Speciation of Mg in biogenic calcium carbonates

NASA Astrophysics Data System (ADS)

Farges, F.; Meibom, A.; Flank, A.-M.; Lagarde, P.; Janousch, M.; Stolarski, J.

2009-11-01

A selection of marine biominerals, mostly aragonitic coral skeletons were probed at the Mg K-edge by XANES spectroscopy coupled to μXRF methods and compared to an extensive set of relevant model compounds (silicates, carbonates, oxides and organic). Extensive methodologies are required to better describe the speciation of Mg in those minerals. A combination of ab-initio XANES calculations for defective clusters around Mg in aragonite together with wavelets analyzes of the XANES region are required to robustly interpret the spectra. When using those methodologies, the speciation of Mg ranges from a magnesite-type environment in some scleractinian corals to an organic-type environment. In all environments, the Mg-domains probed appear to be less than 1 nm in size.

Carbon speciation and surface tension of fog

USGS Publications Warehouse

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

1990-01-01

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

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

PubMed

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

2016-02-01

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

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

PubMed

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

2015-09-01

Street dust and soil from high, medium and low populated cities and natural area were analysed for selected physical-chemical properties, total and chemical speciation of Zn, Pb, Cu, Cr, Cd, Co, Ni to understand the influence of human activities on metal accumulation and mobility in the environment. The pH, salinity, carbonates and organic carbon contents were similar between soil and dust from the same city. Population density increases dust/soil salinity but has no influence on metals concentrations in soils. Increases in metal concentrations with population density were observed in dusts. Cu, Zn, Pb, Cr can be mobilized more easily from dust compared to the soil. In addition, population density increase the percentage of Pb and Zn associated to reducible and carbonate phase in the dust. The behaviour of metals except Cd in soil is mainly affected by physico-chemical properties, while total metal influenced the speciation except Cr and Ni in dusts. Copyright © 2015 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.

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.

Noninvasive Synchrotron-Based X-ray Raman Scattering Discriminates Carbonaceous Compounds in Ancient and Historical Materials [ In situ synchrotron-based X-Ray Raman scattering discriminates carbonaceous compounds in ancient and historical materials

DOE PAGES

Gueriau, Pierre; Rueff, Jean -Pascal; Bernard, Sylvain; ...

2017-09-13

Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280–350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard X-ray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Heremore » we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, thereby augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. As a result, we show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques.« less

Selenium speciation in phosphate mine soils and evaluation of a sequential extraction procedure using XAFS.

PubMed

Favorito, Jessica E; Luxton, Todd P; Eick, Matthew J; Grossl, Paul R

2017-10-01

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, PO 4 -extractable, carbonate, amorphous Fe-oxide, crystalline Fe-oxide, organic, and residual Se forms. For whole soils, XANES analyses 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. Copyright © 2017 Elsevier Ltd. All rights reserved.

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn

2011-01-01

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

Subcellular Distribution and Chemical Forms of Pb in Corn: Strategies Underlying Tolerance in Pb Stress.

PubMed

Sun, Jianling; Luo, Liqiang

2018-06-22

Studying the accumulation position and forms of heavy metals (HMs) in organisms and cells is helpful to understand the transport process and detoxification mechanism. As typical HMs, lead (Pb) subcellular content, localization, and speciation of corn subcellular fractions were studied by a series of technologies, including transmission electron microscopy, inductively coupled plasma mass spectrometry, and X-ray absorption near edge structure. The results revealed that the electrodense granules of Pb were localized in the cell wall, intercellular space, and plasma membranes. About 71% Pb was localized at the cell wall and soluble fraction. In cell walls, the total amount of pyromorphite and Pb carbonate was about 80% and the remaining was Pb stearate. In the nuclear and chloroplast fraction, which demonstrated significant changes, major speciations were Pb sulfide (72%), basic Pb carbonate (16%), and Pb stearate (12%). Pb is blocked by cell walls as pyromorphite and Pb carbonate sediments and compartmentalized by vacuoles, which both play an inportant role in cell detoxification. Besides, sulfur-containing compounds form inside the cells.

Inorganic carbon speciation and fluxes in the Congo River

NASA Astrophysics Data System (ADS)

Wang, Zhaohui Aleck; Bienvenu, Dinga Jean; Mann, Paul J.; Hoering, Katherine A.; Poulsen, John R.; Spencer, Robert G. M.; Holmes, Robert M.

2013-02-01

Seasonal variations in inorganic carbon chemistry and associated fluxes from the Congo River were investigated at Brazzaville-Kinshasa. Small seasonal variation in dissolved inorganic carbon (DIC) was found in contrast with discharge-correlated changes in pH, total alkalinity (TA), carbonate species, and dissolved organic carbon (DOC). DIC was almost always greater than TA due to the importance of CO2*, the sum of dissolved CO2 and carbonic acid, as a result of low pH. Organic acids in DOC contributed 11-61% of TA and had a strong titration effect on water pH and carbonate speciation. The CO2* and bicarbonate fluxes accounted for ~57% and 43% of the DIC flux, respectively. Congo River surface water released CO2 at a rate of ~109 mol m-2 yr-1. The basin-wide DIC yield was ~8.84 × 104 mol km-2 yr-1. The discharge normalized DIC flux to the ocean amounted to 3.11 × 1011 mol yr-1. The DOC titration effect on the inorganic carbon system may also be important on a global scale for regulating carbon fluxes in rivers.

Speciation of the trivalent f-elements Eu(III) and Cm(III) in digestive media.

PubMed

Wilke, Claudia; Barkleit, Astrid; Stumpf, Thorsten; Ikeda-Ohno, Atsushi

2017-10-01

In case radioactive materials are released into the environment, their incorporation into our digestive system would be a significant concern. Trivalent f-elements, i.e., trivalent actinides and lanthanides, could potentially represent a serious health risk due to their chemo- and radiotoxicity, nevertheless the biochemical behavior of these elements are mostly unknown even to date. This study, therefore, focuses on the chemical speciation of trivalent f-elements in the human gastrointestinal tract. To simulate the digestive system artificial digestive juices (saliva, gastric juice, pancreatic juice and bile fluid) were prepared. The chemical speciation of lanthanides (as Eu(III)) and actinides (as Cm(III)) was determined experimentally by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and the results were compared with thermodynamic modeling. The results indicate a dominant inorganic species with phosphate/carbonate in the mouth, while the aquo ion is predominantly formed with a minor contribution of the enzyme pepsin in the stomach. In the intestinal tract the most significant species are with the protein mucin. We demonstrated the first experimental results on the chemical speciation of trivalent f-elements in the digestive media by TRLFS. The results highlight a significant gap in chemical speciation between experiments and thermodynamic modeling due to the limited availability of thermodynamic stability constants particularly for organic species. Chemical speciation strongly influences the in vivo behavior of metal ions. Therefore, the results of this speciation study will help to enhance the assessment of health risks and to improve decorporation strategies after ingestion of these (radio-)toxic heavy metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

Linkage between speciation of Cd in mangrove sediment and its bioaccumulation in total soft tissue of oyster from the west coast of India.

PubMed

Chakraborty, Parthasarathi; Ramteke, Darwin; Gadi, Subhadra Devi; Bardhan, Pratirupa

2016-05-15

This study established a mechanistic linkage between Cd speciation and bioavailability in mangrove system from the west coast of India. High bioaccumulation of Cd was found in the oyster (Crassostrea sp.) even at low Cd loading in the bottom sediment. Bioaccumulation of Cd in the oyster gradually increased with the increasing concentrations of water soluble, exchangeable and carbonate/bicarbonate forms of Cd in the sediments. Fe/Mn oxyhydroxide phase was found to control Cd bioavailability in the sediment system. Cd-associated with sedimentary organic matter was bioavailable and organic ligands in the sediments were poor chelating agents for Cd. This study suggests that bioaccumulation of Cd in oyster (Crassostrea sp.) depends not on the total Cd concentration but on the speciation of Cd in the system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Multi-scale analysis of the occurrence of Pb, Cr and Mn in the NIST standards: Urban dust (SRM 1649a) and indoor dust (SRM 2584)

NASA Astrophysics Data System (ADS)

Jiang, Mingyu; Nakamatsu, Yuki; Jensen, Keld A.; Utsunomiya, Satoshi

2014-01-01

Adverse health effects of ambient particulate matters are closely related to the speciation of the constituting organic matters and toxic metals. To determine multi-parameters of the metal speciation in urban and indoor dusts, we have performed systematic bulk- to nano-scale (“multi-scale”) analysis on the speciation of Pb, Mn, and Cr in two National Institute of Standards and Technology (NIST) standard reference materials (SRMs): urban dust (SRM 1649a) and indoor dust (SRM 2584), utilizing X-ray absorption near-edge structure, powder X-ray diffraction analysis, electron microprobe analysis, scanning electron microscopy, and transmission electron microscopy. Major crystalline phases are quartz, gypsum, kaolinite, and muscovite in SRM 1649a, while quartz, gypsum, calcite, and possibly muscovite (or chabazite) in SRM 2584. A number of Pb sulfate nanoparticles (50-200 nm) occur in SRM 1649a, whereas micron-sized Pb carbonate is present containing various concentrations of Zn and Ti in the complex texture in SRM 2584. Relatively soluble Mn(II) sulfate is the bulk-averaged Mn speciation in SRM 1649a, although discrete Mn sulfate particles are not characterized by individual particle analysis, implying the diluted Mn distribution within other sulfate. In SRM 2584, Mn speciation includes a mixture of oxides and carbonates, and trace Mn in chromite. Chromite (FeCr2O4) is the major Cr speciation in SRM1694a, while unidentified Cr(III) phases with minor chromite and Pb chromate are present in SRM 2584, among which the Pb chromate is composed of Cr(VI). A significant number of the metal-bearing particles are distributed to the submicron-size fraction in the urban dust, SRM 1649a, suggesting that these metal nanoparticles can potentially penetrate into the deep respiratory system. This study demonstrates that multi-scale analysis combining nano and bulk analytical techniques is a powerful approach to investigate the multi-parameters of metal-bearing nanoparticles in heterogeneous PM samples.

[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%.

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

We have conducted aqueous speciation analyses of the Great Salt Lake (GSL) brine sample (Table 1) and a mock geo sample (Table 2) spiked with 1 ppb Tb and 100 ppb Tb. The GSL speciation (Figure 1) aligns with our basic speciation expectations that strong carbonate complexes would form at mid to higher pH's. Although we expected strong aqueous complexes with fluorides at neutral pH and with chlorides, and hydroxides at low pH, we observe that the dominant species in the low to mid pH range to be Tb3+ as a free ion. Still, we do see the presence of fluoride and chloride complexes within the expected low to mid pH range.

In situ Raman study of dissolved CaCO3 minerals under subduction zone conditions

NASA Astrophysics Data System (ADS)

Facq, S.; Daniel, I.; Sverjensky, D. A.

2012-12-01

The fate and the characteristics of the Earth's deep carbon reservoirs are still not well understood [1]. The connection between the surficial and the deep-Earth carbon cycles occurs at subduction zones where carbon is transported into the mantle and where hydrous silicates and carbonate minerals break down releasing H2O and C-species in fluids associated with mantle metasomatism and the generation of arc volcanism [2]. In order to obtain mass balance between recycling and burial in the deep mantle, the study of the dissolution of CaCO3 minerals in equilibrium with aqueous fluids under mantle conditions is crucial. We report a novel integrated experimental and theoretical study of the equilibration of CaCO3 minerals with aqueous solutions (pure water or NaCl solutions) at high pressures and temperatures (0.5 to 8 GPa and 250 to 500 °C). The fluid speciation was studied using in situ Raman spectroscopy coupled to an externally heated membrane type DAC equipped with 500 μm pure synthetic diamond anvils. In a typical experiment, the aqueous fluid and a calcite crystal [3] were loaded in a rhenium gasket. The pressure was determined from the calibrated shift of the carbonate υ1 symmetric stretching mode of aragonite and the temperature measured with a K-type thermocouple. Raman spectra were recorded using a Labram HR800 Raman spectrometer (Horiba Jobin-Yvon) coupled to a Spectra Physics Ar+ laser. At equilibrium with an aragonite crystal, the Raman data show that bicarbonate is the most abundant species in low-pressure fluids (below 4 GPa) whereas carbonate becomes progressively dominant at higher pressure. After correction from their Raman cross-sections [4], the relative amounts of dissolved carbonate and bicarbonate were estimated from the areas of the Raman bands of the carbonate and bicarbonate ions (υ1 and υ5 symmetric stretching modes, respectively). The presence of sodium chloride influences the speciation by extending the pressure field where the bicarbonate species is dominant in the fluid. The Raman data were also used to constrain a theoretical thermodynamic model of the fluid speciation in equilibrium with CaCO3. Building on published calcite solubility data from 400 - 700 °C and 2 - 16 kb [3, 5], revised thermodynamic properties of aqueous CO2 and HCO3-, data for the aqueous CaHCO3+ complex from 4 to 90 °C [6], and estimated dielectric constants of water, enabled an equation of state characterization of the standard Gibbs free energy of CaHCO3+ at the conditions of the Raman study. At 300 - 400 °C, the Raman speciation results were used to constrain equilibrium constants involving the carbonate ion. The results indicate that CO2 is a minor species in fluids in equilibrium with aragonite at 300 - 500 °C and P > 1.0 GPa. Instead, the CaHCO3+ species becomes important at high pressures until carbonate ion becomes the dominant C-species. [1] Marty, B. and Tolstikhin, I.N., Chemical Geology 145, 233 (1998) [2] Schmidt, M.W. and Poli, S., Earth and Planetary Science Letters 163, 163 (1998) [3] Caciagli, N.C. and Manning, C.E., Contributions to Mineralogy and Petrology 146, 275 (2003) [4] Frantz, J., Chemical Geology 152, 211 (1998) [5] Fein, J.B. and Walther, J.V., Contributions to Mineralogy and Petrology 103, 317 (1989) [6] Plummer, L.N. and Busenberg, E., Geochimica et Cosmochimica Acta 46, 1011 (1982)

Estimating PM2.5 speciation concentrations using prototype 4.4 km-resolution MISR aerosol properties over Southern California

NASA Astrophysics Data System (ADS)

Meng, Xia; Garay, Michael J.; Diner, David J.; Kalashnikova, Olga V.; Xu, Jin; Liu, Yang

2018-05-01

Research efforts to better characterize the differential toxicity of PM2.5 (particles with aerodynamic diameters less than or equal to 2.5 μm) speciation are often hindered by the sparse or non-existent coverage of ground monitors. The Multi-angle Imaging SpectroRadiometer (MISR) aboard NASA's Terra satellite is one of few satellite aerosol sensors providing information of aerosol shape, size and extinction globally for a long and continuous period that can be used to estimate PM2.5 speciation concentrations since year 2000. Currently, MISR only provides a 17.6 km product for its entire mission with global coverage every 9 days, a bit too coarse for air pollution health effects research and to capture local spatial variability of PM2.5 speciation. In this study, generalized additive models (GAMs) were developed using MISR prototype 4.4 km-resolution aerosol data with meteorological variables and geographical indicators, to predict ground-level concentrations of PM2.5 sulfate, nitrate, organic carbon (OC) and elemental carbon (EC) in Southern California between 2001 and 2015 at the daily level. The GAMs are able to explain 66%, 62%, 55% and 58% of the daily variability in PM2.5 sulfate, nitrate, OC and EC concentrations during the whole study period, respectively. Predicted concentrations capture large regional patterns as well as fine gradients of the four PM2.5 species in urban areas of Los Angeles and other counties, as well as in the Central Valley. This study is the first attempt to use MISR prototype 4.4 km-resolution AOD (aerosol optical depth) components data to predict PM2.5 sulfate, nitrate, OC and EC concentrations at the sub-regional scale. In spite of its low temporal sampling frequency, our analysis suggests that the MISR 4.4 km fractional AODs provide a promising way to capture the spatial hotspots and long-term temporal trends of PM2.5 speciation, understand the effectiveness of air quality controls, and allow our estimated PM2.5 speciation data to be linked with common spatial units such as census tract or zip code in epidemiological studies. This modeling strategy needs to be validated in other regions when more MISR 4.4 km data becoming available in the future.

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.

Biology and toxicology of tellurium explored by speciation analysis.

PubMed

Ogra, Yasumitsu

2017-05-24

Tellurium (Te) is widely used in industry because it has unique physicochemical properties. Although Te is a non-essential element in animals and plants, it is expected to be metabolized to organometallic compounds having a carbon-Te bond in living organisms exposed to inorganic Te compounds. Thus, the speciation and identification of tellurometabolites are expected to contribute to the depiction of the metabolic chart of Te. Speciation by elemental mass spectrometry and identification by molecular mass spectrometry coupled with separation techniques have significantly contributed to the discovery of tellurometabolites in animals and plants. The aim of this mini review is to present recent advances in the biology and toxicology of tellurium as revealed by speciation and identification by molecular mass spectrometry.

Gas and aerosol carbon in California: comparison of measurements and model predictions in Pasadena and Bakersfield.

EPA Science Inventory

Co-located measurements of fine particulate matter (PM2.5) organic carbon (OC), elemental carbon, radiocarbon (14C), speciated volatile organic compounds (VOCs),and OH radicals during the CalNex field campaign provide a unique opportunity to evaluate the Community Multiscale Air ...

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...

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.

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

Estimating particle speciation concentrations using MISR retrieved aerosol properties in southern California

NASA Astrophysics Data System (ADS)

Meng, X.; Liu, Y.; Diner, D. J.; Garay, M. J.

2016-12-01

Ambient fine particle (PM2.5) has been positively associated with increased mortality and morbidity worldwide. Recent studies highlight the characteristics and differential toxicity of PM2.5 chemical components, which are important for identifying sources, developing targeted particulate matter (PM) control strategies, and protecting public health. Modelling with satellite retrieved data has been proved as the most cost-effective way to estimate ground PM2.5 levels; however, limited studies have predict PM2.5 chemical components with this method. In this study, the experimental MISR 4.4 km aerosol retrievals were used to predict ground-level particle sulfate, nitrite, organic carbon and element carbon concentrations in 16 counties of southern California. The PM2.5 chemical components concentrations were obtained from the National Chemical Speciation Network (CSN) and the Interagency Monitoring of Protected Visual Environments (IMPROVE) network. A generalized additive model (GAM) was developed based on 16-years data (2000-2015) by combining the MISR aerosol retrievals, meteorological variables and geographical indicators together. Model performance was assessed by model fitted R2 and root-mean-square error (RMSE) and 10-fold cross validation. Spatial patterns of sulfate, nitrate, OC and EC concentrations were also examined with 2-D prediction surfaces. This is the first attempt to develop high-resolution spatial models to predict PM2.5 chemical component concentrations with MISR retrieved aerosol properties, which will provide valuable population exposure estimates for future studies on the characteristics and differential toxicity of PM2.5 speciation.

Sulphurisation of homohopanoids: Effects on carbon number distribution, speciation, and 22 S/22 R epimer ratios

NASA Astrophysics Data System (ADS)

Köster, Jürgen; Van Kaam-Peters, Heidy M. E.; Koopmans, Martin P.; De Leeuw, Jan W.; Sinninghe Damsté, Jaap S.

1997-06-01

Sulphurisation has been recognised as the most important diagenetic pathway acting on hopanoids in the organic-rich limestones, marlstone, and dolomite investigated. The qualitative and quantitative analysis of free and S-bound hopanoid moieties revealed that the incorporation of sulphur has a major impact on the carbon number distribution, the speciation and on the 22 S/(22S+22 R) ratio of the hopanoids. C 35 carbon skeletons are preferentially preserved by sulphur incorporation at the end of the side chain. Hopanoid sulphides, with the sulphur atom attached to one carbon atom of ring D or E and to one carbon atom of the side chain (condensed-type), are predominantly formed from precursors with a partially degraded side chain. In all samples the degree of sulphurisation of hopanoids increases with increasing carbon number. The carbon skeleton speciation changes with maturation in favour of hopanoid thiophenes, which are evidently the most stable hopanoid sulphur compounds, and hopanes. Hopanes are mainly formed via a sulphurisation/desulphurisation pathway and increase in concentration with maturity. Their original carbon number distribution is strongly shifted towards the lower homologues. With increasing maturity only a slight dominance of the C 35 members emerges. The most abundant series of condensed-type hopanoid sulphides have a 22R homohopane carbon skeleton that is not isomerised during maturation. The generation of hopanes from these condensed-type hopanoid sulphides during maturation leads to 22 S/(22S+22 R) ratios which increase with carbon number (e.g., from about 0.2 for C 31 to 0.5 for C 35 homologues). Data acquired from the sedimentary rock samples are supported by those obtained from artificial maturation experiments of a limestone by hydrous pyrolysis at different temperatures. The data show that generally accepted molecular maturation parameters have to be applied with caution.

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

1994-01-01

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Effect of pressure on the short-range structure and speciation of carbon in alkali silicate and aluminosilicate glasses and melts at high pressure up to 8 GPa: 13C, 27Al, 17O and 29Si solid-state NMR study

NASA Astrophysics Data System (ADS)

Kim, Eun Jeong; Fei, Yingwei; Lee, Sung Keun

2018-03-01

Despite the pioneering efforts to explore the nature of carbon in carbon-bearing silicate melts under compression, experimental data for the speciation and the solubility of carbon in silicate melts above 4 GPa have not been reported. Here, we explore the speciation of carbon and pressure-induced changes in network structures of carbon-bearing silicate (Na2O-3SiO2, NS3) and sodium aluminosilicate (NaAlSi3O8, albite) glasses quenched from melts at high pressure up to 8 GPa using multi-nuclear solid-state NMR. The 27Al triple quantum (3Q) MAS NMR spectra for carbon-bearing albite melts revealed the pressure-induced increase in the topological disorder around 4 coordinated Al ([4]Al) without forming [5,6]Al. These structural changes are similar to those in volatile-free albite melts at high pressure, indicating that the addition of CO2 in silicate melts may not induce any additional increase in the topological disorder around Al at high pressure. 13C MAS NMR spectra for carbon-bearing albite melts show multiple carbonate species, including [4]Si(CO3)[4]Si, [4]Si(CO3)[4]Al, [4]Al(CO3)[4]Al, and free CO32-. The fraction of [4]Si(CO3)[4]Al increases with increasing pressure, while those of other bridging carbonate species decrease, indicating that the addition of CO2 may enhance mixing of Si and Al at high pressure. A noticeable change is not observed for 29Si NMR spectra for the carbon-bearing albite glasses with varying pressure at 1.5-6 GPa. These NMR results confirm that the densification mechanisms established for fluid-free, polymerized aluminosilicate melts can be applied to the carbon-bearing albite melts at high pressure. In contrast, the 29Si MAS NMR spectra for partially depolymerized, carbon-bearing NS3 glasses show that the fraction of [5,6]Si increases with increasing pressure at the expense of Q3 species ([4]Si species with one non-bridging oxygen as the nearest neighbor). The pressure-induced increase in topological disorder around Si is evident from an increase in peak width of [4]Si with pressure. 17O NMR spectrum shows that the fraction of Na⋯Osbnd [5]Si in carbon-bearing NS3 glasses is less than that of carbon-free NS3 glasses at 6 GPa potentially due to the formation of bridging carbonate species. While its presence is not evident from the 17O NMR spectrum primarily due to low carbon concentration, 13C MAS NMR results imply the formation of bridging carbonates, [4]Si(CO3)[4]Si, above 6 GPa. The spin-lattice relaxation time (T1) of CO2 in albite melts increases with increasing pressure from 42 s (at 1.5 GPa) to 149 s (at 6 GPa). Taking the pressure-induced change in T1 of carbon species into consideration, total carbon content in carbon-bearing albite melts increases with pressure from ∼1 wt% at 1.5 GPa to ∼4.1 wt% at 6 GPa. The results also reveal a noticeable drop in the peak intensity of free carbonates in carbon-bearing NS3 melts at 6 GPa, implying a potential non-linear change in the carbon solubility with pressure. The current results of carbon speciation in the silicate melts above 4 GPa provide an improved link among the atomic configurations around carbon species, their carbon contents, and isotope composition of carbon-bearing melts in the upper mantle.

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.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

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

Bone, Sharon E.; Dynes, James J.; Cliff, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2) in anoxic sediments; yet studies now show that UO 2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yetmore » been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO 2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.« less

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

NASA Astrophysics Data System (ADS)

Morgan, G. B., VI; Chou, I.-Ming; Pasteris, J. D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H 2C 2O 4 · 2H 2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750°C, with bulk fluid densities in the range 0.01-0.53 g/cm 3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350°C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3 H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H 2O-CO 2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of SAXENA and FEI (1988). Such disagreement suggests that the formations of CH 4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650°C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H 2O-CO 2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions.

