron- and organic-bound phases during sequential extractions supports the proposed dominant removal mechanisms. The use of a mixture of peat and gravel resulted in lower removal efficiencies and stronger partitioning in organic phases during sequential extractions. Chromium was efficiently removed by wetlands, retained through chemical and biological processes. Future research will focus on further exploring removal mechanisms and proposing management strategies for the chromium-containing wetland media.

A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

NASA Astrophysics Data System (ADS)

Chalmin, E.; Farges, F.; Brown, G. E.

2009-01-01

High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses.

Application of polyurethane foam as a sorbent for trace metal pre-concentration — A review

NASA Astrophysics Data System (ADS)

Lemos, V. A.; Santos, M. S.; Santos, E. S.; Santos, M. J. S.; dos Santos, W. N. L.; Souza, A. S.; de Jesus, D. S.; das Virgens, C. F.; Carvalho, M. S.; Oleszczuk, N.; Vale, M. G. R.; Welz, B.; Ferreira, S. L. C.

2007-01-01

The first publication on the use of polyurethane foam (PUF) for sorption processes dates back to 1970, and soon after the material was applied for separation processes. The application of PUF as a sorbent for solid phase extraction of inorganic analytes for separation and pre-concentration purposes is reviewed. The physical and chemical characteristics of PUF (polyether and polyester type) are discussed and an introduction to the characterization of these sorption processes using different types of isotherms is given. Separation and pre-concentration methods using unloaded and loaded PUF in batch and on-line procedures with continuous flow and flow injection systems are presented. Methods for the direct solid sampling analysis of the PUF after pre-concentration are discussed as well as approaches for speciation analysis. Thermodynamic proprieties of some extraction processes are evaluated and the interpretation of determined parameters, such as enthalpy, entropy and Gibbs free energy in light of the physico-chemical processes is explained.

Molecular Level Investigation of CH 4 and CO 2 Adsorption in Hydrated Calcium–Montmorillonite

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

Lee, Mal-Soon; McGrail, B. Peter; Rousseau, Roger

2017-11-17

We have studied the mechanism of intercalation and methane adsorption from a H2O/CH4/CO2 mixture on a prototypical shale component, Ca-montmorillonite. We employed ab initio molecular dynamics simulations at 323 K and 90 bar to obtain molecular level information of adsorption energetics, speciation, and structural and thermodynamic properties. Interaction of CH4 with surface Lewis acidic sites (Ca2+, surface OH) results in large induced dipoles (~1 D) that lead to relatively strong adsorption energies that level off once a full CH4 layer is formed. Intercalated CH4, also exhibits induced dipoles at low hydration levels, when the interaction with Ca2+ cations are lessmore » hindered. CO2 displaces CH4 in the coordination sphere of the cations (in the interlayer) or in the surface, thereby driving CH4 extraction. Our simulations indicate that there is a Goldilocks pressure range (~60-100 bar) where scCO2 –facilitated CH4 extraction will be maximized.« less

Complex temporal topic evolution modelling using the Kullback-Leibler divergence and the Bhattacharyya distance.

PubMed

Andrei, Victor; Arandjelović, Ognjen

2016-12-01

The rapidly expanding corpus of medical research literature presents major challenges in the understanding of previous work, the extraction of maximum information from collected data, and the identification of promising research directions. We present a case for the use of advanced machine learning techniques as an aide in this task and introduce a novel methodology that is shown to be capable of extracting meaningful information from large longitudinal corpora and of tracking complex temporal changes within it. Our framework is based on (i) the discretization of time into epochs, (ii) epoch-wise topic discovery using a hierarchical Dirichlet process-based model, and (iii) a temporal similarity graph which allows for the modelling of complex topic changes. More specifically, this is the first work that discusses and distinguishes between two groups of particularly challenging topic evolution phenomena: topic splitting and speciation and topic convergence and merging, in addition to the more widely recognized emergence and disappearance and gradual evolution. The proposed framework is evaluated on a public medical literature corpus.