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

USGS Publications Warehouse

Morgan, G.B.; Chou, I.-Ming; Pasteris, J.D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H2C2O4 ?? 2H2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750??C, with bulk fluid densities in the range 0.01-0.53 g/cm3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350??C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H2O-CO2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650??C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H2O-CO2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions. ?? 1992.

Volatile and semivolatile organic compounds in laboratory ...

EPA Pesticide Factsheets

Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particulate organics were quantified by gas chromatography/mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (~60 %) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. Speciated organic PM2.5 mass was dominated by the following compound classes: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for PM2.5 organic acids including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12 %) of all speciated compound classes measured in this work. Levoglucosan contributed 2-3 % of the OC mass, while methoxyphenols represented 0.2-0.3 % of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon. Total HAP VOC and particulate polycyclic aromatic hydrocarbon emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions. This p

Feasibility of coupling a thermal/optical carbon analyzer to a quadrupole mass spectrometer for enhanced PM2.5 speciation.

PubMed

Riggio, Gustavo M; Chow, Judith C; Cropper, Paul M; Wang, Xiaoliang; Yatavelli, Reddy L N; Yang, Xufei; Watson, John G

2018-05-01

A thermal/optical carbon analyzer (TOA), normally used for quantification of organic carbon (OC) and elemental carbon (EC) in PM 2.5 (fine particulate matter) speciation networks, was adapted to direct thermally evolved gases to an electron impact quadrupole mass spectrometer (QMS), creating a TOA-QMS. This approach produces spectra similar to those obtained by the Aerodyne aerosol mass spectrometer (AMS), but the ratios of the mass to charge (m/z) signals differ and must be remeasured using laboratory-generated standards. Linear relationships are found between TOA-QMS signals and ammonium (NH 4 + ), nitrate (NO 3 - ), and sulfate (SO 4 2- ) standards. For ambient samples, however, positive deviations are found for SO 4 2- , compensated by negative deviations for NO 3 - , at higher concentrations. This indicates the utility of mixed-compound standards for calibration or separate calibration curves for low and high ion concentrations. The sum of the QMS signals across all m/z after removal of the NH 4 + , NO 3 - , and SO 4 2- signals was highly correlated with the carbon content of oxalic acid (C₂H₂O₄) standards. For ambient samples, the OC derived from the TOA-QMS method was the same as the OC derived from the standard IMPROVE_A TOA method. This method has the potential to reduce complexity and costs for speciation networks, especially for highly polluted urban areas such as those in Asia and Africa. Ammonium, nitrate, and sulfate can be quantified by the same thermal evolution analysis applied to organic and elemental carbon. This holds the potential to replace multiple parallel filter samples and separate laboratory analyses with a single filter and a single analysis to account for a large portion of the PM 2.5 mass concentration.

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

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.

[Speciation Characteristics and Bioavailability of Heavy Metals in Oasis Soil Under Pb, Zn Combined Stress].

PubMed

Jin, Cheng; Zhao, Zhuan-jun; Nan, Zhong-ren; Wang, Sheng-li; Wu, Wen-fei; Wang, Hou-cheng

2015-05-01

Pot experiments were conducted on cole (Brassica) grown in oasis soil under combined stress of lead and zinc, to study the effect of heavy metal combined pollution on cole growth as well as the speciation conversion rules and bioavailability. The result showed that the promoting effect on cole growth was shown in the low concentration treatments, especially on stem leaves. With addition of exotic heavy metals, the main speciations of Pb and Zn in the soil transformed from tight-bound to loose-bound forms as compared to the control, and the bioavailability of heavy metals was increased. And, the exchangeable Pb and the carbonate bound form of Zn were the major contributing speciations which were absorbed in different parts of cole. What's more, the capabilities of uptake and translocation of Pb and Zn by cole were stronger at lower stress levels, and the enrichment and migration coefficients decreased with the increasing content of bioavailable fraction of the corresponding element or the coexisting element. In all treatments, the Pb concentration in the stem leaves of cole exceeded the food safety threshold, therefore it is recommended to conduct detection of relevant indicators before planting foliage vegetables in this kind of soil.

Lead speciation in indoor dust: a case study to assess old paint contribution in a Canadian urban house

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

Beauchemin, Suzanne; MacLean, Lachlan C.W.; Rasmussen, Pat E.

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg{sup -1}) and dust (200-1,000 mg Pb kg{sup -1}) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pbmore » species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 {micro}m house dust samples. In the dust fraction <36 {micro}m, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.« less

Lead Speciation in Indoor Dust: A Case Study to Assess Old Paint Contribution in a Canadian Urban House

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

S Beauchemin; L MacLean; P Rasmussen

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg{sup -1}) and dust (200-1,000 mg Pb kg{sup -1}) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pbmore » species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 m house dust samples. In the dust fraction <36 {mu}m, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.« less

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

PubMed

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

2008-08-01

A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as an intentional quantitative tracer for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 microg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions.

Detailed Characterization and Profiles of Crankcase and Diesel Particular Matter Exhaust Emissions Using Speciated Organics

PubMed Central

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

2008-01-01

A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as intentional quantitative tracers for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes, and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 μg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions. PMID:18754490

Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

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

Prywer, Jolanta, E-mail: jolanta.prywer@p.lodz.pl; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

2015-11-15

Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation ofmore » carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca{sup 2+} ions and causes the formation of CaCit{sup −} and Ca{sub 10}(PO{sub 4}){sub 6}CO{sub 3} complexes. Trisodium citrate binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed. - Highlights: • Trisodium citrate (TC) increases induction time of carbonate apatite (CA) formation. • TC decreases the efficiency of CA precipitation. • The inhibitory effect of TC is explained in base of chemical speciation analysis. • The inhibitory effect is mainly related with the fact that TC binds Ca{sup 2+} ions. • TC binds Ca{sup 2+} ions in the range of pH from 6 to 9.5 for which CA is formed.« less

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.

The influence of metal speciation in combustion waste on the efficiency of Cu, Pb, Zn, Cd, Ni and Cr bioleaching in a mixed culture of sulfur-oxidizing and biosurfactant-producing bacteria.

PubMed

Karwowska, Ewa; Wojtkowska, Małgorzata; Andrzejewska, Dorota

2015-12-15

Metal leachability from ash and combustion slag is related to the physico-chemical properties, including their speciation in the waste. Metals speciation is an important factor that influences the efficiency of metal bioleaching from combustion wastes in a mixed culture of acidophilic and biosurfactant-producing bacteria. It was observed that individual metals tended to occur in different fractions, which reflects their susceptibility to bioleaching. Cr and Ni were readily removed from wastes when present with a high fraction bound to carbonates. Cd and Pb where not effectively bioleached when present in high amounts in a fraction bound to organic matter. The best bioleaching results were obtained for power plant slag, which had a high metal content in the exchangeable, bound to carbonates and bound to Fe and Mg oxides fractions- the metal recovery percentage for Zn, Cu and Ni from this waste exceeded 90%. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Selenium Speciation in the Fountain Creek Watershed (Colorado, USA) Correlates with Water Hardness, Ca and Mg Levels.

PubMed

Carsella, James S; Sánchez-Lombardo, Irma; Bonetti, Sandra J; Crans, Debbie C

2017-04-30

The environmental levels of selenium (Se) are regulated and strictly enforced by the Environmental Protection Agency (EPA) because of the toxicity that Se can exert at high levels. However, speciation plays an important role in the overall toxicity of Se, and only when speciation analysis has been conducted will a detailed understanding of the system be possible. In the following, we carried out the speciation analysis of the creek waters in three of the main tributaries-Upper Fountain Creek, Monument Creek and Lower Fountain Creek-located in the Fountain Creek Watershed (Colorado, USA). There are statistically significant differences between the Se, Ca and Mg, levels in each of the tributaries and seasonal swings in Se, Ca and Mg levels have been observed. There are also statistically significant differences between the Se levels when grouped by Pierre Shale type. These factors are considered when determining the forms of Se present and analyzing their chemistry using the reported thermodynamic relationships considering Ca 2+ , Mg 2+ , SeO₄ 2- , SeO₃ 2- and carbonates. This analysis demonstrated that the correlation between Se and water hardness can be explained in terms of formation of soluble CaSeO₄. The speciation analysis demonstrated that for the Fountain Creek waters, the Ca 2+ ion may be mainly responsible for the observed correlation with the Se level. Considering that the Mg 2+ level is also correlating linearly with the Se levels it is important to recognize that without Mg 2+ the Ca 2+ would be significantly reduced. The major role of Mg 2+ is thus to raise the Ca 2+ levels despite the equilibria with carbonate and other anions that would otherwise decrease Ca 2+ levels.

Preignition and Autoignition Behavior of the Xylene Isomers

DTIC Science & Technology

2010-03-01

of the carbon-carbon bond at the carbon atom one removed from the radical site (Law, 2006). 10 ketohydroperoxide produces another hydroxyl radical...paraffin, naphthene , and aromatic content of jet fuel samples fairly well (Holley et al., 2007). A more detailed chemical speciation has been...an intermediate from toluene oxidation in the PFR facility. This also removes concern that phenol may have reacted during the quenching process, if

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.

Mercury speciation in coastal sediments from the central east coast of India by modified BCR method.

PubMed

Chakraborty, Parthasarathi; Raghunadh Babu, P V; Vudamala, Krushna; Ramteke, Darwin; Chennuri, Kartheek

2014-04-15

This is the first study to describe distribution and speciation of Hg in coastal sediments from the central east coast of India. The concentrations of Hg in the studied sediments were found to be much lower than the Hg concentration recommended in coastal sediments by the United State Environmental Protection Agency and the Canadian Council of Ministers of the Environment for the protection of aquatic life. This study suggests that the interactions between Hg and coastal sediments are influenced by particle size (sand, silt and clay) of the sediments and the total organic carbon (TOC) content in the sediments. It was found that the coastal sediments from the central east coast of India could act as a sink for Hg. The availability of strong uncomplexed-Hg binding sites in the coastal sediments was observed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Alleviation of environmental risks associated with severely contaminated mine tailings using amendments: Modeling of trace element speciation, solubility, and plant accumulation.

PubMed

Pardo, Tania; Bes, Cleménce; Bernal, Maria Pilar; Clemente, Rafael

2016-11-01

Tailings are considered one of the most relevant sources of contamination associated with mining activities. Phytostabilization of mine spoils may need the application of the adequate combination of amendments to facilitate plant establishment and reduce their environmental impact. Two pot experiments were set up to assess the capability of 2 inorganic materials (calcium carbonate and a red mud derivate, ViroBind TM ), alone or in combination with organic amendments, for the stabilization of highly acidic trace element-contaminated mine tailings using Atriplex halimus. The effects of the treatments on tailings and porewater physico-chemical properties and trace-element accumulation by the plants, as well as the processes governing trace elements speciation and solubility in soil solution and their bioavailability were modeled. The application of the amendments increased tailings pH and decreased (>99%) trace elements solubility in porewater, but also changed the speciation of soluble Cd, Cu, and Pb. All the treatments made A. halimus growth in the tailings possible; organic amendments increased plant biomass and nutritional status, and reduced trace-element accumulation in the plants. Tailings amendments modified trace-element speciation in porewater (favoring the formation of chlorides and/or organo-metallic forms) and their solubility and plant uptake, which were found to be mainly governed by tailing/porewater pH, electrical conductivity, and organic carbon content, as well as soluble/available trace-element concentrations. Environ Toxicol Chem 2016;35:2874-2884. © 2016 SETAC. © 2016 SETAC.

Toward the use of surface modified activated carbon in speciation: selective preconcentration of selenite and selenate in environmental waters.

PubMed

Tsoi, Yeuk-Ki; Leung, Kelvin Sze-Yin

2011-04-22

This paper describes a novel application of tetrabutylammonium hydroxide-modified activated carbon (AC-TBAH) to the speciation of ultra-trace Se(IV) and Se(VI) using LC-ICP-DRC-MS. The anion exchange functionality was immobilized onto the AC surface enables selective preconcentration of inorganic Se anions in a wide range of working pHs. Simultaneous retention and elution of both analytes, followed by subsequent analysis with LC-ICP-DRC-MS, allows to accomplish speciation analysis in natural samples without complicated redox pre-treatment. The laboratory-made column of immobilized AC (0.4 g of sorbent packed in a 6 mL syringe barrel) has achieved analyte enrichment factors of 76 and 93, respectively, for Se(IV) and Se(VI), thus proving its superior preconcentration efficiency and selectivity over common AC. The considerable enhancement in sensitivity achieved by using the preconcentration column has improved the method's detection limits to 1.9-2.2 ng L(-1), which is a 100-fold improvement compared with direct injection. The analyte recoveries from heavily polluted river matrix were between 95.3 and 107.7% with less than 5.0% RSD. The robustness of the preconcentration and speciation method was validated by analysis of natural waters collected from rivers and reservoirs in Hong Kong. The modified AC material is hence presented as a low-cost yet robust substitute for conventional anion exchange resins for routine applications. Copyright © 2011 Elsevier B.V. All rights reserved.

Arsenic speciation and sorption in natural environments

USGS Publications Warehouse

Campbell, Kate M.; Nordstrom, D. Kirk

2014-01-01

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

In situ mid-infrared spectroscopic titration of forsterite with water in supercritical CO2: Dependence of mineral carbonation on quantitative water speciation

NASA Astrophysics Data System (ADS)

Loring, J. S.; Thompson, C. J.; Wang, Z.; Schaef, H. T.; Martin, P.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2011-12-01

Geologic sequestration of carbon dioxide holds promise for helping mitigate CO2 emissions generated from the burning of fossil fuels. Supercritical CO2 (scCO2) plumes containing variable water concentrations (wet scCO2) will displace aqueous solution and dominate the pore space adjacent to caprocks. It is important to understand possible mineral reactions with wet scCO2 to better predict long-term caprock integrity. We introduce novel in situ instrumentation that enables quantitative titrations of reactant minerals with water in scCO2 at temperatures and pressures relevant to target geologic reservoirs. The system includes both transmission and attenuated total reflection mid-infrared optics. Transmission infrared spectroscopy is used to measure concentrations of water dissolved in the scCO2, adsorbed on mineral surfaces, and incorporated into precipitated carbonates. Single-reflection attenuated total reflection infrared spectroscopy is used to monitor water adsorption, mineral dissolution, and carbonate precipitation reactions. Results are presented for the infrared spectroscopic titration of forsterite (Mg2SiO4), a model divalent metal silicate, with water in scCO2 at 100 bar and at both 50 and 75°C. The spectral data demonstrate that the quantitative speciation of water as either dissolved or adsorbed is important for understanding the types, growth rates, and amounts of carbonate precipitates formed. Relationships between dissolved/adsorbed water, water concentrations, and the role of liquid-like adsorbed water are discussed. Our results unify previous in situ studies from our laboratory based on infrared spectroscopy, nuclear magnetic resonance spectroscopy and X-ray diffraction.

Iron solubility driven by speciation in dust sources to the ocean

USGS Publications Warehouse

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

2009-01-01

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

TESTING THE EFFECTS OF OCEAN ACIDIFICATION ON ALGAL METABOLISM: CONSIDERATIONS FOR EXPERIMENTAL DESIGNS(1).

PubMed

Hurd, Catriona L; Hepburn, Christopher D; Currie, Kim I; Raven, John A; Hunter, Keith A

2009-12-01

Ocean acidification describes changes in the carbonate chemistry of the ocean due to the increased absorption of anthropogenically released CO2 . Experiments to elucidate the biological effects of ocean acidification on algae are not straightforward because when pH is altered, the carbon speciation in seawater is altered, which has implications for photosynthesis and, for calcifying algae, calcification. Furthermore, photosynthesis, respiration, and calcification will themselves alter the pH of the seawater medium. In this review, algal physiologists and seawater carbonate chemists combine their knowledge to provide the fundamental information on carbon physiology and seawater carbonate chemistry required to comprehend the complexities of how ocean acidification might affect algae metabolism. A wide range in responses of algae to ocean acidification has been observed, which may be explained by differences in algal physiology, timescales of the responses measured, study duration, and the method employed to alter pH. Two methods have been widely used in a range of experimental systems: CO2 bubbling and HCl/NaOH additions. These methods affect the speciation of carbonate ions in the culture medium differently; we discuss how this could influence the biological responses of algae and suggest a third method based on HCl/NaHCO3 additions. We then discuss eight key points that should be considered prior to setting up experiments, including which method of manipulating pH to choose, monitoring during experiments, techniques for adding acidified seawater, biological side effects, and other environmental factors. Finally, we consider incubation timescales and prior conditioning of algae in terms of regulation, acclimation, and adaptation to ocean acidification. © 2009 Phycological Society of America.

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.

Soil-solution speciation of Cd as affected by soil characteristics in unpolluted and polluted soils.

PubMed

Meers, Erik; Unamuno, Virginia; Vandegehuchte, Michiel; Vanbroekhoven, Karolien; Geebelen, Wouter; Samson, Roeland; Vangronsveld, Jaco; Diels, Ludo; Ruttens, Ann; Du Laing, Gijs; Tack, Filip

2005-03-01

Total metal content by itself is insufficient as a measure to indicate actual environmental risk. Understanding the mobility of heavy metals in the soil and their speciation in the soil solution is of great importance for accurately assessing environmental risks posed by these metals. In a first explorative study, the effects of general soil characteristics on Cd mobility were evaluated and expressed in the form of empirical formulations. The most important factors influencing mobility of Cd proved to be pH and total soil content. This may indicate that current legislation expressing the requirement for soil sanitation in Flanders (Belgium) as a function of total soil content, organic matter, and clay does not successfully reflect actual risks. Current legal frameworks focusing on total content, therefore, should be amended with criteria that are indicative of metal mobility and availability and are based on physicochemical soil properties. In addition, soil-solution speciation was performed using two independent software packages (Visual Minteq 2.23 and Windermere Humic Aqueous model VI [WHAM VI]). Both programs largely were in agreement in concern to Cd speciation in all 29 soils under study. Depending on soil type, free ion and the organically complexed forms were the most abundant species. Additional inorganic soluble species were sulfates and chlorides. Minor species in solution were in the form of nitrates, hydroxides, and carbonates, the relative importance of which was deemed insignificant in comparison to the four major species.

A gas chromatographic method for the determination of bicarbonate and dissolved gases

USDA-ARS?s Scientific Manuscript database

A gas chromatographic method for the rapid determination of aqueous carbon dioxide and its speciation into solvated carbon dioxide and bicarbonate is presented. One-half mL samples are injected through a rubber septum into 20-mL vials that are filled with 9.5 mL of 0.1 N HCl. A one mL portion of the...

Use of X-Ray Absorption Spectroscopy (XAS) to Speciate Manganese in Airborne Particulate Matter from 5 Counties Across the US

PubMed Central

Datta, Saugata; Rule, Ana M; Mihalic, Jana N; Chillrud, Steve N; Bostick, Benjamin C.; Ramos-Bonilla, Juan P; Han, Inkyu; Polyak, Lisa M; Geyh, Alison S; Breysse, Patrick N

2012-01-01

The purpose of this study is to characterize manganese oxidation states and speciation in airborne particulate matter (PM), and describe how these potentially important determinants of PM toxicity vary by location. Ambient PM samples were collected from five counties across the US using a high volume sequential cyclone system that collects PM in dry bulk form segregated into “coarse” and “fine” size fractions. The fine fraction was analyzed for this study. Analyses included total Mn using ICP-MS, and characterization of oxidation states and speciation using X-ray Absorption Spectroscopy (XAS). XAS spectra of all samples and ten standard compounds of Mn were obtained at the National Synchrotron Light Source. XAS data was analyzed using Linear Combination Fitting (LCF). Results of the LCF analysis describe differences in composition between samples. Mn(II) acetate and Mn(II) oxide are present in all samples, while Mn(II) carbonate and Mn(IV) oxide are absent. To the best of our knowledge, this is the first paper to characterize Mn composition of ambient PM and examine differences between urban sites in the US. Differences in oxidation state and composition indicate regional variations in sources and atmospheric chemistry that may help explain differences in health effects identified in epidemiological studies. PMID:22309075

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

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Organic nitrogen chemistry during low-grade metamorphism

USGS Publications Warehouse

Boudou, J.-P.; Schimmelmann, A.; Ader, M.; Mastalerz, Maria; Sebilo, M.; Gengembre, L.

2008-01-01

Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized ??-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade. ?? 2007 Elsevier Ltd. All rights reserved.

Whole-cell bioreporters and risk assessment of environmental pollution: A proof-of-concept study using lead.

PubMed

Zhang, Xiaokai; Qin, Boqiang; Deng, Jianming; Wells, Mona

2017-10-01

As the world burden of environmental contamination increases, it is of the utmost importance to develop streamlined approaches to environmental risk assessment in order to prioritize mitigation measures. Whole-cell biosensors or bioreporters and speciation modeling have both become of increasing interest to determine the bioavailability of pollutants, as bioavailability is increasingly in use as an indicator of risk. Herein, we examine whether bioreporter results are able to reflect expectations based on chemical reactivity and speciation modeling, with the hope to extend the research into a wider framework of risk assessment. We study a specific test case concerning the bioavailability of lead (Pb) in aqueous environments containing Pb-complexing ligands. Ligands studied include ethylene diamine tetra-acetic acid (EDTA), meso-2,3 dimercaptosuccinic acid (DMSA), leucine, methionine, cysteine, glutathione, and humic acid (HA), and we also performed experiments using natural water samples from Lake Tai (Taihu), the third largest lake in China. We find that EDTA, DMSA, cysteine, glutathione, and HA amendment significantly reduced Pb bioavailability with increasing ligand concentration according to a log-sigmoid trend. Increasing dissolved organic carbon in Taihu water also had the same effect, whereas leucine and methionine had no notable effect on bioavailability at the concentrations tested. We find that bioreporter results are in accord with the reduction of aqueous Pb 2+ that we expect from the relative complexation affinities of the different ligands tested. For EDTA and HA, for which reasonably accurate ionization and complexation constants are known, speciation modeling is in agreement with bioreporter response to within the level of uncertainty recognised as reasonable by the United States Environmental Protection Agency for speciation-based risk assessment applications. These findings represent a first step toward using bioreporter technology to streamline the biological confirmation or validation of speciation modeling for use in environmental risk assessment. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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

PubMed

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

2015-10-01

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

Biostabilization of cadmium contaminated sediments using indigenous sulfate reducing bacteria: Efficiency and process.

PubMed

Peng, Weihua; Li, Xiaomin; Liu, Tong; Liu, Yingying; Ren, Jinqian; Liang, Dawei; Fan, Wenhong

2018-06-01

Sulfate reducing bacteria (SRB) was used to stabilize cadmium (Cd) in sediments spiked with Cd. The study found that the Cd in sediments (≤600 mg kg -1 ) was successfully stabilized after 166 d SRB bio-treatment. This was verified by directly and indirectly examining Cd speciation in sediments, mobilization index, and Cd content in interstitial water. After 166 d bio-treatment, compared with control groups, Cd concentrations in interstitial water of Cd-spiked sediments were reduced by 77.6-96.4%. The bioavailable fractions of Cd (e.g., exchangeable and carbonate bound phases) were reduced, while more stable fractions of Cd (e.g., Fe-Mn oxide, organic bound, and residual phases) were increased. However, Cd mobilization in sediment was observed during the first part of bio-treatment (32 d), leading to an increase of Cd concentrations in the overlying water. Bacterial community composition (e.g., richness, diversity, and typical SRB) played an important role in Cd mobilization, dissolution, and stabilization. Bacterial community richness and diversity, including the typical SRB (e.g., Desulfobacteraceae and Desulfobulbaceae), were enhanced. However, bacterial communities were also influenced by Cd content and its speciations (especially the exchangeable and carbonate bound phases) in sediments, as well as total organic carbon in overlying water. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

Solubility of Aragonite in Subduction Water-Rich Fluids

NASA Astrophysics Data System (ADS)

Daniel, I.; Facq, S.; Petitgirard, S.; Cardon, H.; Sverjensky, D. A.

2017-12-01

Carbonate dissolution in subduction zone fluids is critical to the carbon budget in subduction zones. Depending on the solubility of carbonate minerals in aqueous fluids, the subducting lithosphere may be either strongly depleted and the mantle metasomatized if the solubility is high, as recently suggested by natural samples or transport carbon deeper into the Earth's mantle if the solubility is low enough [1, 2]. Dissolution of carbonate minerals strongly depends on pressure and temperature as well as on the chemistry of the fluid, leading to a highly variable speciation of aqueous carbon. Thanks to recent advances in theoretical aqueous geochemistry [3, 4], combined experimental and theoretical efforts now allow the investigation of speciation and solubility of carbonate minerals in aqueous fluids at PT conditions higher than previously feasible [4, 5]. In this study, we present new in situ X-ray fluorescence measurements of aragonite dissolution up to 5 GPa and 500°C and the subsequent thermodynamic model of aragonite solubility in aqueous fluids thanks to the Deep Earth Water model. The amount of dissolved aragonite in the fluid was calculated from challenging and unprecedented measurements of the Ca fluorescence K-lines at low-energy. Experiments were performed at the ESRF, beamline ID27 using a dedicated design of an externally-heated diamond anvil cell and an incident high-flux and highly focused monochromatic X-Ray beam at 20 keV. The results show a spectacularly high solubility of aragonite at HP-HT in water, further enhanced in presence of NaCl and silica in the solution. [1] Frezzotti, M. L. et al. (2011) doi:10.1038/ngeo1246. [2] Ague, J. J. and Nicolescu, S. (2014) doi:10.1038/ngeo2143. [3] Pan, D. et al. (2013) doi: 10.1073/pnas.1221581110. [4] Sverjensky, D. A et al. (2014) doi: 10.1016/j.gca.2013.12.019. [5] Facq, S. et al. (2014) doi: 10.1016/j.gca.2014.01.030.

Iron Speciation and Mixing in Single Aerosol Particles from the Asian Continental Outflow

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

Moffet, Ryan C.; Furutani, Hiroshi; Rodel, Tobias

2012-04-04

Bioavailable iron from atmospheric aerosol is an essential nutrient that can control oceanic productivity, thereby impacting the global carbon budget and climate. Particles collected on Okinawa Island during an atmospheric pollution transport event from China were analyzed using complementary single particle techniques to determine the iron source and speciation. Comparing the spatial distribution of iron within ambient particles and standard Asian mineral dust, it was determined that field-collected atmospheric Fe-containing particles have numerous sources, including anthropogenic sources such as coal combustion. Fe-containing particles were found to be internally mixed with secondary species such as sulfate, soot, and organic carbon. Themore » mass weighted average Fe(II) fraction (defined as Fe(II)/[Fe(II)+Fe(III)]) was determined to be 0.33 {+-} 0.08. Within the experimental uncertainty, this value lies close to the range of 0.26-0.30 determined for representative Asian mineral dust. Previous studies have indicated that the solubility of iron from combustion is much higher than that from mineral dust. Therefore, chemical and/or physical differences other than oxidation state may help explain the higher solubility of iron in atmospheric particles.« less

Speciation of the Potential Antitumor Agent Vanadocene Dichloride in the Blood Plasma and Model Systems.

PubMed

Sanna, Daniele; Ugone, Valeria; Micera, Giovanni; Pivetta, Tiziana; Valletta, Elisa; Garribba, Eugenio

2015-09-08

The speciation of the potential antitumor agent vanadocene dichloride ([Cp2VCl2], abbreviated with VDC) in the blood plasma was studied by instrumental (EPR, ESI-MS, MS-MS, and electronic absorption spectroscopy) and computational (DFT) methods. The behavior of VDC at pH 7.4 in aqueous solution, the interaction with the most important bioligands of the plasma (oxalate, carbonate, phosphate, lactate, citrate, histidine, and glycine among those with low molecular mass and transferrin and albumin between the proteins) was evaluated. The results suggest that [Cp2VCl2] transforms at physiological pH to [Cp2V(OH)2] and that only oxalate, carbonate, phosphate, and lactate are able to displace the two OH(-) ions to yield [Cp2V(ox)], [Cp2V(CO3)], [Cp2V(lactH(-1))], and [Cp2V(HPO4)]. The formation of the adducts with oxalate, carbonate, lactate, and hydrogen phosphate was confirmed also by ESI-MS and MS-MS spectra. The stability order is [Cp2V(ox)] ≫ [Cp2V(CO3)] > [Cp2V(lactH(-1))] > [Cp2V(HPO4)]. No interaction between VDC and plasma proteins was detected under our experimental conditions. Several model systems containing the bioligands (bL) in the same relative ratio as in the blood samples were also examined. Finally, the speciation of VDC in the plasma was studied. The results obtained show that the model systems behave as the blood plasma and indicate that when V concentration is low (10 μM) VDC is transported in the bloodstream as [Cp2V(ox)]; when V concentration is high (100 μM) oxalate binds only 9.2 μM of [Cp2V](2+), whereas the remaining part distributes between [Cp2V(CO3)] (main species) and [Cp2V(lactH(-1))] (minor species); and when V concentration is in the range 10-100 μM [Cp2V](2+) distributes between [Cp2V(ox)] and [Cp2V(CO3)].

[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.

Solubility, Partitioning, and Speciation of Carbon in Shallow Magma Oceans of Terrestrial Planets Constrained by High P-T Experiments

NASA Astrophysics Data System (ADS)

Chi, H.; Dasgupta, R.; Shimizu, N.

2011-12-01

Deep planetary volatile cycles have a critical influence on planetary geodynamics, atmospheres, climate, and habitability. However, the initial conditions that prevailed in the early, largely molten Earth and other terrestrial planets, in terms of distribution of volatiles between various reservoirs - metals, silicates, and atmosphere - remains poorly constrained. Here we investigate the solubility, partitioning, and speciation of carbon-rich volatile species in a shallow magma ocean environment, i.e., in equilibrium with metallic and silicate melts. A series of high pressure-temperature experiments using a piston cylinder apparatus were performed at 1-3 GPa, 1500-1800 °C on synthetic basaltic mixtures + Fe-Ni metal powders contained in graphite capsules. All the experiments produced glassy silicate melt pool in equilibrium with quenched metal melt composed of dendrites of cohenite and kamacite. Major element compositions of the resulting phases and the carbon content of metallic melts were analyzed by EPMA at NASA-JSC. Carbon and hydrogen concentrations of basaltic glasses were determined using Cameca IMS 1280 SIMS at WHOI and speciation of dissolved volatiles was constrained using FTIR and Raman spectroscopy at Rice University. Based on the equilibria - FeO (silicate melt) = Fe (metal alloy melt) + 1/2O2, we estimate the oxygen fugacity of our experiments in the range of ΔIW of -1 to -2. FTIR analysis on doubly polished basaltic glass chips suggests that the concentrations of dissolved CO32- or molecular CO2 are negligible in graphite and metal saturated reduced conditions, whereas the presence of dissolved OH- is evident from the asymmetric peak at 3500 cm-1. Collected Raman spectra of basaltic glasses in the frequency range of 200-4200 cm-1 suggest that hydrogen is present both as dissolved OH- species (band at 3600 cm-1) and as molecular H2 (band near 4150 cm-1) for all of our experiments. Faint peaks near 2915 cm-1 and consistent peaks near 740 cm-1 suggest that possible carbon species in our reduced glasses are likely minor CH4 and Si-C, respectively and are consistent with the recent solubility studies at reduced conditions [1,2]. Carbon solubility (calibrated using 12C/30Si) at graphite saturation in our reduced basaltic glasses is only in the range 20-100 ppm C, with H2O contents in the range of 0.2-0.7 wt.%. In contrast to the low dissolved carbon concentration in the basaltic silicate melts, carbon solubility in quenched metallic melts vary in the range of 5-7 wt.%. Our preliminary work indicates that the solubility of carbon in reduced basaltic melts relevant for early magma conditions may be several orders of magnitude lower compared to the solubility of carbon in modern terrestrial basalts. This coupled with significant solubility of carbon in Fe-Ni metallic melt suggests that most of magma ocean carbon was likely partitioned into deep metallic melts. Further metal-silicate experiments with more depolymerized basaltic melts of variable compositions are underway and will be presented. [1] Kadik et al. JPetrol 45, 1297-1310, 2004; [2] Kadik et al. Geochem Int 44, 33-47, 2006.

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.

Solubility and Speciation in the Water-Carbon Dioxide System

NASA Astrophysics Data System (ADS)

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

2016-12-01

The fluid-fluid miscibility surface of the water-carbon dioxide system contains broad regions (in pressure-composition space) exhibiting gradual variations in the temperature of miscibility; this is as expected. However, there is additionally a line of pressure, extending from roughly 2 GPa and 20 mole% CO2 to 6 GPa and 40 mole%, above which the temperature necessary to complete miscibility falls precipitously. This line, which closely approximates a hard limit, is hypothesized to demark a shift in speciation of dissolved CO2. In the same region of pressure the equilibrium limits of a new solid phase, composed of both water and CO2, have been determined. This new phase, the IR and Raman spectra of which led Wang et al.* to ascribe it to carbonic acid, has an observed associated aqueous form which must, in addition to the well-known bicarbonate and carbonate ions, affect the miscibilities of the system. Since zones of rapid subduction are expected to experience the regions of temperatures and pressures at which these equilibria are observed to shift, the chemical nature of these fluids is expected to undergo significant changes during the subduction process. * Wang H., Zeuschner J., Eremets M., Troyan I. and Willams J. (2016) Sci. Rep. 6, 19902-1-8

Evolution of Early Paleoproterozoic Ocean Chemistry as Recorded by Black Shales

NASA Astrophysics Data System (ADS)

Scott, C.; Bekker, A.; Lyons, T. W.; Planavsky, N. J.; Wing, B. A.

2010-12-01

In recent years, Precambrian biogeochemists have focused largely on the abundance, speciation and isotopic composition of major and trace elements preserved in organic carbon-rich black shales in order to track the co-evolution of ocean chemistry and life on Earth. Despite the fact that the period from 2.5 to 2.0 Ga hosted major events in Earth’s history, such as the Great Oxidation Event (GOE), an era of global glaciations, a massive and long-lived carbon isotope excursion and the end to banded iron formation (BIF) deposition, each with the potential to directly alter global biogeochemical cycles, it is perhaps best known for its unknowns. In order to help close this gap in our understanding of the evolution of Precambrian ocean chemistry we present a detailed biogeochemical study of Paleoproterozoic black shales deposited between 2.5 and 2.0 Ga. Our study integrates Fe speciation, trace metal chemistry and C, S and N isotope analyses to provide a thorough characterization of marine biogeochemical cycles as they responded to the GOE and set the stage for the demise of BIFs at ca. 1.8 Ga. Our data reveal an ocean that was both surprising similar to, and demonstrably different from, Archean and later Proterozoic oceans. Of particular interest, we find that ferruginous and euxinic conditions co-existed during this period and that sea water trace metal inventories fluctuated dramatically in conjunction with major carbon isotope excursions. By comparing our Paleoproterozoic contribution with recent biogeochemical studies of other Precambrian black shales we can begin to track first order changes in ocean chemistry without the major time gaps that have plagued previous attempts.

Reactive transport modeling of the enhancement of density-driven CO 2 convective mixing in carbonate aquifers and its potential implication on geological carbon sequestration

DOE PAGES

Islam, Akand; Sun, Alexander Y.; Yang, Changbing

2016-04-20

We study the convection and mixing of CO 2 in a brine aquifer, where the spread of dissolved CO 2 is enhanced because of geochemical reactions with the host formations (calcite and dolomite), in addition to the extensively studied, buoyancy-driven mixing. The nonlinear convection is investigated under the assumptions of instantaneous chemical equilibrium, and that the dissipation of carbonate rocks solely depends on flow and transport and chemical speciation depends only on the equilibrium thermodynamics of the chemical system. The extent of convection is quantified in term of the CO 2 saturation volume of the storage formation. Our results suggestmore » that the density increase of resident species causes significant enhancement in CO 2 dissolution, although no significant porosity and permeability alterations are observed. Furthermore, early saturation of the reservoir can have negative impact on CO 2 sequestration.« less

Reactive Transport Modeling of the Enhancement of Density-Driven CO2 Convective Mixing in Carbonate Aquifers and its Potential Implication on Geological Carbon Sequestration.

PubMed

Islam, Akand; Sun, Alexander Y; Yang, Changbing

2016-04-20

We study the convection and mixing of CO2 in a brine aquifer, where the spread of dissolved CO2 is enhanced because of geochemical reactions with the host formations (calcite and dolomite), in addition to the extensively studied, buoyancy-driven mixing. The nonlinear convection is investigated under the assumptions of instantaneous chemical equilibrium, and that the dissipation of carbonate rocks solely depends on flow and transport and chemical speciation depends only on the equilibrium thermodynamics of the chemical system. The extent of convection is quantified in term of the CO2 saturation volume of the storage formation. Our results suggest that the density increase of resident species causes significant enhancement in CO2 dissolution, although no significant porosity and permeability alterations are observed. Early saturation of the reservoir can have negative impact on CO2 sequestration.

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.

Characterization of typical metal particles during haze episodes in Shanghai, China.

PubMed

Li, Rui; Yang, Xin; Fu, Hongbo; Hu, Qingqing; Zhang, Liwu; Chen, Jianmin

2017-08-01

Aerosol particles were collected during three heavy haze episodes at Shanghai in the winter of 2013. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy was used to study the morphology and speciation of typical metal particles at a single-particle level. In addition, time-of-flight aerosol mass spectrometry (ATOFMS) was applied to identify the speciation of the Fe-containing particles. TEM analysis indicated that various metal-containing particles were hosted by sulfates, nitrates, and oxides. Fe-bearing particles mainly originated from vehicle emissions and/or steel production. Pb-, Zn-, and Sb-bearing particles were mainly contributed by anthropogenic sources. Fe-bearing particles were clustered into six groups by ATOFMS: Fe-Carbon, Fe-Inorganic, Fe-Trace metal, Fe-CN, Fe-PO 3, and Fe-NO 3 . ATOFMS data suggested that Fe-containing particles corresponded to different origins, including industrial activities, resuspension of dusts, and vehicle emissions. Fe-Carbon and Fe-CN particles displayed significant diurnal variation, and high levels were observed during the morning rush hours. Fe-Inorganic and Fe-Trace metal particle levels peaked at night. Furthermore, Fe-Carbon and Fe-PO 3 were mainly concentrated in the fine particles. Fe-CN, Fe-Inorganic, and Fe-Trace metal exhibited bimodal distribution. The mixing state of the particles revealed that all Fe-bearing particles tended to be mixed with sulfate and nitrate. The data presented herein is essential for elucidating the origin, evolution processes, and health effects of metal-bearing particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Source Apportionment Using Positive Matrix Factorization on Daily Measurements of Inorganic and Organic Speciated PM2.5

PubMed Central

Dutton, Steven J.; Vedal, Sverre; Piedrahita, Ricardo; Milford, Jana B.; Miller, Shelly L.; Hannigan, Michael P.

2012-01-01

Particulate matter less than 2.5 microns in diameter (PM2.5) has been linked with a wide range of adverse health effects. Determination of the sources of PM2.5 most responsible for these health effects could lead to improved understanding of the mechanisms of such effects and more targeted regulation. This has provided the impetus for the Denver Aerosol Sources and Health (DASH) study, a multi-year source apportionment and health effects study relying on detailed inorganic and organic PM2.5 speciation measurements. In this study, PM2.5 source apportionment is performed by coupling positive matrix factorization (PMF) with daily speciated PM2.5 measurements including inorganic ions, elemental carbon (EC) and organic carbon (OC), and organic molecular markers. A qualitative comparison is made between two models, PMF2 and ME2, commonly used for solving the PMF problem. Many previous studies have incorporated chemical mass balance (CMB) for organic molecular marker source apportionment on limited data sets, but the DASH data set is large enough to use multivariate factor analysis techniques such as PMF. Sensitivity of the PMF2 and ME2 models to the selection of speciated PM2.5 components and model input parameters was investigated in depth. A combination of diagnostics was used to select an optimum, 7-factor model using one complete year of daily data with pointwise measurement uncertainties. The factors included 1) a wintertime/methoxyphenol factor, 2) an EC/sterane factor, 3) a nitrate/polycyclic aromatic hydrocarbon (PAH) factor, 4) a summertime/selective aliphatic factor, 5) an n-alkane factor, 6) a middle oxygenated PAH/alkanoic acid factor and 7) an inorganic ion factor. These seven factors were qualitatively linked with known PM2.5 emission sources with varying degrees of confidence. Mass apportionment using the 7-factor model revealed the contribution of each factor to the mass of OC, EC, nitrate and sulfate. On an annual basis, the majority of OC and EC mass was associated with the summertime/selective aliphatic factor and the EC/sterane factor, respectively, while nitrate and sulfate mass were both dominated by the inorganic ion factor. This apportionment was found to vary substantially by season. Several of the factors identified in this study agree well with similar assessments conducted in St. Louis, MO and Pittsburgh, PA using PMF and organic molecular markers. PMID:22768005

Biochars mitigate greenhouse gas emissions and bioaccumulation of potentially toxic elements and arsenic speciation in Phaseolus vulgaris L.

PubMed

Ibrahim, Muhammad; Li, Gang; Khan, Sardar; Chi, Qiaoqiao; Xu, Yaoyang; Zhu, Yongguan

2017-08-01

Anthropogenic and natural activities can lead to increased greenhouse gas emissions and discharge of potentially toxic elements (PTEs) into soil environment. Biochar amendment to soils is a cost-effective technology and sustainable approach used to mitigate greenhouse gas emissions, improve phytoremediation, and minimize the health risks associated with consumption of PTE-contaminated vegetables. Greenhouse pot experiments were conducted to investigate the effects of peanut shell biochar (PNB) and sewage sludge biochar (SSB) on greenhouse gas (GHG) emissions, plant growth, PTE bioaccumulation, and arsenic (As) speciation in bean plants. Results indicated that amendments of PNB and SSB increased plant biomass production by increasing soil fertility and reducing bioavailability of PTEs. Addition of biochars also increased soil pH, total nitrogen (TN), total carbon (TC), dissolved organic carbon (DOC), and ammonium-nitrogen (NH 4 -N) but decreased available concentrations of PTEs such as cadmium (Cd), lead (Pb), and As. The concentration of nitrate-nitrogen (NO 3 - -N) was also decreased in biochar-amended soils. In addition, PNB and SSB amendments significantly (P < 0.01) reduced the bioaccumulation of chromium (Cr), As, Cd, Pb, and nickel (Ni) in stalks, leaves, and fruits of Phaseolus vulgaris L. Similarly, PNB and SSB amendments significantly (P ≤ 0.05) reduced inorganic As species like arsenite (As (III)) and arsenate (As (V)). Greenhouse gases such as carbon dioxide (CO 2 ) and methane (CH 4 ) emissions were significantly (P < 0.01) reduced but nitrous oxide (N 2 O) emissions first increased and then decreased amended with both biochars. Current findings demonstrate that SSB and PNB are two beneficial soil amendments simultaneous mitigating greenhouse gas emissions and PTE bioaccumulation as well as arsenic speciation in P. vulgaris L.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

COH fluids play a fundamental role in many geological processes, controlling the location of melting in subduction zones and promoting mass transfer from the subducting litosphere to the overlying mantle wedge. The properties of COH fluids are strictly dependent on the composition of the fluid in subduction systems, i.e., the speciation of the volatile components of the fluid itself and the presence of solutes deriving from the dissolution of rock-forming minerals. In the scientific literature, the speciation of COH fluids has been generally determined through thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4), equations that do not consider the complexity related to dissolution processes, which are substantially unexplored in COH fluids and limited so far to aqueous fluids (Newton & Manning, 2002). The aim of this work is to investigate experimentally the speciation and the dissolution of mantle minerals in carbon-saturated COH fluids at buffered fO2 conditions. Our experimental approach relies on two different techniques: 1) analysis by means of quadrupole mass spectrometer (QMS) of the fluids from pierced run capsules to retrieve speciation of volatile components and 2) analysis of frozen COH fluid with laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) to measure the amount of solutes. Experiments were conducted at pressure of 1 GPa and temperatures from 800 to 900° C using a rocking piston cylinder apparatus. Mantle minerals in equilibrium with COH fluid are represented by synthetic forsterite. fO2 conditions were controlled using the double capsule technique and NNO buffer (ΔFMQ=-0.61 at 800° C; ΔFMQ =-0.98 at 900° C). For the speciation experiments, oxalic acid dihydrate and graphite have been used to generate carbon-saturated COH fluid. The speciation was determined by analyzing the quenched COH fluid, retrieved by piercing the capsule in a gas-tight vessel at T =80° C and convoying evolved gases to a QMS through a heated line to avoid the condensation of water. This type of analyzer ensures superior performances in terms of selectivity of molecules to be detected, high acquisition rates and extended linear response range. The influence of dissolved solutes on fluid speciation has been evaluated by comparing experiments in the pure COH system and in the COH+forsterite system. To determine the solubility of forsterite in COH fluids we performed a second set of experiments at the same P , T and fO2 conditions above. Fluids trapped in a diamond layer were analysed by the cryogenic LA-ICP-MS technique described by Aerts et al. (2010). With this method the aqueous part of the COH fluid is frozen prior the opening and maintained frozen during the analysis to avoid any precipitation of solutes. The results will highlight the importance of fluids for the mass transport in subduction zones. Comparison between experimental data and thermodynamic calculation will also be shown. References: Aerts, M., Hack, A.C., Reusser, E., Ulmer, P. (2010) Am. Mineral. 95, 1523-1526. Newton, R.C., Manning, C.E. (2002) Geochim. Cosmochim. Ac. 66, 4165-4176.

Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

2015-11-01

Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca2+ ions and causes the formation of CaCit- and Ca10(PO4)6CO3 complexes. Trisodium citrate binds Ca2+ ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed.

Modeling Anaerobic Soil Organic Carbon Decomposition in Arctic Polygon Tundra: Insights into Soil Geochemical Influences on Carbon Mineralization: Modeling Archive

DOE Data Explorer

Zheng, Jianqiu; Thornton, Peter; Painter, Scott; Gu, Baohua; Wullschleger, Stan; Graham, David

2018-06-13

This anaerobic carbon decomposition model is developed with explicit representation of fermentation, methanogenesis and iron reduction by combining three well-known modeling approaches developed in different disciplines. A pool-based model to represent upstream carbon transformations and replenishment of DOC pool, a thermodynamically-based model to calculate rate kinetics and biomass growth for methanogenesis and Fe(III) reduction, and a humic ion-binding model for aqueous phase speciation and pH calculation are implemented into the open source geochemical model PHREEQC (V3.0). Installation of PHREEQC is required to run this model.

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

Determination of an organic-acid analog of DOC for use in copper toxicity studies on salmonids

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

MacRae, R.K.; Meyer, J.S.; Hansen, J.A.

1995-12-31

Concentrations of dissolved copper in streams draining mine sites often exceed concentrations shown to cause acute and chronic mortality in salmonids. However, toxicity and impaired behaviors may be modified by dissolved organic carbon (DOC) and other inorganic components present in the site water. The effects of DOC on copper speciation, and thus bioavailability and toxicity, were determined by titrating stream waters with copper, using a cupric ion-specific electrode to detect free copper concentrations. Effects of various competing cations (e.g., Ca{sup +2}, Co{sup +2}) on copper-DOC binding were also evaluated. Titration results were evaluated using Scatchard and non-linear regression analyses tomore » quantify the strength and capacity of copper-DOC binding. Inorganic speciation was determined using the geochemical model MINEQL{sup +}. Results of these titrations indicated the presence of two or three distinct copper binding components in site water DOC. Three commercially available organic acids where then chosen to mimic the binding characteristics of natural DOC. This DOC-analog was used successfully in fish toxicity studies to evaluate the influence of DOC on copper bioavailability. Geochemical models were developed to predict copper speciation in both laboratory test waters and site waters, for any typical combination of water chemistry parameters (pH, alkalinity, [DOC], etc.). A combined interpretation of fish toxicity and modeling results indicate that some DOC-bound copper was bioavailable.« less

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.

Speciation and Release Kinetics of Cadmium in an Alkaline Paddy Soil Under Various Flooding Periods and Draining Conditions

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

S Khaokaew; R Chaney; G Landrot

2011-12-31

This study determined Cd speciation and release kinetics in a Cd-Zn cocontaminated alkaline paddy soil, under various flooding periods and draining conditions, by employing synchrotron-based techniques, and a stirred-flow kinetic method. Results revealed that varying flooding periods and draining conditions affected Cd speciation and its release kinetics. Linear least-squares fitting (LLSF) of bulk X-ray absorption fine structure (XAFS) spectra of the air-dried, and the 1 day-flooded soil samples, showed that at least 50% of Cd was bound to humic acid. Cadmium carbonates were found as the major species at most flooding periods, while a small amount of cadmium sulfide wasmore » found after the soils were flooded for longer periods. Under all flooding and draining conditions, at least 14 mg/kg Cd was desorbed from the soil after a 2-hour desorption experiment. The results obtained by micro X-ray fluorescence ({mu}-XRF) spectroscopy showed that Cd was less associated with Zn than Ca, in most soil samples. Therefore, it is more likely that Cd and Ca will be present in the same mineral phases rather than Cd and Zn, although the source of these two latter elements may originate from the same surrounding Zn mines in the Mae Sot district.« less

Impact of ozonation on naphthenic acids speciation and toxicity of oil sands process-affected water to Vibrio fischeri and mammalian immune system.