THE NATURE OF THE GECKO VISUAL PIGMENT

PubMed Central

Crescitelli, Frederick

1956-01-01

Retinal extracts of the Australian gecko, Phyllurus milii (White), have revealed the presence of a photosensitive pigment, unusual for terrestrial animals, because of its absorption maximum at 524 mµ. This pigment has an absorption spectrum which is identical in form with that of other visual chromoproteins. It is not a porphyropsin, for bleaching revealed the presence, not of retinene2, but of retinene1 as a chromophore. Photolabile pigments with characteristics similar to those of the Phyllurus visual pigment were also detected in retinal extracts of six other species of nocturnal geckos. The presence of this retinal chromoprotein adequately accounts for the unusual visual sensitivity curve described by Denton for the nocturnal gecko. This pigment may have special biological significance in terms of the unique phylogenetic position of geckos as living representatives of nocturnal animals which retain some of the characteristics of their diurnal ancestors. The occurrence of this retinene1 pigment, intermediate in spectral position between rhodopsin and iodopsin, is interpreted in support of the transmutation theory of Walls. The results and interpretation of this investigation point up the fact that, from a phylogenetic point of view, too great an emphasis on the duplicity theory may serve to detract attention from the evolutionary history of the retina and the essential unitarianism of the visual cells. PMID:13385449

Lumichrome and phenyllactic acid as chemical markers of thistle (Galactites tomentosa Moench) honey.

PubMed

Tuberoso, Carlo I G; Bifulco, Ersilia; Caboni, Pierluigi; Sarais, Giorgia; Cottiglia, Filippo; Floris, Ignazio

2011-01-12

HPLC-DAD-MS/MS chromatograms of thistle (Galactites tomentosa Moench) unifloral honeys, previously selected by sensory evaluation and melissopalynological analysis, showed high levels of two compounds. One was characterized as phenyllactic acid, a common acid found in honeys, but the other compound was very unusual for honeys. This compound was extracted from honey with ethyl acetate and purified by SPE using C(18), SiOH, and NH(2) phases. Its structure was elucidated on the basis of extensive 1D and 2D NMR experiments as well as HPLC-MS/MS and Q-TOF analysis, and it was identified as lumichrome (7,8-dimethylalloxazine). Lumichrome is known to be the main product of degradation obtained in acid medium from riboflavin (vitamin B(2)), and this is the first report of the presence of lumichrome in honeys. Analysis of the G. tomentosa raw honey and flowers extracts confirmed the floral origin of this compound. The average amount of lumichrome in thistle honey was 29.4 ± 14.9 mg/kg, while phenyllactic acid was 418.6 ± 168.9 mg/kg. Lumichrome, along with the unusual high level of phenyllactic acid, could be used as a marker for the botanical classification of unifloral thistle (G. tomentosa) honey.

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

PubMed Central

Suvarapu, Lakshmi Narayana; Baek, Sung-Ok

2015-01-01

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. PMID:26236539

Rapid neo-sex chromosome evolution and incipient speciation in a major forest pest

Treesearch

Ryan R. Bracewell; Barbara J. Bentz; Brian T. Sullivan; Jeffrey M. Good

2017-01-01

Genome evolution is predicted to be rapid following the establishment of new (neo) sex chromosomes, but it is not known if neo-sex chromosome evolution plays an important role in speciation. Here we combine extensive crossing experiments with population and functional genomic data to examine neo-XY chromosome evolution and incipient speciation in the mountain pine...

Monte Carlo simulations of parapatric speciation

NASA Astrophysics Data System (ADS)

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

2006-06-01

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

Presumptive speciation of Streptococcus bovis and other group D streptococci from human sources by using arginine and pyruvate tests.

PubMed Central

Gross, K C; Houghton, M P; Senterfit, L B

1975-01-01

A simplified method for speciation of group D streptococci is described. A total of 4,156 streptococcal isolates from human clinical material was tested for ability to hydrolyze esculin in the presence of 40% bile, ferment pyruvate, hydrolyze arginine, and grow in media containing 40% bile or 6.5% NaCl. Streptococci which hydrolyzed esculin in 40% bile, but which did not hydrolyze arginine, were also tested for their ability to ferment raffinose or sorbose. Sixty percent (2,503) of the isolates hydrolyzed esculin in the presence of 40% bile and were thus presumptively identified as group D. By application of the other criteria, 84% of these were speciated as Streptococcus faecalis, 7% were speciated as S. faecium, 6% were speciated as S. bovis, 2% were speciated as S. avium, and 1% were not identified. This scheme was shown to be both reliable and practical for use in the diagnostic laboratory. S. avium and S. bovis isolates were characterized, and 18 S. bovis isolates from patients with bacterial endocarditis were compared physiologically with 151 isolates of this species from other sources. PMID:1176592

Pleistocene phylogeographic effects on avian populations and the speciation process.