PubMed

Wang, Nan; Chelme-Ayala, Pamela; Perez-Estrada, Leonidas; Garcia-Garcia, Erick; Pun, Jonathan; Martin, Jonathan W; Belosevic, Miodrag; Gamal El-Din, Mohamed

2013-06-18

Oil sands process-affected water (OSPW) is the water contained in tailings impoundment structures in oil sands operations. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. In this study, ozonation followed by biodegradation was used to remediate OSPW. The impacts of the ozone process evolution on the naphthenic acids (NAs) speciation and acute toxicity were evaluated. Ion-mobility spectrometry (IMS) was used to preliminarily separate isomeric and homologous species. The results showed limited effects of the ozone reactor size on the treatment performance in terms of contaminant removal. In terms of NAs speciation, high reactivity of NAs with higher number of carbons and rings was only observed in a region of high reactivity (i.e., utilized ozone dose lower than 50 mg/L). It was also found that nearly 0.5 mg/L total NAs was oxidized per mg/L of utilized ozone dose, at utilized ozone doses lower than 50 mg/L. IMS showed that ozonation was able to degrade NAs, oxidized NAs, and sulfur/nitrogenated NAs. Complete removal of toxicity toward Vibrio fischeri was achieved after ozonation followed by 28-day biodegradation period. In vitro and in vivo assays indicated that ozonation reduced the OSPW toxicity to mice.

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.

Environmental controls on the speciation and distribution of mercury in surface sediments of a tropical estuary, India.

PubMed

Chakraborty, Parthasarathi; Babu, P V Raghunadh

2015-06-15

Distribution and speciation of mercury (Hg) in the sediments from a tropical estuary (Godavari estuary) was influenced by the changing physico-chemical parameters of the overlying water column. The sediments from the upstream and downstream of the estuary were uncontaminated but the sediments from the middle of the estuary were contaminated by Hg. The concentrations of Hg became considerably less during the monsoon and post monsoon period. Total Hg concentrations and its speciation (at the middle of the estuary) were dependent on the salinity of the overlying water column. However, salinity had little or no effect on Hg association with organic phases in the sediments at downstream. Increasing pH of the overlying water column corresponded with an increase in the total Hg content in the sediments. Total organic carbon in the sediments played an important role in controlling Hg partitioning in the system. Uncomplexed Hg binding ligands were available in the sediments. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

THE POTENTIAL INFLUENCES OF FACE VELOCITY ON PM ARTIFACT LOSSES FOR EXPOSURE SAMPLERS USING TEFLON FILTER COLLECTION SUBSTRATES

EPA Science Inventory

The influences of artifact formations and losses on Particulate Matter (PM) sampler collection surfaces are well documented, especially for nitrates (Hering and Cass, 1999), and SVOC's (McDow, 1999), and more recently for speciated carbon (Turpin and Lim, 2001). These artifact...

Citric-acid preacidification enhanced electrokinetic remediation for removal of chromium from chromium-residue-contaminated soil.

PubMed

Meng, Fansheng; Xue, Hao; Wang, Yeyao; Zheng, Binghui; Wang, Juling

2018-02-01

Electrokinetic experiments were conducted on chromium-residue-contaminated soils collected from a chemical plant in China. Acidification-electrokinetic remediation technology was proposed in order to solve the problem of removing inefficient with ordinary electrokinetic. The results showed that electrokinetic remediation removal efficiency of chromium from chromium-contaminated soil was significantly enhanced with acidizing pretreatment. The total chromium [Cr(T)] and hexavalent chromium [Cr(VI)] removal rate of the group acidized by citric acid (0.9 mol/L) for 5 days was increased from 6.23% and 19.01% in the acid-free experiments to 26.97% and 77.66% in the acidification-treated experiments, respectively. In addition, part of chromium with the state of carbonate-combined will be converted into water-soluble state through acidification to improve the removal efficiency. Within the appropriate concentration range, the higher concentration of acid was, the more chromium was released. So the removal efficiency of chromium depended on the acid concentration. The citric acid is also a kind of complexing agent, which produced complexation with Cr that was released by the electrokinetic treatment and then enhanced the removal efficiency. The major speciation of chromium that was removed from soils by acidification-electrokinetics remediation was acid-soluble speciation, revivification speciation and oxidation speciation, which reduced biological availability of chromium.

A review of the contrasting behavior of two magmatic volatiles: Chlorine and carbon dioxide

USGS Publications Warehouse

Lowenstern, J. B.

2000-01-01

Chlorine (Cl) and carbon dioxide (CO2) are common magmatic volatiles with contrasting behaviors. CO2 solubility increases with pressure whereas Cl solubility shows relatively little pressure or temperature effect. CO2 speciation changes with silicate melt composition, dissolving as carbonate in basaltic magmas and molecular CO2 in more silicic compositions. In H2O-bearing systems, the strongly non-ideal behavior of alkali chlorides causes unmixing of the volatile phase to form a H2O-rich vapor and a hydrosaline phase with important implications for the maximum concentration of Cl in magmas. Addition of CO2 to magma hastens immiscibility at crustal pressures (<500 MPa), inducing the formation of CO2-rich vapors and Cl-rich hydrosaline melts. (C) 2000 Elsevier Science B.V. All rights reserved.Chlorine (Cl) and carbon dioxide (CO2) are common magmatic volatiles with contrasting behaviors. CO2 solubility increases with pressure whereas Cl solubility shows relatively little pressure or temperature effect. CO2 speciation changes with silicate melt composition, dissolving as carbonate in basaltic magmas and molecular CO2 in more silicic compositions. In H2O-bearing systems, the strongly non-ideal behavior of alkali chlorides causes unmixing of the volatile phase to form a H2O-rich vapor and a hydrosaline phase with important implications for the maximum concentration of Cl in magmas. Addition of CO2 to magma hastens immiscibility at crustal pressures (<500 MPa), inducing the formation of CO2-rich vapors and Cl-rich hydrosaline melts.

Evaluation of factors that affect diesel exhaust toxicity. Final report

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

Norbeck, J.M.; Smith, M.R.; Arey, J.

1998-07-01

The scope of this project was to obtain a preliminary assessment of the potential impact of the fuel formulation on the speciation and toxic components of diesel exhaust. The test bed was a Cummins L10 engine operating over the heavy-duty transient test cycle using three diesel fuels: a pre-1993 diesel fuel, a low aromatic diesel fuel, and an alternative formulation diesel fuel. The sampling/analysis plan included: determination of the criteria pollutant emission rates (THC, CO, NOx, and PM); determination of PM(10) and PM(2.5) emission rates; collection and analysis of particulate samples for elemental, inorganic ion and elemental/organic carbon analyses; collectionmore » of bas samples for VOC speciation analyses; collection of 2,4-dinitrophenylhydrazine (DNPH) cartridges for determination of oxygenates; collection of nitrosomorpholine with Thermosorb N cartridges; collection of semi-volatiles on PF/XAD and particulate samples for PAH, nitro-PAH, and mutagenicity studies; and collection and analysis of dioxins for the pre-1993 and alternative formulation diesel fuels.« less

Release of aged contaminants from weathered sediments: Effects of sorbate speciation on scaling of reactive transport

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

Chorover, Jon; Perdrial, Nico; Mueller, Karl

2012-11-05

Hanford sediments impacted by hyperalkaline high level radioactive waste have undergone incongruent silicate mineral weathering concurrent with contaminant uptake. In this project, we studied the impact of background pore water (BPW) on strontium, cesium and iodine desorption and transport in Hanford sediments that were experimentally weathered by contact with simulated hyperalkaline tank waste leachate (STWL) solutions. Using those lab-weathered Hanford sediments (HS) and model precipitates formed during nucleation from homogeneous STWL solutions (HN), we (i) provided thorough characterization of reaction products over a matrix of field-relevant gradients in contaminant concentration, partial pressure of carbon dioxide, and reaction time; (ii) improvedmore » molecular-scale understanding of how sorbate speciation controls contaminant desorption from weathered sediments upon removal of caustic sources; and (iii) developed a mechanistic, predictive model of meso- to field-scale contaminant reactive transport under these conditions. In this final report, we provide detailed descriptions of our results from this three-year study, completed in 2012 following a one-year no cost extension.« less

Effect of sewage sludge hydrochar on soil properties and Cd immobilization in a contaminated soil.

PubMed

Ren, Jie; Wang, Fenghua; Zhai, Yunbo; Zhu, Yun; Peng, Chuan; Wang, Tengfei; Li, Caiting; Zeng, Guangming

2017-12-01

To investigate hydrochar as a soil amendment for the immobilization of Cd, the characteristics of hydrochars (HCs) under three temperatures and residence times, were studied, with a particular interest in soil properties, as well as the speciation, availability and plant uptake of Cd. HCs were obtained by a hydrothermal carbonization (HTC) reaction of sewage sludge (SS). Based on the study of HC properties, we found that HCs present weak acidity with relatively high ash content and low electrical conductivity (EC) values. The addition of HCs to soil decreased soil pH and EC values but increased the abundance of soil microorganism. HCs also promoted the transformation of Cd from unstable to stable speciation and can decrease the content of phyto-available Cd (optimum condition and efficiency: A13, 2 15.38%), which restrained cabbage from assimilating Cd from soil both the aboveground (optimum condition and efficiency: A35, 52.29%) and underground (optimum condition and efficiency: C15, 57.53%) parts of it. Copyright © 2017 Elsevier Ltd. All rights reserved.

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study.

PubMed

Watson, John G; Chow, Judith C; Lowenthal, Douglas H; Antony Chen, L-W; Shaw, Stephanie; Edgerton, Eric S; Blanchard, Charles L

2015-09-01

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM(2.5) (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM(2.5) mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27-38% of PM(2.5), followed by biomass burning (21-24%) and motor vehicle exhaust (9-24%) at both sites, with 4-6% of PM(2.5) attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13-23% deficit for PM(2.5) mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident. Organic markers can be measured on currently acquired PM(2.5) filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.

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

PubMed

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

2016-02-16

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

Mesozoic Calcareous Nannofossil Evolution: Relation to Paleoceanographic Events

NASA Astrophysics Data System (ADS)

Roth, Peter H.

1987-12-01

The taxonomic evolution of Jurassic and Cretaceous calcareous nannofossil species is described using the following indices: species diversity, rate of speciation, rate of extinction, rate of diversification, rate of turnover, survivorship, and species accretion. The Jurassic prior to the late Oxfordian is characterized by positive diversification rates, that is, rates of speciation exceeded rates of extinction. Highest rates of diversification occurred in the late Lias and early Oxfordian. During the generally regressive latest Jurassic, diversification rates remained low and rates of extinctions exceed rates of speciation. In the early Cretaceous, rates of diversification are positive and peak in the early Valanginian, early Aptian, and middle Albian, after which time rates of extinction generally exceed rates of speciation. Such peaks in rate of evolution coincide with times of increased accumulation of organic carbon in the ocean ("anoxic events"). Peaks in rates of extinction result in very high rates of turnover during times of major regressions, in particular, in the Tithonian and Maastrichtian. Survivorship analyses for three datum planes (74.5, 144, and 160 Ma) show relatively constant extinction rates with some stepping in the older part; they are best explained by a temporally fluctuating abiotic environment causing changes in the probability of extinction. Species accretion curves are also relatively linear with some indication of changing rates of speciation. The coincidences of major changes in evolutionary rates with major paleoceanographic events are indicative of a predominantly abiotic control of nannoplankton evolution. Relationships of evolutionary rates of calcareous nannoplankton with deep ocean ventilation, sea level, and ocean fertility indicates that global tectonic processes are the ultimate causes of evolutionary change.

Genomic Speciation and Adaptation in Aquilegia (2011 JGI User Meeting)

ScienceCinema

Hodges, Scott

2018-02-14

The U.S. Department of Energy Joint Genome Institute (JGI) invited scientists interested in the application of genomics to bioenergy and environmental issues, as well as all current and prospective users and collaborators, to attend the annual DOE JGI Genomics of Energy & Environment Meeting held March 22-24, 2011 in Walnut Creek, Calif. The emphasis of this meeting was on the genomics of renewable energy strategies, carbon cycling, environmental gene discovery, and engineering of fuel-producing organisms. The meeting features presentations by leading scientists advancing these topics. Scott Hodges of the University of California, Santa Barbara gives a presentation on Genomic Speciation and Adaptation in Aquilegia at the 6th annual Genomics of Energy & Environment Meeting on March 23, 2011.

Volatile and semivolatile organic compounds in laboratory peat fire emissions

NASA Astrophysics Data System (ADS)

George, Ingrid J.; Black, Robert R.; Geron, Chris D.; Aurell, Johanna; Hays, Michael D.; Preston, William T.; Gullett, Brian K.

2016-05-01

In this study, volatile and semi-volatile organic compound (VOCs and SVOCs) mass emission factors were determined from laboratory peat fire experiments. The peat samples originated from two National Wildlife Refuges on the coastal plain of North Carolina, U.S.A. Gas- and particle-phase organic compounds were quantified by gas chromatography-mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (∼60%) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. In the fine particle mass (PM2.5), the following organic compound classes were dominant: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for the organic acids in PM2.5 including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12%) of all speciated compound classes measured in this work. Levoglucosan contributed to 2-3% of the OC mass, while methoxyphenols represented 0.2-0.3% of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon (PAH). Total HAP VOC and particulate PAH emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions.

Indirect effects of climate change on zinc cycling in sediments: The role of changing water levels.

PubMed

Nedrich, Sara M; Burton, G Allen

2017-09-01

Increased variability in lake and river water levels associated with changing climate could impact the fate and effects of metals in redox-sensitive sediments through the alteration of microbial communities and of acid-base and redox chemistry. The objective of the present study was to determine the influence of water level fluctuation on metal speciation in porewater and predict environmental risk to high-carbonate systems. Using experimental microcosms with sediments collected from 4 metal-contaminated coastal freshwater wetlands in Michigan, USA, we conducted water level fluctuation experiments. Porewater and sediment metals (Ca, Cu, Fe, Mg, Mn, Ni, Zn) and important metal binding phases (iron-oxide speciation, acid-volatile sulfide) were quantified. In a short-term drying (seiche) experiment, there were decreases in all porewater metals after inundation of saturated sediments. During a drought experiment, re-inundation of oxidized sediments increased porewater Cu, Zn, Mg, Ca for most sites. Porewater Zn increased after inundation to levels exceeding the US Environmental Protection Agency threshold for chronic toxicity. These data show that the dissolution of metal carbonates and metal sulfates contributes to metal release after re-flooding and indicate that we might expect increased ecological risk to organisms present in drought-sensitive regions where altered hydroperiods are likely to increase metal bioavailability. Environ Toxicol Chem 2017;36:2456-2464. © 2017 SETAC. © 2017 SETAC.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

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

USGS Publications Warehouse

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

2004-01-01

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and <45 ??m size fractions (e.g., from 97-810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8-18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg LIII-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg3O2SO4), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments. ?? 2003 Elsevier Ltd. All rights reserved.

Selective Separation and Determination of Heavy Metals (Cd, Pb, Cr) Speciation Forms from Hortic Antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.

2009-04-01

The speciation, inter-phases distribution and biodisponibility of heavy metals in soils represent one of main problem of environmental geochemistry and agro-chemistry. This problem is very important in case of hortic antrosols (soils from glasshouses) for the elimination of agricultural products (fruits, vegetables) contamination with heavy metals. In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have bee performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07).

Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE): Emissions of particulate matter from wood and dung cooking fires, brick kilns, generators, trash and crop residue burning

NASA Astrophysics Data System (ADS)

Stone, Elizabeth; Jayarathne, Thilina; Stockwell, Chelsea; Christian, Ted; Bhave, Prakash; Siva Praveen, Puppala; Panday, Arnico; Adhikari, Sagar; Maharjan, Rashmi; Goetz, Doug; DeCarlo, Peter; Saikawa, Eri; Yokelson, Robert

2016-04-01

The Nepal Ambient Monitoring and Source Testing Experiment (NAMASTE) field campaign targeted the in situ characterization of widespread and under-sampled combustion sources. In Kathmandu and the Terai, southern Nepal's flat plains, samples of fine particulate matter (PM2.5) were collected from wood and dung cooking fires (n = 22), generators (n = 2), groundwater pumps (n = 2), clamp kilns (n = 3), zig-zag kilns (n = 3), trash burning (n = 4), one heating fire, and one crop residue fire. Co-located measurements of carbon dioxide, carbon monoxide, and volatile organic compounds allowed for the application of the carbon mass balance approach to estimate emission factors for PM2.5, elemental carbon, organic carbon, and water-soluble inorganic ions. Organic matter was chemically speciated using gas chromatography - mass spectrometry for polycyclic aromatic hydrocarbons, sterols, n-alkanes, hopanes, steranes, and levoglucosan, which accounted for 2-8% of the measured organic carbon. These data were used to develop molecular-marker based profiles for use in source apportionment modeling. This study provides quantitative emission factors for particulate matter and its constituents for many important combustion sources in Nepal and South Asia.

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%).

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.

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.

Pilot scale study on the ex situ electrokinetic removal of heavy metals from municipal wastewater sludges.

PubMed

Kim, Soon-Oh; Moon, Seung-Hyeon; Kim, Kyoung-Woong; Yun, Seong-Taek

2002-11-01

In order to remove toxic heavy metals from municipal wastewater sludges, the ex situ electrokinetic technique was studied at pilot scale. This study focused on the feasibility of the electrokinetic removal of heavy metals from sludge and the effectiveness of this technique on the variations of abiotic (physicochemical) and biotic (intracellular and extracellular) speciations of heavy metals using several analytical methods. Even though the sludge used was taken from a municipal wastewater treatment plant, the sludge contained relatively high concentrations of target metal contaminants (Cd = 6.8 mg/kg, Cr = 115.6 mg/kg, Cu = 338.7 mg/kg, and Pb = 62.8 mg/kg). The removal efficiencies of heavy metals were significantly dependent on their speciations in the sludge matrices. The electrokinetic removal efficiencies of abiotic heavy metals exceeded 70% for the mobile and weakly bound fractions, such as, the exchangeable and carbonate fractions and were lower than 35% for the strongly bound fractions, such as, the organic/sulfide and residual fractions. In the case of the biotic heavy metals, the removal efficiencies of the extracellular fractions were slightly higher than those of the intracellular fractions.

SOURCE APPORTIONMENT OF PM 2.5 AND CARBON IN SEATTLE USING CHEMICAL MASS BALANCE AND POSITIVE MATRIX FACTORIZATION

EPA Science Inventory

Three years of PM2.5 speciated data were collected and chemically analyzed using the IMPROVE protocol at the Beacon Hill site in Seattle. The data were analyzed by the Chemical Mass Balance Version 8 (CMB8) and Positive Matrix Factorization (PMF) source apportionment models. T...

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.

Relative contributions of mercury bioavailability and microbial growth rate on net methylmercury production by anaerobic mixed cultures

DOE PAGES

Kucharzyk, Katarzyna H.; Deshusses, Marc A.; Porter, Kaitlyn A.; ...

2015-07-17

Monomethylmercury (MeHg) is produced in many aquatic environments by anaerobic microorganisms that take up and methylate inorganic forms of Hg(II). Net methylation of Hg(II) appears to be correlated with factors that affect the activity of the anaerobic microbial community and factors that increase the bioavailability of Hg(II) to these organisms. However, the relative importance of one versus the other is difficult to elucidate even though this information can greatly assist remediation efforts and risk assessments. Here in this study, we investigated the effects of Hg speciation (dissolved Hg and nanoparticulate HgS) and microbial activity on the net production of MeHgmore » using two mixed microbial cultures that were enriched from marine sediments under sulfate reducing conditions. The cultures were amended with dissolved Hg (added as a dissolved nitrate salt) and nanoparticulate HgS, and grown under different carbon substrate concentrations. The results indicated that net mercury methylation was the highest for cultures incubated in the greatest carbon substrate concentration (60 mM) compared to incubations with less carbon (0.6 and 6 mM), regardless of the form of mercury amended. Net MeHg production in cultures exposed to HgS nanoparticles was significantly slower than in cultures exposed to dissolved Hg; however, the difference diminished with slower growing cultures with low carbon addition (0.6 mM). The net Hg methylation rate was found to correlate with sulfate reduction rate in cultures exposed to dissolved Hg, while methylation rate was roughly constant for cultures exposed to nanoparticulate HgS. These results indicated a potential threshold of microbial productivity: below this point net MeHg production was limited by microbial activity, regardless of Hg bioavailability. Lastly, above this threshold of productivity, Hg speciation became a contributing factor towards net MeHg production.« less

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.

Effects of soil properties on the transfer of cadmium from soil to wheat in the Yangtze River delta region, China--a typical industry-agriculture transition area.

PubMed

Wang, Cheng; Ji, Junfeng; Yang, Zhongfang; Chen, Lingxiao; Browne, Patrick; Yu, Ruilian

2012-08-01

In order to identify the effects of soil properties on the transfer of Cd from soil to wheat under actual field conditions, 126 pairs of topsoil and wheat samples were collected from the Yangtze River delta region, China. Relevant parameters (Cd, Ca, Mg, Fe, Mn, Zn, N, P, K, S, pH, total organic carbon, and speciation of soil Cd) in soil and wheat tissues were analyzed, and the results were treated by statistical methods. Soil samples (19.8%) and 14.3% of the wheat grain samples exceeded the relevant maximum permissible Cd concentrations in China for agricultural soil and wheat grain, respectively. The major speciations of Cd in soil were exchangeable, bound to carbonates and fulvic and humic acid fraction, and they were readily affected by soil pH, total Ca, Mg, S and P, DTPA-Fe, Ex-Ca, and Ex-Mg. Cadmium showed a strong correlation with Fe, S, and P present in the grain and the soil, whereas there was no significant correlation in the straw or root. Generally, soil pH, Ca, Mg, Mn, P, and slowly available K restricted Cd transfer from soil to wheat, whereas soil S, N, Zn, DTPA-Fe, and total organic carbon enhance Cd uptake by wheat.

Influences of organic carbon speciation on hyporheic corridor biogeochemistry and microbial ecology

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

Stegen, James C.; Johnson, Tim; Fredrickson, James K.

The hyporheic corridor (HC) is a critical component of riverine ecosystems that encompasses the river-11 groundwater continuum. The mixing of groundwater (GW) with river water (RW) in the HC can 12 stimulate biogeochemical activity, and here we (i) propose a novel thermodynamic mechanism 13 underlying this phenomenon, and (ii) reveal broader impacts on dissolved organic carbon (DOC) 14 biogeochemistry and microbial ecology. We show that thermodynamically-favorable DOC 15 accumulates in GW despite decreases in DOC concentration along subsurface flow paths, and that RW 16 contains less thermodynamically-favorable DOC, but at higher concentrations. This indicates that DOC 17 in GW ismore » protected from microbial oxidation by low total energy contained within the DOC pool, while 18 RW DOC is protected by lower thermodynamic favorability of carbon species. We propose that GW-19 RW mixing overcomes these protection mechanisms and stimulates respiration. Mixing models 20 coupled with time-lapse electrical resistance tomography revealed that stimulated respiration leads 21 to tipping points in spatiotemporal dynamics of DOC across the HC. Further, shifts in DOC speciation 22 and biochemical pathways were associated with shifts in microbiome composition, highlighting 23 feedbacks among hydrology, DOC biochemistry, and microbial ecology. These results reveal that 24 previously unrecognized thermodynamic-based mechanisms regulated by GW-RW mixing can strongly 25 influence biogeochemical and microbial dynamics in riverine ecosystems.« less

Influences of organic carbon speciation on hyporheic corridor biogeochemistry and microbial ecology

DOE PAGES

Stegen, James C.; Johnson, Tim; Fredrickson, James K.; ...

2018-02-08

The hyporheic corridor (HC) is a critical component of riverine ecosystems that encompasses the river-11 groundwater continuum. The mixing of groundwater (GW) with river water (RW) in the HC can 12 stimulate biogeochemical activity, and here we (i) propose a novel thermodynamic mechanism 13 underlying this phenomenon, and (ii) reveal broader impacts on dissolved organic carbon (DOC) 14 biogeochemistry and microbial ecology. We show that thermodynamically-favorable DOC 15 accumulates in GW despite decreases in DOC concentration along subsurface flow paths, and that RW 16 contains less thermodynamically-favorable DOC, but at higher concentrations. This indicates that DOC 17 in GW ismore » protected from microbial oxidation by low total energy contained within the DOC pool, while 18 RW DOC is protected by lower thermodynamic favorability of carbon species. We propose that GW-19 RW mixing overcomes these protection mechanisms and stimulates respiration. Mixing models 20 coupled with time-lapse electrical resistance tomography revealed that stimulated respiration leads 21 to tipping points in spatiotemporal dynamics of DOC across the HC. Further, shifts in DOC speciation 22 and biochemical pathways were associated with shifts in microbiome composition, highlighting 23 feedbacks among hydrology, DOC biochemistry, and microbial ecology. These results reveal that 24 previously unrecognized thermodynamic-based mechanisms regulated by GW-RW mixing can strongly 25 influence biogeochemical and microbial dynamics in riverine ecosystems.« less

Organic carbon, and major and trace element dynamic and fate in a large river subjected to poorly-regulated urban and industrial pressures (Sebou River, Morocco).

PubMed

Hayzoun, H; Garnier, C; Durrieu, G; Lenoble, V; Le Poupon, C; Angeletti, B; Ouammou, A; Mounier, S

2015-01-01

An annual-basis study of the impacts of the anthropogenic inputs from Fez urban area on the water geochemistry of the Sebou and Fez Rivers was conducted mostly focusing on base flow conditions, in addition to the sampling of industrial wastewater characteristic of the various pressures in the studied environment. The measured trace metals dissolved/particulate partitioning was compared to the ones predicted using the WHAM-VII chemical speciation code. The Sebou River, upstream from Fez city, showed a weakly polluted status. Contrarily, high levels of major ions, organic carbon and trace metals were encountered in the Fez River and the Sebou River downstream the Fez inputs, due to the discharge of urban and industrial untreated and hugely polluted wastewaters. Trace metals were especially enriched in particles with levels even exceeding those recorded in surface sediments. The first group of elements (Al, Fe, Mn, Ti, U and V) showed strong inter-relationships, impoverishment in Fez particles/sediments and stable partition coefficient (Kd), linked to their lithogenic origin from Sebou watershed erosion. Conversely, most of the studied trace metals/metalloids, originated from anthropogenic sources, underwent significant changes of Kd and behaved non-conservatively in the Sebou/Fez water mixing. Dissolved/particulate partitioning was correctly assessed by WHAM-VII modeling for Cu, Pb and Zn, depicting significant differences in chemical speciation in the Fez River when compared to that in the Sebou River. The results of this study demonstrated that a lack of compliance in environmental regulations certainly explained this poor status. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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

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...

Technical Evaluation of Biogeochemical Transformation of Iodine at 200-UP-1, Hanford, WA

NASA Astrophysics Data System (ADS)

Lee, M. H.; Cordova, E.; Brooks, S.; Moser, E.; Wells, J.; Lee, B.

2015-12-01

From the 1940s through the early 1990s, liquid wastes from materials used and produced at the Hanford Site were disposed to the ground through cribs, ditches, ponds, and trenches. Primary groundwater and vadose zone contaminants include carbon tetrachloride, uranium, nitrate, chromium, 129I, 99Tc, and tritium. Iodine-129 is of environmental concern due to its long half-life, mobility, and hazardous potential to humans through bioaccumulation, and is one of the primary risk drivers for the Hanford site. The 200 West area of the Hanford Site contains two separate plumes covering 1,500 acres where 129I concentrations are ~3.5 pCi/L in Hanford groundwater. Speciation analysis shows that iodate comprises 70.6% of the iodine present, and organo-iodide and iodide comprise 25.8% and 3.6% respectively. While hydraulic containment is the currently selected remedy for 129I in the groundwater, there is currently no remedy selected for controlling migration of 129I from the vadose zone to the groundwater. Research is currently underway to develop a site conceptual model for understanding the biogeochemical drivers for iodine speciation and determine the processes that drive the fate and transport of 129I through the vadose zone and into groundwater. These data will provide the information to decrease the uncertainty related to the inventory, distribution, and transport properties which will lead to appropriate treatment strategies for the 129I plume(s). Understanding the mechanisms and contributors to iodine speciation is important in order to develop bioremediation strategies for contaminated areas. The effect that microbial communities and humic acid have on iodine speciation and sorption was explored using Ringold sediment from the 200 West Area exposed to varying levels of 129I contamination in conjunction with varying growth media constituents. Several isolates obtained from these batch studies have been shown to reduce over 80% of iodate present in growth media when nitrate was present. No iodate reduction was observed in the absence of nitrate. Additionally, several isolates have been identified that can oxidize iodide. Currently, analytical techniques are underway to quantify the effect of microbial interaction on iodine speciation along with characterization of these diverse microbial isolates.

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.

Chemistry of transuranium elements in salt-base repository

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

Borkowski, Marian; Reed, Donald T; Lucchini, Jean - Francois

2010-12-02

The mobility and potential release of actinides into the accessible environment continues to be the key performance assessment concern of nuclear repositories. Actinide, in particular plutonium speciation under the wide range of conditions that can exist in the subsurface is complex and depends strongly on the coupled effects of redox conditions, inorganic/organic complexation, and the extent/nature of aggregation. Understanding the key factors that define the potential for actinide migration is, in this context, an essential and critical part of making and sustaining a licensing case for a nuclear repository. Herein we report on recent progress in a concurrent modeling andmore » experimental study to determine the speciation of plutonium, uranium and americium in high ionic strength Na-CI-Mg brines. This is being done as part of the ongomg recertification effort m the Waste Isolation Pilot Plant (WIPP). The oxidation-state specific solubility of actinides were established in brine as function of pC{sub H+}, brine composition and the presence and absence of organic chelating agents and carbonate. An oxidation-state invariant analog approach using Nd{sup 3+} and Th{sup 4+} was used for An{sup 3+} and An{sup 4+} respectively. These results show that organic ligands and hydrolysis are key factors for An(III) solubility, hydrolysis at pC{sub H+} above 8 is predominate for An(IV) and carbonates are the key factor for U(VI) solubility. The effect of high ionic strength and brine components measured in absence of carbonates leads to measurable increased in overall solubility over analogous low ionic strength groundwater. Less is known about the bioreduction of actinides by halo-tolerant microorganisms, but there is now evidence that bioreduction does occur and is analogous, in many ways, to what occurs with soil bacteria. Results of solubility studies that focus on Pitzer parameter corrections, new species (e.g. borate complexation), and the thermodynamic parameters for modeling are discussed.« less

Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

DOE PAGES

Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.; ...

2016-02-02

Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range aremore » complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15H 24 (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15H 22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.« less

Speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) in a pine forest during BEACHON-RoMBAS 2011

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

Chan, A. W. H.; Kreisberg, N. M.; Hohaus, T.

Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SV-TAG-AMS) deployed at Manitou Forest, CO, during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range aremore » complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C 15H 24 (e.g., β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpenoids with molecular formula C 15H 22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 µg m –3 and their volatility distributions are estimated for modeling aerosol formation chemistry.« less

Shock vaporization of carbonate and sulfate minerals

NASA Astrophysics Data System (ADS)

Shen, A. H.; Ahrens, T. J.; O'Keefe, J. D.

2001-12-01

Strong shock waves induced by impacts can cause vaporization of rocks and minerals. The products of such process play important roles in planetary differentiation (Yakovlev et al., Geochem. International, 38, 1027, 2000) and in effecting the planetary climate. Many experiments and computer simulations have been performed to simulate the Chicxulub impact at Cretaceous/Tertiary boundary (see, for example, Pierazzo et al., J. Geophys. Res., 103, 28607, 1998 and Pope et al., J. Geophys. Res., 102, 21645, 1997). However, the pressure range for incipient and complete vaporization of carbonates and sulfates are not well constrained, especially, for minerals with various initial porosities. Furthermore, evidence for chemical species in the products of vaporized carbonate and sulfate minerals is almost non-existing. In this study, we employed published Hugoniot data for carbonate and sulfate minerals. By using the methods described in Ahrens (J. Appl. Phys., 43, 2443, 1972) and Ahrens and O'Keefe (The Moon, 4, 214, 1972), we calculated the entropy associated with the thermodynamic states produced by hypervelocity impacts at various velocities for carbonate and sulfate minerals with different initial porosities. The results were compared with the entropy of incipient vaporization and complete vaporization of these minerals to determine the degree of vaporization due to impacts. Moreover, these results are utilized to guide our experimental study in speciation reactions in shock-induced vaporization of carbonates and sulfates.

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.

Effects of ozonation, powdered activated carbon adsorption, and coagulation on the removal of disinfection by-product precursors in reservoir water.

PubMed

Wang, Feng; Gao, Baoyu; Yue, Qinyan; Bu, Fan; Shen, Xue

2017-07-01

Effects of ozonation and powdered activated carbon on removal of dissolved organic matter (DOM) and disinfection by-product (DBP) in reservoir water were intensively investigated in this study. Both the formation of carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) as well as their speciation were analyzed. Results exhibited that the addition of powdered activated carbon (PAC) greatly improved the removal of aromatic protein. Trihalomethanes (THMs) and haloacetonitriles (HANs) were the dominant species in C-DBP and N-DBP. The integrated coagulation and PAC processes could remove more than 70% of THMs and 93% of HANs precursors, while only 10.5 and 45% of capture were achieved by the single coagulation. The added ozone lowered the yields of HANs but synchronously increased the more toxic bromine-containing THMs from 78.5 to 128.1 μg/L. Kinetics parameters for THM formation indicated that the precursor creating the THMs fast could be easily removed by both the coagulation and PAC adsorption.

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

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

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

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

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

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

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

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

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.

Selenium Distribution and Speciation in the Hyperaccumulator Astragalus bisulcatus and Associated Ecological Partners1[W][OA

PubMed Central

Valdez Barillas, José R.; Quinn, Colin F.; Freeman, John L.; Lindblom, Stormy D.; Fakra, Sirine C.; Marcus, Matthew A.; Gilligan, Todd M.; Alford, Élan R.; Wangeline, Ami L.; Pilon-Smits, Elizabeth A.H.

2012-01-01

The goal of this study was to investigate how plant selenium (Se) hyperaccumulation may affect ecological interactions and whether associated partners may affect Se hyperaccumulation. The Se hyperaccumulator Astragalus bisulcatus was collected in its natural seleniferous habitat, and x-ray fluorescence mapping and x-ray absorption near-edge structure spectroscopy were used to characterize Se distribution and speciation in all organs as well as in encountered microbial symbionts and herbivores. Se was present at high levels (704–4,661 mg kg−1 dry weight) in all organs, mainly as organic C-Se-C compounds (i.e. Se bonded to two carbon atoms, e.g. methylselenocysteine). In nodule, root, and stem, up to 34% of Se was found as elemental Se, which was potentially due to microbial activity. In addition to a nitrogen-fixing symbiont, the plants harbored an endophytic fungus that produced elemental Se. Furthermore, two Se-resistant herbivorous moths were discovered on A. bisulcatus, one of which was parasitized by a wasp. Adult moths, larvae, and wasps all accumulated predominantly C-Se-C compounds. In conclusion, hyperaccumulators live in association with a variety of Se-resistant ecological partners. Among these partners, microbial endosymbionts may affect Se speciation in hyperaccumulators. Hyperaccumulators have been shown earlier to negatively affect Se-sensitive ecological partners while apparently offering a niche for Se-resistant partners. Through their positive and negative effects on different ecological partners, hyperaccumulators may influence species composition and Se cycling in seleniferous ecosystems. PMID:22645068

Comparative in vitro studies on disodium EDTA effect with and without Proteus mirabilis on the crystallization of carbonate apatite and struvite

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Olszynski, Marcin; Torzewska, Agnieszka; Mielniczek-Brzóska, Ewa

2014-06-01

Effect of disodium EDTA (salt of ethylenediamine tetraacetic acid) on the crystallization of struvite and carbonate apatite was studied. To evaluate such an effect we performed an experiment of struvite and carbonate apatite growth from artificial urine. The crystallization process was induced by Proteus mirabilis to mimic the real urinary tract infection, which usually leads to urinary stone formation. The results demonstrate that disodium EDTA exhibits the effect against P. mirabilis retarding the activity of urease - an enzyme produced by these microorganisms. The spectrophotometric results demonstrate that, with and without P. mirabilis, the addition of disodium EDTA increases the induction time and decreases the growth efficiency compared to the baseline (without disodium EDTA). These results are discussed from the standpoint of speciation of complexes formed in the solution of artificial urine in the presence of disodium EDTA. The size of struvite crystals was found to decrease in the presence of disodium EDTA. However, struvite crystals are larger in the presence of bacteria while the crystal morphology and habit remain unchanged.

Speciation of residual carbon contained in UO{sub 2}

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

Ziouane, Yannis; Arab-Chapelet, Bénédicte; Tamain, Christelle

2016-12-15

UO{sub 2} powders were synthesized thanks to oxalic precipitation (platelet morphology) and sol-gel route and completely characterized. A secondary phase was found depending on the calcination atmospheres. This phase has been identified by Raman spectroscopy as graphitic material (i.e. carbon-based secondary compound) and quantified by thermogravimetric analyses. Its amount varies with the calcination atmosphere. The presence of this secondary phase has no significant effect on the lattice parameter and its specific surface area. - Graphical abstract: Figure 2: Raman spectroscopy of the three UO{sub 2} powders and of the dissolution residues.

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy.

PubMed

Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

2018-07-01

We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 ). Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Spatial and seasonal patterns in urban influence on regional concentrations of speciated aerosols across the United States

NASA Astrophysics Data System (ADS)

Hand, J. L.; Schichtel, B. A.; Malm, W. C.; Pitchford, M.; Frank, N. H.

2014-11-01

Monthly, seasonal, and annual mean estimates of urban influence on regional concentrations of major aerosol species were computed using speciated aerosol data from the rural IMPROVE network (Interagency Monitoring of Protected Visual Environments) and the United States Environmental Protection Agency's urban Chemical Speciation Network for the 2008 through 2011 period. Aggregated for sites across the continental United States, the annual mean and one standard error in urban excess (defined as the ratio of urban to nearby rural concentrations) was highest for elemental carbon (3.3 ± 0.2), followed by ammonium nitrate (2.5 ± 0.2), particulate organic matter (1.78 ± 0.08), and ammonium sulfate (1.23 ± 0.03). The seasonal variability in urban excess was significant for carbonaceous aerosols and ammonium nitrate in the West, in contrast to the low seasonal variability in the urban influence of ammonium sulfate. Generally for all species, higher excess values in the West were associated with localized urban sources while in the East excess was more regional in extent. In addition, higher excess values in the western United States in winter were likely influenced not only by differences in sources but also by combined meteorological and topographic effects. This work has implications for understanding the spatial heterogeneity of major aerosol species near the interface of urban and rural regions and therefore for designing appropriate air quality management strategies. In addition, the spatial patterns in speciated mass concentrations provide constraints for regional and global models.

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.

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

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.

Selective determination of heavy metals (Cd, Pb, Cr) speciation forms from hortic anthrosols

NASA Astrophysics Data System (ADS)

Bulgariu, Dumitru; Bulgariu, Laura; Filipov, Feodor; Astefanei, Dan; Stoleru, Vasile

2010-05-01

In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have been performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 and project PNCDI 2 - D5 no. 52-141 / 2008).

Evidence of Enhanced Respired Carbon in Eastern Equatorial Pacific Deep-Waters over the last 30,000 years

NASA Astrophysics Data System (ADS)

Umling, N. E.; Thunell, R.

2016-12-01

Rapid decreases in glacial deep water reservoir ages have been observed in the Eastern Equatorial Pacific (EEP; this study), North Pacific (Rae et al., 2014), Southwest Pacific (Sikes et al., 2016), and North Atlantic (Skinner et al., 2013). It has been hypothesized that release of a deep ocean 14C-depleted, respired-carbon reservoir to the surface ocean and atmosphere is the most likely mechanism for the observed increases in atmospheric CO2 concentrations recorded in ice cores during the last glacial-interglacial transition (Broecker and Barker, 2007). This study examines whether oxygenation, organic carbon flux, and carbonate chemistry in the EEP deep-waters reflect an increase in respired carbon associated with recorded 14C-depletions using isotopic and trace element records from three Panama Basin cores (2,650-3,200 m water-depth). An increase in glacial deep-water respired carbon storage would result in a shift of DIC speciation towards lower carbonate ion concentrations along with deoxygenation of bottom waters. Specifically, we use the boron to calcium (B/Ca) and uranium to calcium (U/Ca) ratios of the benthic foraminifera Cibicidoides wuellerstorfi to reconstruct deep-water carbonate ion concentration (Yu and Elderfield, 2007; Raizsch et al., 2011). Additionally, bottom water oxygenation is estimated from the difference in δ13C of benthic foraminifera living in pore waters at the anoxic boundary and of those living in bottom water (Δ δ13C; Hoogakker et al., 2015, 2016), while carbon flux was assessed from the U/Ca and Cd/Ca of foraminiferal authigenic coatings.

The role of iron-sulfides on cycling of organic carbon in the St Lawrence River system: Evidence of sulfur-promoted carbon sequestration?

NASA Astrophysics Data System (ADS)

Balind, K.; Barber, A.; Gélinas, Y.

2017-12-01

The biogeochemical cycle of sulfur is intimately linked with that of carbon, as well as with that of iron through the formation of iron-sulfur complexes. Iron-sulfide minerals such as mackinawite (FeS) and greigite (Fe3S4) form below the oxic/anoxic redox boundary in marine and lacustrine sediments and soils. Reactive iron species, abundant in surface sediments, can undergo reductive dissolution leading to the formation of soluble Fe(II) which can then precipitate in the form of iron sulfur species. While sedimentary iron-oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) (Lalonde et al.; 2012), the role of FeS in the long-term preservation of OC remains undefined. In this study, we present depth profiles for carbon, iron, and sulfur in the aqueous-phase, along with data from sequential extractions of sulfur speciation in the solid-phase collected from sediment cores from the St Lawrence River and estuarine system, demonstrating the transition from fresh to saltwater sediments. Additionally, we present synthetic iron sulfur sorption experiments using both model and natural organic molecules in order to assess the importance of FeS in sedimentary carbon storage.

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.

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.

Particulate matter speciation profiles for light-duty gasoline vehicles in the United States.

PubMed

Sonntag, Darrell B; Baldauf, Richard W; Yanca, Catherine A; Fulper, Carl R

2014-05-01

Representative profiles for particulate matter particles less than or equal to 2.5 microm (PM2.5) are developed from the Kansas City Light-Duty Vehicle Emissions Study for use in the US. Environmental Protection Agency (EPA) vehicle emission model, the Motor Vehicle Emission Simulator (MOVES), and for inclusion in the EPA SPECIATE database for speciation profiles. The profiles are compatible with the inputs of current photochemical air quality models, including the Community Multiscale Air Quality Aerosol Module Version 6 (AE6). The composition of light-duty gasoline PM2.5 emissions differs significantly between cold start and hot stabilized running emissions, and between older and newer vehicles, reflecting both impacts of aging/deterioration and changes in vehicle technology. Fleet-average PM2.5 profiles are estimated for cold start and hot stabilized running emission processes. Fleet-average profiles are calculated to include emissions from deteriorated high-emitting vehicles that are expected to continue to contribute disproportionately to the fleet-wide PM2.5 emissions into the future. The profiles are calculated using a weighted average of the PM2.5 composition according to the contribution of PM2.5 emissions from each class of vehicles in the on-road gasoline fleet in the Kansas City Metropolitan Statistical Area. The paper introduces methods to exclude insignificant measurements, correct for organic carbon positive artifact, and control for contamination from the testing infrastructure in developing speciation profiles. The uncertainty of the PM2.5 species fraction in each profile is quantified using sampling survey analysis methods. The primary use of the profiles is to develop PM2.5 emissions inventories for the United States, but the profiles may also be used in source apportionment, atmospheric modeling, and exposure assessment, and as a basis for light-duty gasoline emission profiles for countries with limited data. PM2.5 speciation profiles were developed from a large sample of light-duty gasoline vehicles tested in the Kansas City area. Separate PM2.5 profiles represent cold start and hot stabilized running emission processes to distinguish important differences in chemical composition. Statistical analysis was used to construct profiles that represent PM2.5 emissions from the U.S. vehicle fleet based on vehicles tested from the 2005 calendar year Kansas City metropolitan area. The profiles have been incorporated into the EPA MOVES emissions model, as well as the EPA SPECIATE database, to improve emission inventories and provide the PM2.5 chemical characterization needed by CMAQv5.0 for atmospheric chemistry modeling.

Adsorbents for capturing mercury in coal-fired boiler flue gas.

PubMed

Yang, Hongqun; Xu, Zhenghe; Fan, Maohong; Bland, Alan E; Judkins, Roddie R

2007-07-19

This paper reviews recent advances in the research and development of sorbents used to capture mercury from coal-fired utility boiler flue gas. Mercury emissions are the source of serious health concerns. Worldwide mercury emissions from human activities are estimated to be 1000 to 6000 t/annum. Mercury emissions from coal-fired power plants are believed to be the largest source of anthropogenic mercury emissions. Mercury emissions from coal-fired utility boilers vary in total amount and speciation, depending on coal types, boiler operating conditions, and configurations of air pollution control devices (APCDs). The APCDs, such as fabric filter (FF) bag house, electrostatic precipitator (ESP), and wet flue gas desulfurization (FGD), can remove some particulate-bound and oxidized forms of mercury. Elemental mercury often escapes from these devices. Activated carbon injection upstream of a particulate control device has been shown to have the best potential to remove both elemental and oxidized mercury from the flue gas. For this paper, NORIT FGD activated carbon was extensively studied for its mercury adsorption behavior. Results from bench-, pilot- and field-scale studies, mercury adsorption by coal chars, and a case of lignite-burned mercury control were reviewed. Studies of brominated carbon, sulfur-impregnated carbon and chloride-impregnated carbon were also reviewed. Carbon substitutes, such as calcium sorbents, petroleum coke, zeolites and fly ash were analyzed for their mercury-adsorption performance. At this time, brominated activated carbon appears to be the best-performing mercury sorbent. A non-injection regenerable sorbent technology is briefly introduced herein, and the issue of mercury leachability is briefly covered. Future research directions are suggested.

Miscibility and Speciation in the Water/carbon Dioxide System

NASA Astrophysics Data System (ADS)

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

2017-12-01

We have been exploring fluid-fluid solubilities and speciation in mixed systems of CO2-H2O. Fluid-fluid immiscibility extends to the highest pressures and temperatures yet explored (7 GPa, 700K). In this region, commonly used COH fluid models agree neither with the data nor among themselves. The range of immiscibility is extended by addition of NaCl, but miscibility limits determined in preliminary experiments are not as expected from extrapolation of lower pressure (<0.2 GPa) results. For majority-water systems (XCO2<0.5) an abrupt increase of solubility with pressure is linked to an observed change in speciation as CO2(aq) reacts with water. The identity of the newly formed species is, as of the writing of this abstract, unknown, but presumed to be either H2CO3 or HCO3-. A reasonable match between the observed equilibria and an application of HKF theory suggests that the new species is, indeed, HCO3-, but with a Raman frequency shifted from that found in the dilute aqueous solution. Application of HKF theory to the CO2(f)-CO2(aq) equilibrium suffers from an incompatibility of the usual formulation of the theory with known molar volumes of CO2(f) at higher pressures. On the basis of these studies we conclude that models of CO2-H2O fluids must take into account major changes in speciation, and that simple equations-of-state, of a few fitted parameters, will not afford an adequate description of such fluids. "First principles" models, tested against real data, seem more likely to yield the desired results. This statement extends as well to the calculation of the dielectric constants of these mixed fluids, the basis of ionic solution chemistry. Further, semi-empirical formulations of solution thermodynamics, which function well at pressures of kbars, ought to be re-worked for use over larger pressure ranges.

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.

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.

On-line Field Measurements of Speciated PM1 Emission Factors from Common South Asian Combustion Sources

NASA Astrophysics Data System (ADS)

DeCarlo, P. F.; Goetz, J. D.; Giordano, M.; Stockwell, C.; Maharjan, R.; Adhikari, S.; Bhave, P.; Praveen, P. S.; Panday, A. K.; Jayarathne, T. S.; Stone, E. A.; Yokelson, R. J.