PubMed Central

Avise, J C; Walker, D

1998-01-01

Pleistocene biogeographic events have traditionally been ascribed a major role in promoting speciations and in sculpting the present-day diversity and distributions of vertebrate taxa. However, this paradigm has recently come under challenge from a review of interspecific mtDNA genetic distances in birds: most sister-species separations dated to the Pliocene. Here we summarize the literature on intraspecific mtDNA phylogeographic patterns in birds and reinterpret the molecular evidence bearing on Pleistocene influences. At least 37 of the 63 avian species surveyed (59%) are sundered into recognizable phylogeographic units, and 28 of these separations (76%) trace to the Pleistocene. Furthermore, use of phylogroup separation times within species as minimum estimates of 'speciation durations' also indicates that many protracted speciations, considered individually, probably extended through time from Pliocene origins to Pleistocene completions. When avian speciation is viewed properly as an extended temporal process rather than as a point event, Pleistocene conditions appear to have played an active role both in initiating major phylogeographic separations within species, and in completing speciations that had been inaugurated earlier. Whether the Pleistocene was exceptional in these regards compared with other geological times remains to be determined. PMID:9569664

Quantitative traits and diversification.

PubMed

FitzJohn, Richard G

2010-12-01

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

Prevalence of disruptive selection predicts extent of species differentiation in Lake Victoria cichlids.

PubMed

van Rijssel, Jacco C; Moser, Florian N; Frei, David; Seehausen, Ole

2018-01-31

Theory suggests that speciation with gene flow is most likely when both sexual and ecological selection are divergent or disruptive. Divergent sexual and natural selection on the visual system have been demonstrated before in sympatric, morphologically similar sister species of Lake Victoria cichlids, but this does not explain the subtle morphological differences between them. To investigate the significance of natural selection on morphology during speciation, we here ask whether the prevalence of disruptive ecological selection differs between sympatric sister species that are at different stages of speciation. Some of our species pairs do ( Pundamilia ) and others do not ( Neochromis ) differ distinctively in sexually selected male nuptial coloration. We find that (i) evidence for disruptive selection, and for evolutionary response to it, is prevalent in traits that are differentiated between sister species; (ii) prevalence of both predicts the extent of genetic differentiation; and (iii) genetic differentiation is weaker in species pairs with conserved male nuptial coloration. Our results speak to the existence of two different mechanisms of speciation with gene flow: speciation mainly by sexual selection tightly followed by ecological character displacement in some cases and speciation mainly by divergent ecological selection in others. © 2018 The Author(s).

Comparative study of adaptive radiations with an example using parasitic flatworms (Platyhelminthes): Cercomeria

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

Brooks, D.R.; McLennan, D.A.

1993-11-01

Studies of adaptive radiations require robust phylogenies, estimates of species numbers for monophyletic groups within clades, assessments of the adaptive value of putative key innovations, and estimates of the frequency of speciation modes. Four criteria are necessary to identify an adaptive radiation within the parasitic platyhelminths: (1) a group contains significantly more species than its sister group, (2) species richness is apomorphic, (3) apomorphic traits enhance the potential for adaptively driven modes of speciation (sympatric speciation and speciation by peripheral isolation via host switching), and (4) the frequency of adaptively driven speciation modes is high within the group when comparedmore » with data from free-living groups. Only the species-rich Monogenea fulfill all four criteria. The Digenea and Eucestoda also are more species rich than their sister groups, their species richness is derived, and they possess unique characters that increase the potential for host switching to occur. However, because there is not enough information to determine whether the frequency of adaptive modes of speciation is high for those groups, we cannot yet assert that their radiations have been adaptive. 102 refs., 3 figs., 1 tab.« less

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

PubMed

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.