2017-12-01

Characterization of aerosol emissions from prevalent but under sampled combustion sources in South Asia was performed as part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) in April 2015. Targeted emission sources included cooking stoves with a variety of solid fuels, brick kilns, garbage burning, crop-residue burning, diesel irrigation pumps, and motorcycles. Real-time measurements of submicron non-refractory particulate mass concentration and composition were obtained using an Aerodyne mini Aerosol Mass Spectrometer (mAMS). Speciated PM1 mass emission factors were calculated for all particulate species (e.g. organics, sulfates, nitrates, chlorides, ammonium) and for each source type using the carbon mass balance approach. Size resolved emission factors were also acquired using a novel high duty cycle particle time-of-flight technique (ePTOF). Black carbon and brown carbon absorption emission factors and absorption Angström exponents were measured using filter loading and scattering corrected attenuation at 370 nm and 880 nm with a dual spot aethalometer (Magee Scientific AE-33). The results indicate that open garbage burning is a strong emitter of organic aerosol, black carbon, and internally mixed particle phase hydrogen chloride (HCl). Emissions of HCl were attributed to the presence chlorinated plastics. The primarily coal fired brick kilns were found to be large emitters of sulfate but large differences in the organic and light absorbing component of emissions were observed between the two kiln types investigated (technologically advanced vs. traditional). These results, among others, bring on-line and field-tested aerosol emission measurements to an area of atmoshperic research dominated by off-line or laboratory based measurements.

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

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...

Foraminiferal calcification and CO2

NASA Astrophysics Data System (ADS)

Nooijer, L. D.; Toyofuku, T.; Reichart, G. J.

2017-12-01

Ongoing burning of fossil fuels increases atmospheric CO2, elevates marine dissolved CO2 and decreases pH and the saturation state with respect to calcium carbonate. Intuitively this should decrease the ability of CaCO3-producing organisms to build their skeletons and shells. Whereas on geological time scales weathering and carbonate deposition removes carbon from the geo-biosphere, on time scales up to thousands of years, carbonate precipitation increases pCO2 because of the associated shift in seawater carbon speciation. Hence reduced calcification provides a potentially important negative feedback on increased pCO2 levels. Here we show that foraminifera form their calcium carbonate by active proton pumping. This elevates the internal pH and acidifies the direct foraminiferal surrounding. This also creates a strong pCO2 gradient and facilitates the uptake of DIC in the form of carbon dioxide. This finding uncouples saturation state from calcification and predicts that the added carbon due to ocean acidification will promote calcification by these organisms. This unknown effect could add substantially to atmospheric pCO2 levels, and might need to be accounted for in future mitigation strategies.

Floodplain influence on carbon speciation and fluxes from the lower Pearl River, Mississippi

NASA Astrophysics Data System (ADS)

Cai, Yihua; Shim, Moo-Joon; Guo, Laodong; Shiller, Alan

2016-08-01

To investigate the floodplain influence on carbon speciation and export to the northern Gulf of Mexico, water samples were collected monthly from two sites in the East Pearl River (EPR) basin during 2006-2008. Additionally, four spatial surveys in the river basin between those two sites were also conducted. Compared with the upstream sampling site at Bogalusa, MS, dissolved inorganic carbon (DIC) and particulate organic carbon (POC) concentrations were 36% and 55% lower, respectively, and dissolved organic carbon (DOC) concentration was 49% higher at the downstream Stennis Space Center (SSC) site. In addition, the bulk DOC pool at SSC had a higher colloidal fraction than at Bogalusa (75% vs. 68%). Detailed spatial surveys revealed the differences between the upstream and downstream stations resulted both from input from Hobolochitto Creek, a tributary of the EPR, and from influence of the swamp-rich floodplain. The contributions from Hobolochitto Creek to the carbon pool in the EPR basin were lowest during a high flow event and reached a maximum during the dry season. Meanwhile, the floodplain in the EPR basin acted as a significant sink for DOC, POC and particulate nitrogen during summer and for suspended sediment during a high flow event. However, the floodplain was converted into a source of suspended sediment, DOC, and POC to the EPR during winter, revealing a dynamic nature and seasonality in the floodplain influence. Consistent with its dominant forest coverage, abundant wetlands along the river corridor, and mild anthropogenic disturbance, the Pearl River basin above Bogalusa generally had higher yields of DOC and POC (1903 and 1386 kg-C km-2 yr-1, respectively), but a lower yield of DIC (2126 kg-C km-2 yr-1) compared to other North American rivers. An estimation based on a mass balance approach suggests the interactions between floodplain and the main river stem could reduce the annual DIC and POC export fluxes from downstream of the EPR by 24% and 40%, respectively, but enhance the annual riverine DOC export by 25%. Similar scenarios likely occur in other wetland-rich coastal rivers and are capable of significantly altering the current estimation of riverine carbon export.

Suspended particulate matter determines physical speciation of Fe, Mn, and trace metals in surface waters of Loire watershed.

PubMed

Baalousha, Mohamed; Stoll, Serge; Motelica-Heino, Mikaël; Guigues, Nathalie; Braibant, Gilles; Huneau, Frédéric; Le Coustumer, Philippe

2018-02-10

This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (< 10 nm), colloidal (10-450 nm) and particulate (> 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.

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

NASA Astrophysics Data System (ADS)

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

2014-07-01

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

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.

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 :...

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.

Effects of Dissolved Carbonate on Arsenate Adsorption and Surface Speciation at the Hematite-Water Interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2004-01-01

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [PCO2 = 10 -3.5 atm and ???0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L -1, [As(V)]0 = 1.5 mM and / = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L-1, [As(V)] 0 = 0.5 mM and / = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (PCO2 = 10-3.5 atm)than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (???2.8 A??) and bidentate binuclear (???3.3 A??) bonding at pH 4.5-8 and loading levels of 0.46-3.10 ??M m-2. Using the results of the pseudoequilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the PCO2 = 10-3.5 atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).

Comparative study on pharmaceuticals adsorption in reclaimed water desalination concentrate using biochar: Impact of salts and organic matter.

PubMed

Lin, Lu; Jiang, Wenbin; Xu, Pei

2017-12-01

The synergistic impact of salts and organic matter on adsorption of ibuprofen and sulfamethoxazole by three types of biochar and an activated carbon was investigated using reclaimed water reverse osmosis (RO) concentrate and synthetic solutions spiked with target organic compounds and non-target water constituents (e.g., Na + , Ca 2+ , Mg 2+ , K + , Cl - , SO 4 2- , alkalinity, humic acid (HA), and bovine serum albumin (BSA)). Kinetic modeling was used to better understand the adsorption process between the carbon adsorbents and pharmaceuticals and to elucidate the impact of water chemistry on pharmaceuticals adsorption. The adsorption capacity of pharmaceuticals by biochar was affected by their physicochemical properties including ash content, specific surface area, charge, pore volume, as well as hydrophobicity, π-energy, and speciation of pharmaceuticals. The adsorption of pharmaceuticals in concentrate was pH-dependent, the kinetic rate constant increased with deceasing pH due to the electrical interactions between pharmaceutical molecules and adsorbents. High salinity and electrolyte ions in RO concentrate improved adsorption, whereas the presence of carbonate species, HA, and BSA hindered the removal of ibuprofen and sulfamethoxazole. This study revealed the correlation of concentrate water quality on adsorption of pharmaceuticals by biochar and activated carbon. Biochar provides a promising alternative to activated carbon for removal of organic contaminants of emerging concerns in various wastewater and concentrate streams. Copyright © 2017 Elsevier B.V. All rights reserved.

Manganese and iron geochemistry in sediments underlying the redox-stratified Fayetteville Green Lake

NASA Astrophysics Data System (ADS)

Herndon, Elizabeth M.; Havig, Jeff R.; Singer, David M.; McCormick, Michael L.; Kump, Lee R.

2018-06-01

Manganese and iron are redox-sensitive elements that yield clues about biogeochemistry and redox conditions both in modern environments and in the geologic past. Here, we investigated Mn and Fe-bearing minerals preserved in basin sediments underlying Fayetteville Green Lake, a redox-stratified lake that serves as a geochemical analogue for Paleoproterozoic oceans. Synchrotron-source microprobe techniques (μXRF, μXANES, and μXRD) and bulk geochemical analyses were used to examine the microscale distribution and speciation of Mn, Fe, and S as a function of depth in the top 48 cm of anoxic lake sediments. Manganese was primarily associated with calcite grains as a manganese-rich carbonate that precipitated in the chemocline of the water column and settled through the euxinic basin to collect in lake sediments. Iron was preserved in framboidal iron sulfides that precipitated in euxinic bottom waters and underwent transformation to pyrite and marcasite in the sediments. Previous studies attribute the formation of manganese-rich carbonates to the diagenetic alteration of manganese oxides deposited in basins underlying oxygenated water. Our study challenges this paradigm by providing evidence that Mn-bearing carbonates form in the water column and accumulate in sediments below anoxic waters. Consequently, manganoan carbonates preserved in the rock record do not necessarily denote the presence of oxygenated bottom waters in ocean basins.

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

PubMed

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

2014-05-01

We evaluated the effects of pH and soluble organic carbon affected by organic amendments on metal mobility to find out the optimal conditions for their application in the stabilization of metals in mine soils. Soil samples (pH 5.5-6.2) were mixed with 0, 30 and 60 th a(-1) of sheep-horse manure (pH 9.4) and pine bark compost (pH 5.7). A single-step extraction procedure was performed using 0.005 M CaCl2 adjusted to pH 4.0-7.0 and metal speciation in soil solution was simulated using NICA-Donnan model. Sheep-horse manure reduced exchangeable metal concentrations (up to 71% Cu, 75% Zn) due to its high pH and degree of maturity, whereas pine bark increased them (32% Cu, 33% Zn). However, at increasing dose and hence pH, sheep-horse manure increased soluble Cu because of higher soluble organic carbon, whereas soluble Cu and organic carbon increased at increasing dose and correspondingly decreasing pH in pine bark and non-amended treatments. Near the native pH of these soils (at pH 5.8-6.3), with small doses of amendments, there was minimum soluble Cu and organic carbon. Pine bark also increased Zn solubility, whereas sheep-horse manure reduced it as soluble Zn always decreased with increasing pH. Sheep-horse manure also reduced the proportion of free metals in soil solution (from 41% to 4% Cu, from 97% to 94% Zn), which are considered to be more bioavailable than organic species. Sheep-horse manure amendment could be efficiently used for the stabilization of metals with low risk of leaching to groundwater at low doses and at relatively low pH, such as the native pH of mine soils. Copyright © 2013 Elsevier Ltd. All rights reserved.

Copper speciation and binding by organic matter in copper-contaminated streamwater

USGS Publications Warehouse

Breault, R.F.; Colman, J.A.; Aiken, G.R.; McKnight, D.

1996-01-01

Fulvic acid binding sites (1.3-70 ??M) and EDTA (0.0017-0.18 ??M) accounted for organically bound Cu in seven stream samples measured by potentiometric titration. Cu was 84-99% organically bound in filtrates with 200 nM total Cu. Binding of Cu by EDTA was limited by competition from other trace metals. Water hardness was inversely related to properties of dissolved organic carbon (DOC) that enhance fulvic acid binding: DOC concentration, percentage of DOC that is fulvic acid, and binding sites per fulvic acid carbon. Dissolved trace metals, stabilized by organic binding, occurred at increased concentration in soft water as compared to hard water.

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.

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.

Investigation of uranium binding forms in selected German mineral waters.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Bernhard, Gert; Worch, Eckhard

2013-12-01

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 μg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca2UO2(CO3)3 in all investigated waters, while other uranyl-carbonate complexes, viz, UO2CO3(aq) and UO2(CO3)2 (2-), only existed as minor species. The pH value, alkalinity (CO3 (2-)), and the main water inorganic constituents, specifically the Ca(2+) concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.

Biogeochemical controls on mercury methylation in the Allequash Creek wetland.

PubMed

Creswell, Joel E; Shafer, Martin M; Babiarz, Christopher L; Tan, Sue-Zanne; Musinsky, Abbey L; Schott, Trevor H; Roden, Eric E; Armstrong, David E

2017-06-01

We measured mercury methylation potentials and a suite of related biogeochemical parameters in sediment cores and porewater from two geochemically distinct sites in the Allequash Creek wetland, northern Wisconsin, USA. We found a high degree of spatial variability in the methylation rate potentials but no significant differences between the two sites. We identified the primary geochemical factors controlling net methylmercury production at this site to be acid-volatile sulfide, dissolved organic carbon, total dissolved iron, and porewater iron(II). Season and demethylation rates also appear to regulate net methylmercury production. Our equilibrium speciation modeling demonstrated that sulfide likely regulated methylation rates by controlling the speciation of inorganic mercury and therefore its bioavailability to methylating bacteria. We found that no individual geochemical parameter could explain a significant amount of the observed variability in mercury methylation rates, but we found significant multivariate relationships, supporting the widely held understanding that net methylmercury production is balance of several simultaneously occurring processes.

Trace gas and particle emissions from domestic and industrial biofuel use and garbage burning in central Mexico

Treesearch

T. J. Christian; R. J. Yokelson; B. Cardenas; L. T. Molina; G. Engling; S.-C. Hsu

2009-01-01

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl-, NO-3 , and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Biofuel use has been estimated at over 2600...

Trace gas and particle emissions from domestic and industrial biofuel use and garbage burning in central Mexico

Treesearch

T. J. Christian; R. J. Yokelson; B. Cardenas; L. T. Molina; G. Engling; S.-C. Hsu

2010-01-01

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl-, NO-3 , and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Global biofuel use has been...

Carbon-bearing MgSiO3 melt at deep mantle conditions

NASA Astrophysics Data System (ADS)

Ghosh, D. B.; Bajgain, S. K.; Mookherjee, M.; Karki, B. B.

2016-12-01

Carbon di-oxide and water are two important volatiles that are often present in silicate magmas and volcanic eruptions. To address the influence of these volatiles in deep seated melts, their properties (e.g., structure, transport, thermodynamics) at relevant pressure-temperature (P-T) conditions along with compositional variance need to be explored. MgSiO3 being one of the major components of the mantle, the study of carbonated MgSiO3 melts is of great contextual relevance. In the present work we investigate the structure and thermodynamics of carbon bearing MgSiO3 melts under conditions of the entire mantle.Our first-principles molecular dynamics (MD) simulations of the MgSiO3-CO2 system show that pressure profoundly influences the behavior of carbon-bearing silicate melts. Our results encompassing from 5 - 30 wt.% CO2 in MgSiO3 demonstrate that: (1) carbon speciation consists of distinct molecular CO2 and carbonate ions ( (CO3)2-) below 15 GPa and interestingly almost all of the carbonate ions are bound to Mg polyhedra; (2) with compression they evolve to silicon-polyhedral bound carbonate (along with Mg polyhedra bound), CO4 , and di-carbonate species. Accordingly, carbon solubility in the silicate melt becomes nearly ideal and carbon remains completely miscible with increasing pressure. Carbon reduces the melt density modestly by 0.015 to 0.005 g cm-3 per wt.% CO2 between 15 and 140 GPa. These results imply that deep-seated silicate melts above and below the transition zone, and atop the core-mantle boundary may be able to sequester significant amounts of carbon without making melts gravitationally unstable.

Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

USGS Publications Warehouse

Leenheer, Jerry A.; Reddy, Michael M.

2008-01-01

Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

Comparison of nickel release in solutions used for the identification of water-soluble nickel exposures and in synthetic lung fluids.

PubMed

Oller, Adriana R; Cappellini, Danielle; Henderson, Rayetta G; Bates, Hudson K

2009-04-01

Chemical speciation of workplace nickel exposures is critical because nickel-containing substances often differ in toxicological properties. Exposure matrices based on leaching methods have been used to ascertain which chemical forms of nickel are primarily associated with adverse respiratory effects after inhalation. Misjudgments in the relative proportion of each of the main fractions of nickel in workplace exposures could translate into possible misattributions of risk to the various forms of nickel. This preliminary study looked at the efficiency of the first step of the Zatka leaching method for accurately assessing the 'water-soluble' fraction of several substances present in nickel production operations, compared to leaching in synthetic lung fluid. The present results demonstrate that for nickel sulfate or chloride, the current Zatka solution is adequate to assess the 'water-soluble' fraction. However, when sparingly water-soluble compounds like nickel carbonates or water-insoluble substances like nickel subsulfide and fine metallic nickel powders are present, the first step of the Zatka method can greatly over estimate the amount of nickel that could be released in pure water. In contrast, the releases of nickel from nickel carbonate, nickel subsulfide, and nickel metal powders in pure water are consistent with their releases in synthetic lung fluid, indicating that deionized water is a better leaching solution to estimate the biologically relevant 'water-soluble' nickel fraction of workplace exposures. Exposure matrices relying mostly on the Zatka speciation method to estimate the main forms of nickel need to be re-evaluated to account for any possible misattributions of risk.

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

NASA Astrophysics Data System (ADS)

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; Davis, J. A.

2018-01-01

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonite edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites ('spillover' effect). A series of U(VI) - Na-montmorillonite batch adsorption experiments was conducted as a function of pH, with variable U(VI), Ca, and dissolved carbonate concentrations. Based on the experimental data, a new type of surface complexation model (SCM) was developed for montmorillonite, that specifically accounts for the spillover effect using the edge surface speciation model by Tournassat et al. (2016a). The SCM allows for a prediction of U(VI) adsorption under varying chemical conditions with a minimum number of fitting parameters, not only for our own experimental results, but also for a number of published data sets. The model agreed well with many of these datasets without introducing a second site type or including the formation of ternary U(VI)-carbonato surface complexes. The model predictions were greatly impacted by utilizing analytical measurements of dissolved inorganic carbon (DIC) concentrations in individual sample solutions rather than assuming solution equilibration with a specific partial pressure of CO2, even when the gas phase was laboratory air. Because of strong aqueous U(VI)-carbonate solution complexes, the measurement of DIC concentrations was even important for systems set up in the 'absence' of CO2, due to low levels of CO2 contamination during the experiment.

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

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.

Lineage-Specific Responses of Tooth Shape in Murine Rodents (Murinae, Rodentia) to Late Miocene Dietary Change in the Siwaliks of Pakistan

PubMed Central

Kimura, Yuri; Jacobs, Louis L.; Flynn, Lawrence J.

2013-01-01

Past ecological responses of mammals to climate change are recognized in the fossil record by adaptive significance of morphological variations. To understand the role of dietary behavior on functional adaptations of dental morphology in rodent evolution, we examine evolutionary change of tooth shape in late Miocene Siwalik murine rodents, which experienced a dietary shift toward C4 diets during late Miocene ecological change indicated by carbon isotopic evidence. Geometric morphometric analysis in the outline of upper first molars captures dichotomous lineages of Siwalik murines, in agreement with phylogenetic hypotheses of previous studies (two distinct clades: the Karnimata and Progonomys clades), and indicates lineage-specific functional responses to mechanical properties of their diets. Tooth shapes of the two clades are similar at their sympatric origin but deviate from each other with decreasing overlap through time. Shape change in the Karnimata clade is associated with greater efficiency of propalinal chewing for tough diets than in the Progonomys clade. Larger body mass in Karnimata may be related to exploitation of lower-quality food items, such as grasses, than in smaller-bodied Progonomys. The functional and ecophysiological aspects of Karnimata exploiting C4 grasses are concordant with their isotopic dietary preference relative to Progonomys. Lineage-specific selection was differentially greater in Karnimata, and a faster rate of shape change toward derived Karnimata facilitated inclusion of C4 grasses in the diet. Sympatric speciation in these clades is most plausibly explained by interspecific competition on resource utilization between the two, based on comparisons of our results with the carbon isotope data. Interspecific competition with Karnimata may have suppressed morphological innovation of the Progonomys clade. Pairwise analyses of morphological and carbon isotope data can uncover ecological causes of sympatric speciation and define functional adaptations of teeth to resources. PMID:24155885

Lineage-specific responses of tooth shape in murine rodents (murinae, rodentia) to late Miocene dietary change in the Siwaliks of Pakistan.

PubMed

Kimura, Yuri; Jacobs, Louis L; Flynn, Lawrence J

2013-01-01

Past ecological responses of mammals to climate change are recognized in the fossil record by adaptive significance of morphological variations. To understand the role of dietary behavior on functional adaptations of dental morphology in rodent evolution, we examine evolutionary change of tooth shape in late Miocene Siwalik murine rodents, which experienced a dietary shift toward C4 diets during late Miocene ecological change indicated by carbon isotopic evidence. Geometric morphometric analysis in the outline of upper first molars captures dichotomous lineages of Siwalik murines, in agreement with phylogenetic hypotheses of previous studies (two distinct clades: the Karnimata and Progonomys clades), and indicates lineage-specific functional responses to mechanical properties of their diets. Tooth shapes of the two clades are similar at their sympatric origin but deviate from each other with decreasing overlap through time. Shape change in the Karnimata clade is associated with greater efficiency of propalinal chewing for tough diets than in the Progonomys clade. Larger body mass in Karnimata may be related to exploitation of lower-quality food items, such as grasses, than in smaller-bodied Progonomys. The functional and ecophysiological aspects of Karnimata exploiting C4 grasses are concordant with their isotopic dietary preference relative to Progonomys. Lineage-specific selection was differentially greater in Karnimata, and a faster rate of shape change toward derived Karnimata facilitated inclusion of C4 grasses in the diet. Sympatric speciation in these clades is most plausibly explained by interspecific competition on resource utilization between the two, based on comparisons of our results with the carbon isotope data. Interspecific competition with Karnimata may have suppressed morphological innovation of the Progonomys clade. Pairwise analyses of morphological and carbon isotope data can uncover ecological causes of sympatric speciation and define functional adaptations of teeth to resources.

Compacted Sewage Sludge as a Barrier for Tailings: The Heavy Metal Speciation and Total Organic Carbon Content in the Compacted Sludge Specimen

PubMed Central

Zhang, Huyuan; Zhang, Qing; Yang, Bo; Wang, Jinfang

2014-01-01

Acid mine drainage (AMD) was the main environmental problem facing the mining industry. For AMD had high heavy metals content and low pH, the compacted sewage sludge might be a barrier for tailings whose oxidation and weathering produced AMD, with its own carbon source, microorganism reduction ability and impermeability. To study the heavy metals environmental risk, under the simulate AMD, the deionized water (DW), and the pH 2.1 sulfuric acid water (SA) seepage conditions, respectively, the changes of the chemical speciation of heavy metals Cd, Cu, Fe, Ni, Zn and total organic carbon (TOC) content in the compacted sewage sludge were assessed in the different periods. The results indicated according to the distribution of heavy metals, the potential mobility was for Cd: 6.08 under AMD, 7.48 under SA, ∞ under DW; for Cu: 0.08 under AMD, 0.17 under SA, 0.59 under DW; for Fe: 0.15 under AMD, 0.22 under SA, 0.22 under DW; for Ni: 2.60 under AMD, 1.69 under SA, 1.67 under DW; and for Zn: 0.15 under AMD, 0.23 under SA and 0.21 under DW at the second checking time. TOC content firstly decreased from 67.62±0% to 66.29±0.35%, then increased to 67.74±0.65% under the AMD seepage while TOC decreased to 63.30±0.53%, then to 61.33±0.37% under the DW seepage, decreased to 63.86±0.41%, then to 63.28±0.49% under SA seepage. That indicated under the AMD seepage, the suitable microorganisms communities in the compacted sewage sludge were activated. And the heavy metals environmental risk of compacted sewage sludge was lower with AMD condition than with other two. So the compacted sewage sludge as a barrier for tailings was feasible as the aspect of environmental risk assessment. PMID:24979755

Disentangling the record of diagenesis, local redox conditions, and global seawater chemistry during the latest Ordovician glaciation

NASA Astrophysics Data System (ADS)

Ahm, Anne-Sofie C.; Bjerrum, Christian J.; Hammarlund, Emma U.

2017-02-01

The Late Ordovician stratigraphic record integrates glacio-eustatic processes, water-column redox conditions and carbon cycle dynamics. This complex stratigraphic record, however, is dominated by deposits from epeiric seas that are susceptible to local physical and chemical processes decoupled from the open ocean. This study contributes a unique deep water basinal perspective to the Late Ordovician (Hirnantian) glacial record and the perturbations in seawater chemistry that may have contributed to the Hirnantian mass extinction event. We analyze recently drilled cores and outcrop samples from the upper Vinini Formation in central Nevada and report combined trace- and major element geochemistry, Fe speciation (FePy /FeHR and FeHR /FeT), and stable isotope chemostratigraphy (δ13COrg and δ34SPy). Measurements of paired samples from outcrop and core reveal that reactive Fe is preserved mainly as pyrite in core samples, while outcrop samples have been significantly altered as pyrite has been oxidized and remobilized by modern weathering processes. Fe speciation in the more pristine core samples indicates persistent deep water anoxia, at least locally through the Late Ordovician, in contrast to the prevailing interpretation of increased Hirnantian water column oxygenation in shallower environments. Deep water redox conditions were likely decoupled from shallower environments by a basinal shift in organic matter export driven by decreasing rates of organic matter degradation and decreasing shelf areas. The variable magnitude in the record of the Hirnantian carbon isotope excursion may be explained by this increased storage of isotopically light carbon in the deep ocean which, in combination with increased glacio-eustatic restriction, would strengthen lateral- and vertical gradients in seawater chemistry. We adopt multivariate statistical methods to deconstruct the spatial and temporal re-organization of seawater chemistry during the Hirnantian glaciation and attempt to isolate the latent magnitude and global perturbation in the carbon cycle. We speculate, using a two component mixing model and residual estimates from principal component analysis, that the secular open ocean Hirnantian C isotope excursion possibly amounts to only ∼ +1.5‰. Such an increase could be mechanistically driven by the combination of sea-level fall, persistent deep water anoxia, and cooler glacial temperatures that increased the organic carbon burial efficiency in the deeper basins.

Carbon and nitrogen speciation in nitrogen-rich C-O-H-N fluids at 5.5-7.8 GPa

NASA Astrophysics Data System (ADS)

Sokol, Alexander G.; Palyanov, Yury N.; Tomilenko, Anatoly A.; Bul'bak, Taras A.; Palyanova, Galina A.

2017-02-01

Carbon and nitrogen speciation has been studied in high-pressure experiments in the C-O-H-N and C-O-H-N-Fe3C systems at 5.5 to 7.8 GPa and 1100 to 1500 °C using a split-sphere multi-anvil apparatus. Oxygen fugacity in the samples was either buffered by the Mo-MoO2 (MMO) and Fe-FeO (IW) equilibria using a double-capsule technique or left unbuffered. fO2 varied from 2 log units below to +4 log units above the iron-wüstite oxygen buffer (IW) depending on water contents in the charges and buffering. Ultra-reduced fluids contained NH3 as the dominant species, but its concentration was slightly lower, while CH4 was higher at higher temperatures. As oxygen fugacity and temperature increased to fO2 0.7 log units above IW and T ≥ 1400 °C, N2 became the predominant nitrogen species; the dominance among carbon species changed from CH4 and C2-C5 alkanes to oxygenated hydrocarbons and higher alkanes. It has been found out for the first time that the N2-rich fluid lacks methane at fO2 4 log units above IW but may bear a few percent of C2H6, C3H8, and C15-C18 alkanes and within one percent of alcohols, aldehydes, ketones, carboxylic acids, and furans. Thus, the NH3 enrichment of fluids and the nitrogen storage capacity of silicates at depths ∼200 km are expected to be the greatest in cold (1100-1200 °C) and reduced continental lithospheric mantle. In a hotter lithosphere of ∼1400 °C, the concentrations of NH3 and N2 in fluids are similar, and the nitrogen storage capacity of silicates should be relatively low. The stability of some higher alkanes and oxygenated hydrocarbons in nitrogen-rich fluids near the enstatite-magnesite-olivine-diamond/graphite (EMOG/D) equilibrium suggest that these carbon species, together with N2, can survive at the redox barrier, where silicate or silicate-carbonate melts capture them and entrain to shallow mantle.

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.

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

PubMed Central

Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.

2016-01-01

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465

Seasonal variation of organic aerosol in PM2.5 at Anmyeondo, a background site in Korea

NASA Astrophysics Data System (ADS)

Lee, J.; Kim, E. S.; Kim, Y. P.; Jung, C. H.; Lee, J.

2016-12-01

Routine measurements of PM2.5 and chemical speciation for 100 individual organic compounds were carried out to understand seasonal variation of organic compounds at a background area in Korea between 2015 and 2016. Organic compounds analyzed in this study were classified into five groups, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), fatty acids (FA), dicarboxylic acids (DCAs), and sugar. Further, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC) and Humic Like Substance-Carbon (HULIS-C) in PM2.5 were simultaneously analyzed to make mass balance of carbonaceous aerosol in PM2.5 at a background site in Korea. PAHs concentrations at this site was lower than that at Seoul, a representative urban site in Korea. PAHs and n-Alkanes concentrations showed clear seasonal variation with summer minimum and winter maximum, while, seasonal variation of DCAs and Sugars were different with PAHs and n-Alkanes.WSOC concentrations were highly correlated with SOC (Secondary Organic Carbon) concentrations which were estimated by the EC tracer method. The results indicate the formation of secondary organic aerosol (SOA) is major factor for the determination of WSOC concentrations in this region. HULIS-C as known one of brown carbon was major component of WSOC which accounts for 39 to 99% in WSOC. The average concentrations of HULIS-C was 2.02±1.42 and the highest concentration was observed in fall.

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin.

PubMed

Fujita, Eric M; Zielinska, Barbara; Campbell, David E; Arnott, W Patrick; Sagebiel, John C; Mazzoleni, Lynn; Chow, Judith C; Gabele, Peter A; Crews, William; Snow, Richard; Clark, Nigel N; Wayne, W Scott; Lawson, Douglas R

2007-06-01

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

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.

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

Carbonaceous aerosol at two rural locations in New York State: Characterization and behavior

NASA Astrophysics Data System (ADS)

Sunder Raman, Ramya; Hopke, Philip K.; Holsen, Thomas M.

2008-06-01

Fine particle samples were collected to determine the chemical constituents in PM2.5 at two rural background sites (Potsdam and Stockton, N. Y.) in the northeastern United States from November 2002 to August 2005. Samples were collected every third day for 24 h with a speciation network sampler. The measured carbonaceous species included thermal-optical organic carbon (OC), elemental carbon (EC), pyrolytic carbon (OP), black carbon (BC), and water-soluble, short-chain (WSSC) organic acids. Concentration time series, autocorrelations, and seasonal variations of the carbonaceous species were examined. During this multiyear period, the contributions of the total carbon (OC + EC) to the measured fine particle mass were 31.2% and 31.1% at Potsdam and Stockton, respectively. The average sum of the WSSC acids carbon accounted for approximately 2.5% of the organic carbon at Potsdam and 3.0% at Stockton. At Potsdam, the seasonal differences in the autocorrelation function (ACF) and partial autocorrelation function (PACF) values for carbonaceous species suggest that secondary formation may be an important contributor to the observed concentrations of species likely to be secondary in origin, particularly during the photochemically active time of the year (May to October). This study also investigated the relationships between carbonaceous species to better understand the behavior of carbonaceous aerosol and to assess the contribution of secondary organic carbon (SOC) to the total organic carbon mass (the EC tracer method was used to estimate SOC). At Potsdam the average SOC contribution to total OC varied between 66% and 72%, while at Stockton it varied between 58% and 64%.

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

Generation and characterization of four dilutions of diesel engine exhaust for a subchronic inhalation study.

PubMed

McDonald, Jacob D; Barr, Edward B; White, Richard K; Chow, Judith C; Schauer, James J; Zielinska, Barbara; Grosjean, Eric

2004-05-01

Exposure atmospheres for a rodent inhalation toxicology study were generated from the exhaust of a 2000 Cummins ISB 5.9L diesel engine coupled to a dynamometer and operated on a slightly modified heavy-duty Federal Test Procedure cycle. Exposures were conducted to one clean air control and four diesel exhaust levels maintained at four different dilution rates (300:1, 100:1, 30:1, 10:1) that yielded particulate mass concentrations of 30, 100, 300, and 1000 microg/m3. Exposures at the four dilutions were characterized for particle mass, particle size distribution (reported elsewhere), detailed chemical speciation of gaseous, semivolatile, and particle-phase inorganic and organic compounds. Target analytes included metals, inorganic ions and gases, organic and elemental carbon, alkanes, alkenes, aromatic and aliphatic acids, aromatic hydrocarbons, polycyclic aromatic hydrocarbons (PAH), oxygenated PAH, nitrogenated PAH, isoprenoids, carbonyls, methoxyphenols, sugar derivatives, and sterols. The majority of the mass of material in the exposure atmospheres was gaseous nitrogen oxides and carbon monoxide, with lesser amounts of volatile organics and particle mass (PM) composed of carbon (approximately 90% of PM) and ions (approximately 10% of PM). Measured particle organic species accounted for about 10% of total organic particle mass and were mostly alkanes and aliphatic acids. Several of the components in the exposure atmosphere scaled in concentration with dilution but did not scale precisely with the dilution rate because of background from the rodents and scrubbed dilution air, interaction of animal derived emissions with diesel exhaust components, and day-to-day variability in the output of the engine. Rodent-derived ammonia reacted with exhaust to form secondary inorganic particles (at different rates dependent on dilution), and rodent respiration accounted for volatile organics (especially carbonyls and acids) in the same range as the diesel exhaust at the lowest exhaust exposure concentrations. Day-to-day variability in the engine output was implicated partially for differences of several components, including some of the particle bound organics. Though these observations have likely occurred in nearly all inhalation exposure atmospheres that contain complex mixtures of material, the speciations conducted here illustrate many of them for the first time.

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 ...

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.

Tracking niche variation over millennial timescales in sympatric killer whale lineages

PubMed Central

Foote, Andrew D.; Newton, Jason; Ávila-Arcos, María C.; Kampmann, Marie-Louise; Samaniego, Jose A.; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S.; Gilbert, M. Thomas P.

2013-01-01

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish. PMID:23945688

Tracking niche variation over millennial timescales in sympatric killer whale lineages.

PubMed

Foote, Andrew D; Newton, Jason; Ávila-Arcos, María C; Kampmann, Marie-Louise; Samaniego, Jose A; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S; Gilbert, M Thomas P

2013-10-07

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish.

Comparison and evaluation of in situ and filter carbon measurements at the Fresno Supersite

NASA Astrophysics Data System (ADS)

Watson, John G.; Chow, Judith C.

2002-11-01

The Fresno Supersite in Fresno, California, USA, acquires in situ 5- to 60-min average PM2.5 organic carbon (OC), elemental carbon (EC), and total carbon (TC) measurements by the following methods: (1) thermal evolution carbon analyzer for organic, elemental, and total carbon; (2) single-wavelength and seven-color aethalometer for black carbon (BC); and (3) photoionization for particle-bound polycyclic aromatic hydrocarbons. Twenty-four-hour average PM2.5 filter-based measurements include (1) nondenuded quartz filters with no backup filter in a PM2.5 Federal Reference Method (FRM) sampler; (2) quartz filters behind an organic carbon denuder with a quartz backup filter in a Reference Ambient Aerosol Sampler (RAAS); (3) nondenuded quartz filters with backup filter in a RAAS; and (4) nondenuded quartz filters with no backup filter in a sequential filter sampler. Filter samples are analyzed after sampling by the Interagency Monitoring of Protected Visual Environments (IMPROVE) thermal/optical reflectance carbon analysis protocol. Collocated measurements are examined for year 2000. Measurement equivalence is found for PM2.5 mass, light transmission, and TC between the FRM and RAAS speciation samplers. The average ratios of front filter carbon between the denuded and nondenuded channels in the RAAS sampler are 0.83 ± 0.19 for TC, 0.81 ± 0.20 for OC, and 1.01 ± 0.33 for EC. The average differences for TC and OC are low (1.2 to 1.4 μg m-3) and are comparable to the measurement uncertainties. Continuous thermal evolution carbon measurements are not comparable to filter measurements. Aethalometer BC and filter EC are highly correlated, but filter EC is consistently 20-25% higher than continuous aethalometer BC. Pairwise comparisons show filter EC measurements acquired in this study are predictable from aethalometer BC measurements.

[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.

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.

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.

Effects of Al(III) and Nano-Al13 Species on Malate Dehydrogenase Activity

PubMed Central

Yang, Xiaodi; Cai, Ling; Peng, Yu; Li, Huihui; Chen, Rong Fu; Shen, Ren Fang

2011-01-01

The effects of different aluminum species on malate dehydrogenase (MDH) activity were investigated by monitoring amperometric i-t curves for the oxidation of NADH at low overpotential using a functionalized multi-wall nanotube (MWNT) modified glass carbon electrode (GCE). The results showed that Al(III) and Al13 can activate the enzymatic activity of MDH, and the activation reaches maximum levels as the Al(III) and Al13 concentration increase. Our study also found that the effects of Al(III) and Al13 on the activity of MDH depended on the pH value and aluminum speciation. Electrochemical and circular dichroism spectra methods were applied to study the effects of nano-sized aluminum compounds on biomolecules. PMID:22163924

Effects of Al(III) and nano-Al13 species on malate dehydrogenase activity.

PubMed

Yang, Xiaodi; Cai, Ling; Peng, Yu; Li, Huihui; Chen, Rong Fu; Shen, Ren Fang

2011-01-01

The effects of different aluminum species on malate dehydrogenase (MDH) activity were investigated by monitoring amperometric i-t curves for the oxidation of NADH at low overpotential using a functionalized multi-wall nanotube (MWNT) modified glass carbon electrode (GCE). The results showed that Al(III) and Al(13) can activate the enzymatic activity of MDH, and the activation reaches maximum levels as the Al(III) and Al(13) concentration increase. Our study also found that the effects of Al(III) and Al(13) on the activity of MDH depended on the pH value and aluminum speciation. Electrochemical and circular dichroism spectra methods were applied to study the effects of nano-sized aluminum compounds on biomolecules.

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

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.

The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

NASA Astrophysics Data System (ADS)

Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

2013-06-01

The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering capacity to previously studied non-halophilic bacteria. The titration data were used to determine the number of types, concentrations, and associated deprotonation constants of functional groups on the bacterial surface; the neptunium adsorption measurements were used to constrain binding constant values for the important neptunium (V)-bacterial surface species. Together, these results can be incorporated into geochemical speciation models to aid in the prediction of neptunium (V) mobility in complex bacteria-bearing geochemical systems.

Speciation and Sources of Brown Carbon in Precipitation at Seoul, Korea: Insights from Excitation-Emission Matrix Spectroscopy and Carbon Isotopic Analysis.

PubMed

Yan, Ge; Kim, Guebuem

2017-10-17

Brown carbon (BrC) plays a significant role in the Earth's radiative balance, yet its sources and chemical composition remain poorly understood. In this work, we investigated BrC in the atmospheric environment of Seoul by characterizing dissolved organic matter in precipitation using excitation-emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC). The two independent fluorescent components identified by PARAFAC were attributed to humic-like substance (HULIS) and biologically derived material based on their significant correlations with measured HULIS isolated using solid-phase extraction and total hydrolyzable tyrosine. The year-long observation shows that HULIS contributes to 66 ± 13% of total fluorescence intensity of our samples on average. By using dual carbon ( 13 C and 14 C) isotopic analysis conducted on isolated HULIS, the HULIS fraction of BrC was found to be primarily derived from biomass burning and emission of terrestrial biogenic gases and particles (>70%), with minor contributions from fossil-fuel combustion. The knowledge derived from this study could contribute to the establishment of a characterizing system of BrC components identified by EEM spectroscopy. Our work demonstrates that, EEM fluorescence spectroscopy is a powerful tool in BrC study, on the basis of its chromophore resolving power, allowing investigation into individual components of BrC by other organic matter characterization techniques.

Speciation and formation of iodinated trihalomethane from microbially derived organic matter during the biological treatment of micro-polluted source water.

PubMed

Wei, Yuanyuan; Liu, Yan; Ma, Luming; Wang, Hongwu; Fan, Jinhong; Liu, Xiang; Dai, Rui-Hua

2013-09-01

Water sources are micro-polluted by the increasing range of anthropogenic activities around them. Disinfection byproduct (DBP) precursors in water have gradually expanded from humic acid (HA) and fulvic acid to other important sources of potential organic matter. This study aimed to provide further insights into the effects of microbially derived organic matter as precursors on iodinated trihalomethane (I-THM) speciation and formation during the biological treatment of micro-polluted source water. The occurrence of I-THMs in drinking water treated by biological processes was investigated. The results showed for the first time that CHCl2I and CHBrClI are emerging DBPs in China. Biological pre-treatment and biological activated carbon can increase levels of microbes, which could serve as DBP precursors. Chlorination experiments with bovine serum albumin (BSA), starch, HA, deoxyribonucleic acid (DNA), and fish oil, confirmed the close correlation between the I-THM species identified during the treatment processes and those predicted from the model compounds. The effects of iodide and bromide on the I-THM speciation and formation were related to the biochemical composition of microbially derived organic precursors. Lipids produced up to 16.98μgL(-1) of CHCl2I at an initial iodide concentration of 2mgL(-1). HA and starch produced less CHCl2I at 3.88 and 3.54μgL(-1), respectively, followed by BSA (1.50μgL(-1)) and DNA (1.35μgL(-1)). Only fish oil produced I-THMs when iodide and bromide were both present in solution; the four other model compounds formed brominated species. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lead toxicity to Lemna minor predicted using a metal speciation chemistry approach.

PubMed

Antunes, Paula M C; Kreager, Nancy J

2014-10-01

In the present study, predictive measures for Pb toxicity and Lemna minor were developed from bioassays with 7 surface waters having varied chemistries (0.5-12.5 mg/L dissolved organic carbon, pH of 5.4-8.3, and water hardness of 8-266 mg/L CaCO3 ). As expected based on water quality, 10%, 20%, and 50% inhibitory concentration (IC10, IC20, and IC50, respectively) values expressed as percent net root elongation (%NRE) varied widely (e.g., IC20s ranging from 306 nM to >6920 nM total dissolved Pb), with unbounded values limited by Pb solubility. In considering chemical speciation, %NRE variability was better explained when both Pb hydroxides and the free lead ion were defined as bioavailable (i.e., f{OH} ) and colloidal Fe(III)(OH)3 precipitates were permitted to form and sorb metals (using FeOx as the binding phase). Although cause and effect could not be established because of covariance with alkalinity (p = 0.08), water hardness correlated strongly (r(2)  = 0.998, p < 0.0001) with the concentration of total Pb in true solution ([Pb]T_True solution ). Using these correlations as the basis for predictions (i.e., [Pb]T_True solution vs water hardness and %NRE vs f{OH} ), IC20 and IC50 values produced were within a factor of 2.9 times and 2.2 times those measured, respectively. The results provide much needed effect data for L. minor and highlight the importance of chemical speciation in Pb-based risk assessments for aquatic macrophytes. © 2014 SETAC.

Chemical and biological consequences of using carbon dioxide versus acid additions in ocean acidification experiments

USGS Publications Warehouse

Yates, Kimberly K.; DuFore, Christopher M.; Robbins, Lisa L.

2013-01-01

Use of different approaches for manipulating seawater chemistry during ocean acidification experiments has confounded comparison of results from various experimental studies. Some of these discrepancies have been attributed to whether addition of acid (such as hydrochloric acid, HCl) or carbon dioxide (CO2) gas has been used to adjust carbonate system parameters. Experimental simulations of carbonate system parameter scenarios for the years 1766, 2007, and 2100 were performed using the carbonate speciation program CO2SYS to demonstrate the variation in seawater chemistry that can result from use of these approaches. Results showed that carbonate system parameters were 3 percent and 8 percent lower than target values in closed-system acid additions, and 1 percent and 5 percent higher in closed-system CO2 additions for the 2007 and 2100 simulations, respectively. Open-system simulations showed that carbonate system parameters can deviate by up to 52 percent to 70 percent from target values in both acid addition and CO2 addition experiments. Results from simulations for the year 2100 were applied to empirically derived equations that relate biogenic calcification to carbonate system parameters for calcifying marine organisms including coccolithophores, corals, and foraminifera. Calculated calcification rates for coccolithophores, corals, and foraminifera differed from rates at target conditions by 0.5 percent to 2.5 percent in closed-system CO2 gas additions, from 0.8 percent to 15 percent in the closed-system acid additions, from 4.8 percent to 94 percent in open-system acid additions, and from 7 percent to 142 percent in open-system CO2 additions.

In Vitro Model To Assess Arsenic Bioaccessibility and Speciation in Cooked Shrimp.

PubMed

Chi, Haifeng; Zhang, Youchi; Williams, Paul N; Lin, Shanna; Hou, Yanwei; Cai, Chao

2018-05-09

Shrimp, a popular and readily consumed seafood, contains high concentrations of arsenic. However, few studies have focused on whether arsenic in the shrimp could be transformed during the cooking process and gastrointestinal digestion. In this study, a combined in vitro model [Unified Bioaccessibility Research Group of Europe (BARGE) Method-Simulator of Human Intestinal Microbial Ecosystem (UBM-SHIME)] was used to investigate arsenic bioaccessibility and its speciation in raw and cooked shrimps. The results showed that the cooking practices had little effect on the arsenic content and speciation. Bioaccessibility of arsenic in raw shrimp was at a high level, averaging 76.9 ± 4.28 and 86.7 ± 3.74% in gastric and small intestinal phases, respectively. Arsenic speciation was stable in all of the shrimp digestions, with nontoxic arsenobetaine (AsB) being the dominated speciation. The cooking practice significantly increased the bioaccessibility of arsenate ( p < 0.05) in shrimp digests, indicating the increase of the potential health risks.

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

PubMed

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

2013-01-01

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

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...

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.

Source apportionment of secondary organic aerosol in China using a regional source-oriented chemical transport model and two emission inventories.

PubMed

Wang, Peng; Ying, Qi; Zhang, Hongliang; Hu, Jianlin; Lin, Yingchao; Mao, Hongjun

2018-06-01

A Community Multiscale Air Quality (CMAQ) model with source-oriented lumped SAPRC-11 (S11L) photochemical mechanism and secondary organic aerosol (SOA) module was applied to determine the contributions of anthropogenic and biogenic sources to SOA concentrations in China. A one-year simulation of 2013 using the Multi-resolution Emission Inventory for China (MEIC) shows that summer SOA are generally higher (10-15 μg m -3 ) due to large contributions of biogenic (country average 60%) and industrial sources (17%). In winter, SOA formation was mostly due to anthropogenic emissions from industries (40%) and residential sources (38%). Emissions from other countries in southeast China account for approximately 14% of the SOA in both summer and winter, and 46% in spring due to elevated open biomass burning in southeast Asia. The Regional Emission inventory in ASia v2.1 (REAS2) was applied in this study for January and August 2013. Two sets of simulations with the REAS2 inventory were conducted using two different methods to speciate total non-methane carbon into model species. One approach uses total non-methane hydrocarbon (NMHC) emissions and representative speciation profiles from the SPECIATE database. The other approach retains the REAS2 speciated species that can be directly mapped to S11L model species and uses source specific splitting factors to map other REAS2 lumped NMHC species. Biogenic emissions are still the most significant contributor in summer based on these two sets of simulations. However, contributions from the transportation sector to SOA in January are predicted to be much more important based on the two REAS2 emission inventories (∼30-40% vs. ∼5% by MEIC), and contributions from residential sources according to REAS2 was much lower (∼21-24% vs. ∼42%). These discrepancies in source contributions to SOA need to be further investigated as the country seeks for optimal emission control strategies to fight severe air pollution. Copyright © 2017 Elsevier Ltd. All rights reserved.

New technique for quantification of elemental hg in mine wastes and its implications for mercury evasion into the atmosphere

USGS Publications Warehouse

Jew, A.D.; Kim, C.S.; Rytuba, J.J.; Gustin, M.S.; Brown, Gordon E.

2011-01-01

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline ??-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica-carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica-carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range. ?? 2011 American Chemical Society.

Potentiometric and spectrophotometric study of the stability of magnesium carbonate and bicarbonate ion pairs to 150 °C and aqueous inorganic carbon speciation and magnesite solubility

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Bénézeth, Pascale; Schott, Jacques

2014-08-01

The formation constants of magnesium bicarbonate and carbonate ion pairs have been experimentally determined in dilute hydrothermal solutions to 150 °C. Two experimental approaches were applied, potentiometric acid-base titrations at 10-60 °C and spectrophotometric pH measurements using two pH indicators, 2-naphthol and 4-nitrophenol, at 25 and 80-150 °C. At a given temperature, the first and second ionization constants of carbonic acid (K1, K2) and the ion pair formation constants for MgHCO3+(aq) (KMgHCO3+) and MgCO3(aq) (KMgCO3) were simultaneously fitted to the data. Results of this study compare well with previously determined values of K1 and K2. The formation constants of MgHCO3+(aq) and MgCO3(aq) ion pairs increased significantly with increasing temperature, with values of logKMgHCO3+ = 1.14 and 1.75 and of logKMgCO3 = 2.86 and 3.48 at 10 °C and 100 °C, respectively. These ion pairs are important aqueous species under neutral to alkaline conditions in moderately dilute to concentrated Mg-containing solutions, with MgCO3(aq) predominating over CO32-(aq) in solutions at pH >8. The predominance of magnesium carbonate over carbonate is dependent on the concentration of dissolved magnesium and the ratio of magnesium over carbonate. With increasing temperature and at alkaline pH, brucite solubility further reduced the magnesium concentration to levels below 1 mmol kg-1, thus limiting availability of Mg2+(aq) for magnesite precipitation.