Speciations of trace metals in the Danube alluvial sediments within an oil refinery.

PubMed

Relić, Dubravka; Dordević, Dragana; Popović, Aleksandar; Blagojević, Tamara

2005-07-01

A sequential extraction procedure was applied to identify forms of Ni, Zn, Pb and Cu with Fe- and Mn-oxides associated in alluvial sediments of the River Danube within Pancevo Oil Refinery (Serbia). The five steps of the sequential extraction procedure partitioned metals into: CH(3)COONH(4) extractable (S1); NH(2)OH.HCl carbonate extractable and easily reducible (S2); (NH(4))(2)C(2)O(2)/H(2)C(2)O(2) moderately reducible (S3); H(2)O(2)-HNO(3) organic extractable (S4); and HCl acid soluble residue (S5). Extracted concentrations of trace metals, analyzed after all five steps, were found to be (mg kg(-1)) for Mn: 656, Fe: 26734, Ni: 32.3, Zn: 72.8, Pb: 13.4 and Cu: 27.0. Most of the elements were found in acid soluble residue, characterizing stable compounds in sediments. Non-residual fractions of trace metals (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were used to understand and visualize the associations between the non-residual fractions of trace metals and certain forms, more or less crystalline of Fe- and Mn-oxides within the analyzed sediments, since Fe- and Mn-oxides play an important role in trace metal sorption within aquatic systems, especially within the Danube alluvium where the fluctuations of groundwater are very frequent and the level of groundwater could come close to surface.

Understanding processes at the origin of species flocks with a focus on the marine Antarctic fauna.

PubMed

Chenuil, Anne; Saucède, Thomas; Hemery, Lenaïg G; Eléaume, Marc; Féral, Jean-Pierre; Améziane, Nadia; David, Bruno; Lecointre, Guillaume; Havermans, Charlotte

2018-02-01

Species flocks (SFs) fascinate evolutionary biologists who wonder whether such striking diversification can be driven by normal evolutionary processes. Multiple definitions of SFs have hindered the study of their origins. Previous studies identified a monophyletic taxon as a SF if it displays high speciosity in an area in which it is endemic (criterion 1), high ecological diversity among species (criterion 2), and if it dominates the habitat in terms of biomass (criterion 3); we used these criteria in our analyses. Our starting hypothesis is that normal evolutionary processes may provide a sufficient explanation for most SFs. We thus clearly separate each criterion and identify which biological (intrinsic) and environmental (extrinsic) traits are most favourable to their realization. The first part focuses on evolutionary processes. We highlight that some popular putative causes of SFs, such as key innovations or ecological speciation, are neither necessary nor sufficient to fulfill some or all of the three criteria. Initial differentiation mechanisms are diverse and difficult to identify a posteriori because a primary differentiation of one type (genetic, ecological or geographical) often promotes other types of differentiation. Furthermore, the criteria are not independent: positive feedbacks between speciosity and ecological diversity among species are expected whatever the initial cause of differentiation, and ecological diversity should enhance habitat dominance at the clade level. We then identify intrinsic and extrinsic factors that favour each criterion. Low dispersal emerges as a convincing driver of speciosity. Except for a genomic architecture favouring ecological speciation, for which assessment is difficult, high effective population sizes are the single intrinsic factor that directly enhances speciosity, ecological diversity and habitat dominance. No extrinsic factor appeared to enhance all criteria simultaneously but a combination of factors (insularity, fragmentation and environmental stability) may favour the three criteria, although the effect is indirect for habitat dominance. We then apply this analytical framework to Antarctic marine environments by analysing data from 18 speciose clades belonging to echinoderms (five unrelated clades), notothenioid fishes (five clades) and peracarid crustaceans (eight clades). Antarctic shelf environments and history appear favourable to endemicity and speciosity, but not to ecological specialization. Two main patterns are distinguished among taxa. (i) In echinoderms, many brooding, species-rich and endemic clades are reported, but without remarkable ecological diversity or habitat dominance. In these taxa, loss of the larval stage is probably a consequence of past Antarctic environmental factors, and brooding is suggested to be responsible for enhanced allopatric speciation (via dispersal limitation). (ii) In notothenioids and peracarids, many clades fulfill all three SF criteria. This could result from unusual features in fish and crustaceans: chromosome instability and key innovations (antifreeze proteins) in notothenioids, ecological opportunity in peracarids, and a genomic architecture favouring ecological speciation in both groups. Therefore, the data do not support our starting point that normal evolutionary factors or processes drive SFs because in these two groups uncommon intrinsic features or ecological opportunity provide the best explanation. The utility of the three-criterion SF concept is therefore questioned and guidelines are given for future studies. © 2017 Cambridge Philosophical Society.

Comparison between fractionation and bioavailability of trace elements in rhizosphere and bulk soils.

PubMed

Wang, Zhongwen; Shan, Xiao-Quan; Zhang, Shuzhen

2002-03-01

Rhizosphere is a microbiosphere and has quite different chemical, physical and biological properties from bulk soils. A greenhouse experiment was performed to compare the difference of fractionation and bioavailability of trace elements Cr, Ni, Zn, Cu, Pb and Cd between rhizosphere soil and bulk soil. In the meantime, the influence of air-drying on the fractionation and bioavailability was also investigated by using wet soil sample as a control. Soils in a homemade rhizobox were divided into four zones: rhizosphere, near rhizosphere, near bulk soil and bulk soil zones, which was designated as S1, S2, S3 and S4. Elemental speciations were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3) by a sequential extraction procedure. Speciation differences were observed for elements Cr, Ni, Zn, Cu, Pb and Cd between the rhizosphere and bulk soils, and between the air-dried and wet soils as well. The concentrations of all six heavy metals in fraction B1 followed the order of S2 > S3 > S1 > S4 and for B2, the order was S2 > S3 S4 > S1. For B3, the order was S1 > S3 S4 > S2, while for Cd the order was S2 > S3 approximately/= S4 > S1. The air-drying increased elemental concentration in fractions B1 and B2 by 20-50% and decreased in fraction B3 by about 20-100%. Correlation analysis also indicated that the bioavailability correlation coefficient of fraction B1 in rhizosphere wet soil to plants was better than that between either air-dried or nonrhizosphere soils. Therefore, application of rhizosphere wet soils should be recommended in the future study on the speciation analysis of trace elements in soils and bioavailability.

Field Deployable Method for Arsenic Speciation in Water.

PubMed

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

2011-01-01

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

Field Deployable Method for Arsenic Speciation in Water

PubMed Central

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

2010-01-01

Contamination of drinking water supplies by arsenic is a world-wide problem. Total arsenic measurements are commonly used to investigate and regulate arsenic in water, but it is well understood that arsenic occurs in several chemical forms, and these exhibit different toxicities. It is problematic to use laboratory-based speciation techniques to assess exposure as it has been suggested that the distribution of species is not stable during transport in some types of samples. A method was developed in this study for the on-site speciation of the most toxic dissolved arsenic species: As (III), As (V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA). Development criteria included ease of use under field conditions, applicable at levels of concern for drinking water, and analytical performance. The approach is based on selective retention of arsenic species on specific ion-exchange chromatography cartridges followed by selective elution and quantification using graphite furnace atomic absorption spectroscopy. Water samples can be delivered to a set of three cartridges using either syringes or peristaltic pumps. Species distribution is stable at this point, and the cartridges can be transported to the laboratory for elution and quantitative analysis. A set of ten replicate spiked samples of each compound, having concentrations between 1 and 60 µg/L, were analyzed. Arsenic recoveries ranged from 78–112 % and relative standard deviations were generally below 10%. Resolution between species was shown to be outstanding, with the only limitation being that the capacity for As (V) was limited to approximately 50 µg/L. This could be easily remedied by changes in either cartridge design, or the extraction procedure. Recoveries were similar for two spiked hard groundwater samples indicating that dissolved minerals are not likely to be problematic. These results suggest that this methodology can be use for analysis of the four primary arsenic species of concern in drinking water supplies. PMID:21822400