Growth patterns of the Cambrian microbialite: Phototropism and speciation of Epiphyton

NASA Astrophysics Data System (ADS)

Woo, J.; Chough, S. K.

2010-07-01

Microbes started constructing shallow marine stromatolitic bioherms in the Archean, but they transferred their role as a major buildup maker to metazoans in Phanerozoic. Microbial buildups often recovered their predominance in the carbonate platform when reefal metazoan communities collapsed. Epiphyton, an extinct taxon of calcified microbe that possessed branching filamentous trichomes, was an important reef builder in the shallow marine carbonate platform during Middle Cambrian, aftermath of an extinction of archaeocyath sponges which were major reef-building sessile organisms in the Early Cambrian. Here we present direct evidence of phototropism of Epiphyton, found from fossilized behavior in micro- and macro-structures of meter-scale microbial bioherms of the Zhangxia Formation (Middle Cambrian), North China Platform, Shandong Province, China. The bioherms consist of stacked growth layers with the inner and outer divisions divided by distinct boundary. The inner division of growth layers of the Epiphyton bioherm is dominated by dense uniform bush-shaped Epiphyton thalli, whereas the curved outer division has layered texture normal to the surface, comprised of elongated and chambered thalli. It suggests that photosynthetic Epiphyton reacted actively to the spatial changes in intensity of sunlight, controlled by angle of illumination on the curved growth surface of the bioherm. The inner and the outer divisions comprise different morpho-types of Epiphyton. The spatial distributions of different morpho-types in variously illuminated divisions of Epiphyton might have caused further speciation of Epiphyton.

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.

Quantification of airborne fossil and biomass carbonylic carbon by combined radiocarbon and liquid chromatography mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, B. R.; Tudos, A.; Slanina, J.; Van der Borg, K.; Kotzias, D.

Airborne carbonyl compounds have been sampled at three European semi-remote to semi-urban test sites for radiocarbon ( 14C) analysis. The used methodology included collection on 2,4-dinitrophenylhydrazine coated silica gel cartridges, chromatographic isolation of the formed hydrazones, combustion into CO 2, reduction into graphite followed by accelerator mass spectrometry. In combination with this, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry was used for chemical speciation of the collected carbonyls. At all sites the carbonyls were found to be of a mixed biogenic/anthropogenic origin. The determining factor for the proportion of fossil (anthropogenic) carbon in the samples was the vicinity of urban sources for carbonyls and their photochemical precursors. At meteorological conditions, which gave the test sites semi-rural/semi-remote characteristics the samples contained an average of 24% (range: 10-34%) of fossil carbonylic carbon. When air masses were transported from urban areas to the test-sites significantly higher proportions of fossil carbonylic carbon were determined with a maximum of 61%. Principal component analysis on this limited data set indicated that a low fossil proportion of carbonylic carbon is associated with high proportions of acetaldehyde, acetone, pentanone and acrolein. Until further radicarbon studies are carried out the conclusion remains that for the carbonyl compounds measured European background levels are of a predominant biogenic origin.

Understanding the PM2.5 imbalance between a far and near-road location: Results of high temporal frequency source apportionment and parameterization of black carbon

NASA Astrophysics Data System (ADS)

Sofowote, U. M.; Healy, R. M.; Su, Y.; Debosz, J.; Noble, M.; Munoz, A.; Jeong, C.-H.; Wang, J. M.; Hilker, N.; Evans, G. J.; Hopke, P. K.

2018-01-01

The differences in PM2.5 concentrations between two relatively close stations, one situated near a major highway and the other much more distant were used to develop a protocol for determining the impact of highway traffic on particulate matter concentrations at the roadside. The roadside station was <15 m away from the edge of a major highway while the other was located ∼170 m away. The roadside station contains a suite of continuous instrumentation capable of near-real-time speciation of PM2.5. The particulate matter difference, formally termed the PM2.5 imbalance was arbitrarily defined as a case wherein |Near-road PM2.5 - Far from road PM2.5|/Near-road PM2.5 ≳50%. Of interest was the variation of multi-time factors based on ME2 analyses of the speciation data from the roadside station during these imbalance events. Of the 7 mass-contributing ME2 factors, a black carbon factor was determined to be the major cause of the PM2.5 imbalance and was especially dominant for the case when PM2.5 concentrations at the roadside station were greater than the farther-station PM2.5. The black carbon concentrations observed during these specific events were further regressed against other traffic-related and meteorological parameters with two nonlinear optimization algorithms (generalized reduced gradient and rules ensemble) in our attempts to model any potential relationships. It was observed that the traffic counts of heavy duty vehicles (predominantly diesel-powered) dominated the relationship with black carbon while contributions from light duty vehicles were negligible during these [PM2.5]Roadside > [PM2.5]Farther events at the roadside station. This work details the most critical ways that highway traffic can contribute to local ambient PM2.5 concentrations that commuters are exposed to and will be important in informing policies and strategies for particulate matter pollution reduction.

Determination of the emissions from an aircraft auxiliary power unit (APU) during the Alternative Aviation Fuel Experiment (AAFEX).

PubMed

Kinsey, John S; Timko, Michael T; Herndon, Scott C; Wood, Ezra C; Yu, Zhenhong; Miake-Lye, Richard C; Lobo, Prem; Whitefield, Philip; Hagen, Donald; Wey, Changlie; Anderson, Bruce E; Beyersdorf, Andreas J; Hudgins, Charles H; Thornhill, K Lee; Winstead, Edward; Howard, Robert; Bulzan, Dan I; Tacina, Kathleen B; Knighton, W Berk

2012-04-01

The emissions from a Garrett-AiResearch (now Honeywell) Model GTCP85-98CK auxiliary power unit (APU) were determined as part of the National Aeronautics and Space Administration's (NASA's) Alternative Aviation Fuel Experiment (AAFEX) using both JP-8 and a coal-derived Fischer Tropsch fuel (FT-2). Measurements were conducted by multiple research organizations for sulfur dioxide (SO2, total hydrocarbons (THC), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), speciated gas-phase emissions, particulate matter (PM) mass and number, black carbon, and speciated PM. In addition, particle size distribution (PSD), number-based geometric mean particle diameter (GMD), and smoke number were also determined from the data collected. The results of the research showed PM mass emission indices (EIs) in the range of 20 to 700 mg/kg fuel and PM number EIs ranging from 0.5 x 10(15) to 5 x 10(15) particles/kg fuel depending on engine load and fuel type. In addition, significant reductions in both the SO2 and PM EIs were observed for the use of the FT fuel. These reductions were on the order of approximately 90% for SO2 and particle mass EIs and approximately 60% for the particle number EI, with similar decreases observed for black carbon. Also, the size of the particles generated by JP-8 combustion are noticeably larger than those emitted by the APU burning the FT fuel with the geometric mean diameters ranging from 20 to 50 nm depending on engine load and fuel type. Finally, both particle-bound sulfate and organics were reduced during FT-2 combustion. The PM sulfate was reduced by nearly 100% due to lack of sulfur in the fuel, with the PM organics reduced by a factor of approximately 5 as compared with JP-8.

Changes in iron, sulfur, and arsenic speciation associated with bacterial sulfate reduction in ferrihydrite-rich systems.

PubMed

Saalfield, Samantha L; Bostick, Benjamin C

2009-12-01

Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

Redox State of the Neoarchean Earth Environment

NASA Technical Reports Server (NTRS)

Zerkle, Aubrey L.; Claire, Mark W.; Domagal-Goldman, Shawn; Farquhar, James; Poulton, Simon W.

2011-01-01

A Titan-like organic haze has been hypothesized for Earth's atmosphere prior to widespread surface oxygenation approx.2.45 billion years ago (Ga). We present a high-resolution record of quadruple sulfur isotopes, carbon isotopes, and Fe speciation from the approx.2.65-2.5 Ga Ghaap Group, South Africa, which suggest a linkage between organic haze and the biogeochemical cycling of carbon, sulfur, oxygen, and iron on the Archean Earth. These sediments provide evidence for oxygen production in microbial mats and localized oxygenation of surface waters. However, this oxygen production occurred under a reduced atmosphere which existed in multiple distinct redox states that correlate to changes in carbon and sulfur isotopes. The data are corroborated by photochemical model results that suggest bi-stable transitions between organic haze and haze-free atmospheric conditions in the Archean. These geochemical correlations also extend to other datasets, indicating that variations in the character of anomalous sulfur fractionation could provide insight into the role of carbon-bearing species in the reducing Archean atmosphere.

Microelectrode characterization of coral daytime interior pH and carbonate chemistry.

PubMed

Cai, Wei-Jun; Ma, Yuening; Hopkinson, Brian M; Grottoli, Andréa G; Warner, Mark E; Ding, Qian; Hu, Xinping; Yuan, Xiangchen; Schoepf, Verena; Xu, Hui; Han, Chenhua; Melman, Todd F; Hoadley, Kenneth D; Pettay, D Tye; Matsui, Yohei; Baumann, Justin H; Levas, Stephen; Ying, Ye; Wang, Yongchen

2016-04-04

Reliably predicting how coral calcification may respond to ocean acidification and warming depends on our understanding of coral calcification mechanisms. However, the concentration and speciation of dissolved inorganic carbon (DIC) inside corals remain unclear, as only pH has been measured while a necessary second parameter to constrain carbonate chemistry has been missing. Here we report the first carbonate ion concentration ([CO3(2-)]) measurements together with pH inside corals during the light period. We observe sharp increases in [CO3(2-)] and pH from the gastric cavity to the calcifying fluid, confirming the existence of a proton (H(+)) pumping mechanism. We also show that corals can achieve a high aragonite saturation state (Ωarag) in the calcifying fluid by elevating pH while at the same time keeping [DIC] low. Such a mechanism may require less H(+)-pumping and energy for upregulating pH compared with the high [DIC] scenario and thus may allow corals to be more resistant to climate change related stressors.

Ocean acidification: the other CO2 problem.

PubMed

Doney, Scott C; Fabry, Victoria J; Feely, Richard A; Kleypas, Joan A

2009-01-01

Rising atmospheric carbon dioxide (CO2), primarily from human fossil fuel combustion, reduces ocean pH and causes wholesale shifts in seawater carbonate chemistry. The process of ocean acidification is well documented in field data, and the rate will accelerate over this century unless future CO2 emissions are curbed dramatically. Acidification alters seawater chemical speciation and biogeochemical cycles of many elements and compounds. One well-known effect is the lowering of calcium carbonate saturation states, which impacts shell-forming marine organisms from plankton to benthic molluscs, echinoderms, and corals. Many calcifying species exhibit reduced calcification and growth rates in laboratory experiments under high-CO2 conditions. Ocean acidification also causes an increase in carbon fixation rates in some photosynthetic organisms (both calcifying and noncalcifying). The potential for marine organisms to adapt to increasing CO2 and broader implications for ocean ecosystems are not well known; both are high priorities for future research. Although ocean pH has varied in the geological past, paleo-events may be only imperfect analogs to current conditions.

X exceptionalism in Caenorhabditis speciation.

PubMed

Cutter, Asher D

2017-11-13

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

Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC.

PubMed

Halim, Cheryl E; Short, Stephen A; Scott, Jason A; Amal, Rose; Low, Gary

2005-10-17

A leaching model was developed using the United States Geological Survey public domain PHREEQC geochemical package to simulate the leaching of Pb, Cd, As, and Cr from cementitious wastes. The model utilises both kinetic terms and equilibrium thermodynamics of key compounds and provides information on leachate and precipitate speciation. The model was able to predict the leaching of Pb, Cd, As, and Cr from cement in the presence of both simple (0.1 and 0.6M acetic acid) and complex municipal landfill leachates. Heavy metal complexation by the municipal landfill leachate was accounted for by the introduction of a monoprotic organic species into the model. The model indicated Pb and As were predominantly incorporated within the calcium silicate hydrate matrix while a greater portion of Cd was seen to exist as discrete particles in the cement pores and Cr (VI) existed mostly as free CrO4(2-) ions. Precipitation was found to be the dominant mechanism controlling heavy metal solubility with carbonate and silicate species governing the solubility of Pb and carbonate, silicate and hydroxide species governing the solubility of Cd. In the presence of acetic acid, at low pH values Pb and Cd acetate complexes were predominant whereas, at high pH values, hydroxide species dominated. At high pH values, the concentration of As in the leachate was governed by the solubility of Ca3(AsO4)2 with the presence of carbonate alkalinity competing with arsenate for Ca ions. In the presence of municipal landfill leachate, Pb and Cd organic complexes dominated the heavy metal species in solution. The reduction of As and Cr in municipal landfill leachate was crucial for determining aqueous speciation, with typical municipal landfill conditions providing the reduced forms of As and Cr.

Heavy metal partitioning of suspended particulate matter-water and sediment-water in the Yangtze Estuary.

PubMed

Feng, Chenghong; Guo, Xiaoyu; Yin, Su; Tian, Chenhao; Li, Yangyang; Shen, Zhenyao

2017-10-01

The partitioning of ten heavy metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, and Zn) between the water, suspended particulate matter (SPM), and sediments in seven channel sections during three hydrologic seasons in the Yangtze Estuary was comprehensively investigated. Special attention was paid to the role of tides, influential factors (concentrations of SPM and dissolved organic carbon, and particle size), and heavy metal speciation. The SPM-water and sediment-water partition coefficients (K p ) of the heavy metals exhibited similar changes along the channel sections, though the former were larger throughout the estuary. Because of the higher salinity, the K p values of most of the metals were higher in the north branch than in the south branch. The K p values of Cd, Co, and As generally decreased from the wet season to the dry season. Both the diagonal line method and paired samples t-test showed that no specific phase transfer of heavy metals existed during the flood and ebb tides, but the sediment-water K p was more concentrated for the diagonal line method, owing to the relatively smaller tidal influences on the sediment. The partition coefficients (especially the K p for SPM-water) had negative correlations with the dissolved organic carbon (DOC) but positive correlations were noted with the particle size for most of the heavy metals in sediment. Two types of significant correlations were observed between K p and metal speciation (i.e., exchangeable, carbonate, reducible, organic, and residual fractions), which can be used to identify the dominant phase-partition mechanisms (e.g., adsorption or desorption) of heavy metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfur Speciation in Peat: a Time-zero Signature for the " Spruce and Peatland Responses Under Climate and Environmental Change" Experiment

NASA Astrophysics Data System (ADS)

Furman, O.; Toner, B. M.; Sebestyen, S. D.; Kolka, R. K.; Nater, E. A.

2014-12-01

As part of the "Spruce and Peatland Responses Under Climate and Environmental Change" (SPRUCE) experiment, we made initial measurements of sulfur speciation in peat. These observations represent a "time-zero" relative to the intended soil warming experiment which begins in 2015. Total sulfur and sulfur speciation were measured in peat cores (solid phase) from nine plots (hollows and hummocks) to a depth of 2 m. Peat samples were packed under nitrogen and frozen in the field immediately after collection. All subsequent sample storage, handling, and processing were conducted under inert gas. Sulfur speciation was measured using bulk sulfur 1s X-ray absorption near edge structure (XANES) spectroscopy at the SXRMB instrument at the Canadian Light Source, Saskatoon, SK, Canada and at the 9-BM instrument, Advanced Photon Source, Argonne National Laboratory, IL, USA. Total sulfur concentrations ranged from 968 to 4077 mg sulfur / kg dry peat. Sulfur content increased with depth from 2 g sulfur / m2 in the 0-10 cm increment to a maximum value of 38 g sulfur / m2 in the 50-60 cm increment. These sulfur loadings produced high quality XANES spectra. The nine cores exhibited reproducible trends with depth in both total sulfur and specific sulfur species; however, variability in sulfur speciation was greatest in the top 40 cm. All sulfur detected within the peat solids was in an organic form. The most abundant sulfur species group was composed of organic mono-sulfide and thiol forms, representing approximately half of the total sulfur at all depths. Sulfonate and ester-sulfate species were 10-15 mol% of sulfur and exhibited low variability with depth. A subsurface maximum in organic di-sulfide was observed in the 20-30 cm depth increment, which is the transition zone between transiently oxidized acrotelm and permanently saturated anaerobic catotelm. Quantification of major sulfur pools is important for the SPRUCE experiment as they are likely to be indicators of changes in the oxidation-reduction (redox) status, and mercury methylation potential, of the peat in response to warming and enhanced carbon dioxide.

The fate of carbon and CO2 - fluid-rock interaction during subduction metamorphism of serpentinites

NASA Astrophysics Data System (ADS)

Menzel, Manuel D.; Garrido, Carlos J.; López Sánchez-Vizcaíno, Vicente; Marchesi, Claudio; Hidas, Károly

2016-04-01

Given to its large relevance for present and past climate studies, the deep carbon cycle received increasing attention recently. However, there are still many open questions concerning total mass fluxes and transport processes between the different carbon reservoirs in the Earth's interior. One key issue is the carbon transfer from the subducting slab into fluids and rocks in the slab and mantle wedge. This transfer is controlled by the amount and speciation of stable carbon-bearing phases, which have a strong impact on the pH, redox conditions and trace-element budget of slab fluids. As recent experiments and thermodynamic modeling have shown, water released from dehydrating serpentinites has a great potential to produce CO2-enriched slab fluids by dissolution of carbonate minerals. To constrain the fate of carbon and CO2-fluid-rock interactions during subduction metamorphism of serpentinites, we have studied carbonate-bearing serpentinites recording different prograde evolutions from antigorite schists to Chl-harzburgites in high-P massifs of the Nevado-Filabride Complex (Betic Cordillera, S. Spain). Our results indicate that dissolution of dolomite in marbles in contact with dehydrating serpentinites is spatially limited during prograde metamorphism of carbonate-bearing serpentinites, but it can lead to the formation of silicate-rich zones in marbles close to the contacts. In lower grade serpentinite massifs (1.0-1.5 GPa / 550 °C), the presence of marble lenses in contact with antigorite schists appears to promote local dehydration of serpentinite coupled with carbonation of antigorite, forming Cpx-Tr-Chl-bearing high grade ophicarbonate zones. At the Cerro del Almirez ultramafic massif, where a dehydration front from antigorite-serpentinite to prograde Chl-harzburgite is preserved (1.9 GPa / 680 °C), a significant amount of carbon is retained in prograde Chl-harzburgites and Tr-Dol-marble lenses. This observation is at odds with thermodynamic models that predict efficient carbonate dissolution during dehydration of carbonate-bearing antigorite serpentinite, and indicates that in natural systems substantial amounts of carbon can be recycled into the deep mantle via subduction of carbonate-bearing serpentinite.

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.

Comparative Transcriptomics of Strawberries (Fragaria spp.) Provides Insights into Evolutionary Patterns.

PubMed

Qiao, Qin; Xue, Li; Wang, Qia; Sun, Hang; Zhong, Yang; Huang, Jinling; Lei, Jiajun; Zhang, Ticao

2016-01-01

Multiple closely related species with genomic sequences provide an ideal system for studies on comparative and evolutionary genomics, as well as the mechanism of speciation. The whole genome sequences of six strawberry species ( Fragaria spp.) have been released, which provide one of the richest genomic resources of any plant genus. In this study, we first generated seven transcriptome sequences of Fragaria species de novo , with a total of 48,557-82,537 unigenes per species. Combined with 13 other species genomes in Rosales, we reconstructed a phylogenetic tree at the genomic level. The phylogenic tree shows that Fragaria closed grouped with Rubus and the Fragaria clade is divided into three subclades. East Asian species appeared in every subclade, suggesting that the genus originated in this area at ∼7.99 Mya. Four species found in mountains of Southwest China originated at ∼3.98 Mya, suggesting that rapid speciation occurred to adapt to changing environments following the uplift of the Qinghai-Tibet Plateau. Moreover, we identified 510 very significantly positively selected genes in the cultivated species F . × ananassa genome. This set of genes was enriched in functions related to specific agronomic traits, such as carbon metabolism and plant hormone signal transduction processes, which are directly related to fruit quality and flavor. These findings illustrate comprehensive evolutionary patterns in Fragaria and the genetic basis of fruit domestication of cultivated strawberry at the genomic/transcriptomic level.

Annual cycle of size-resolved organic aerosol characterization in an urbanized desert environment

NASA Astrophysics Data System (ADS)

Cahill, Thomas M.

2013-06-01

Studies of size-resolved organic speciation of aerosols are still relatively rare and are generally only conducted over short durations. However, size-resolved organic data can both suggest possible sources of the aerosols and identify the human exposure to the chemicals since different aerosol sizes have different lung capture efficiencies. The objective of this study was to conduct size-resolved organic aerosol speciation for a calendar year in Phoenix, Arizona to determine the seasonal variations in both chemical concentrations and size profiles. The results showed large seasonal differences in combustion pollutants where the highest concentrations were observed in winter. Summertime aerosols have a greater proportion of biological compounds (e.g. sugars and fatty acids) and the biological compounds represent the largest fraction of the organic compounds detected. These results suggest that standard organic carbon (OC) measurements might be heavily influenced by primary biological compounds particularly if the samples are PM10 and TSP samples. Several large dust storms did not significantly alter the organic aerosol profile since Phoenix resides in a dusty desert environment, so the soil and plant tracer of trehalose was almost always present. The aerosol size profiles showed that PAHs were generally most abundant in the smallest aerosol size fractions, which are most likely to be captured by the lung, while the biological compounds were almost exclusively found in the coarse size fraction.

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.

Song evolution, speciation, and vocal learning in passerine birds.

PubMed

Mason, Nicholas A; Burns, Kevin J; Tobias, Joseph A; Claramunt, Santiago; Seddon, Nathalie; Derryberry, Elizabeth P

2017-03-01

Phenotypic divergence can promote reproductive isolation and speciation, suggesting a possible link between rates of phenotypic evolution and the tempo of speciation at multiple evolutionary scales. To date, most macroevolutionary studies of diversification have focused on morphological traits, whereas behavioral traits─including vocal signals─are rarely considered. Thus, although behavioral traits often mediate mate choice and gene flow, we have a limited understanding of how behavioral evolution contributes to diversification. Furthermore, the developmental mode by which behavioral traits are acquired may affect rates of behavioral evolution, although this hypothesis is seldom tested in a phylogenetic framework. Here, we examine evidence for rate shifts in vocal evolution and speciation across two major radiations of codistributed passerines: one oscine clade with learned songs (Thraupidae) and one suboscine clade with innate songs (Furnariidae). We find that evolutionary bursts in rates of speciation and song evolution are coincident in both thraupids and furnariids. Further, overall rates of vocal evolution are higher among taxa with learned rather than innate songs. Taken together, these findings suggest an association between macroevolutionary bursts in speciation and vocal evolution, and that the tempo of behavioral evolution can be influenced by variation in developmental modes among lineages. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies.

PubMed

Chen, Chunmei; Kukkadapu, Ravi K; Lazareva, Olesya; Sparks, Donald L

2017-07-18

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57 Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

Understanding the Transformation, Speciation, and Hazard Potential of Copper Particles in a Model Septic Tank System using Zebrafish to Monitor the Effluent

PubMed Central

Lin, Sijie; Taylor, Alicia A.; Zhaoxia, Ji; Chang, Chong Hyun; Kinsinger, Nichola M.; Ueng, William; Walker, Sharon L.; Nel, André E.

2015-01-01

Although copper-containing nanoparticles are used in commercial products such as fungicides and bactericides, we presently do not understand the environmental impact on other organisms that may be inadvertently exposed. In this study, we used the zebrafish embryo as a screening tool to study the potential impact of two nano Cu-based materials, CuPRO and Kocide, in comparison to nano-sized and micron-sized Cu and CuO particles in their pristine form (0 – 10 ppm) as well as following their transformation in an experimental wastewater treatment system. This was accomplished by construction of a modeled domestic septic tank system from which effluents could be retrieved at different stages following particle introduction (10 ppm). The Cu speciation in the effluent was identified as non-dissolvable inorganic Cu(H2PO2)2 and non-diffusible organic Cu by X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), diffusive gradients in thin-films (DGT), and Visual MINTEQ software. While the nanoscale materials, including the commercial particles, were clearly more potent (showing 50% hatching interference above 0.5 ppm) than the micron-scale particulates with no effect on hatching up to 10 ppm, the Cu released from the particles in the septic tank underwent transformation into non-bioavailable species that failed to interfere with the function of the zebrafish embryo hatching enzyme. Moreover, we demonstrate that the addition of humic acid, as an organic carbon component, could lead to a dose-dependent decrease in Cu toxicity in our high content zebrafish embryo screening assay. Thus, the use of zebrafish embryo screening, in combination with the effluents obtained from a modeled exposure environment, enables a bioassay approach to follow the change in the speciation, and hazard potential of Cu particles instead of difficult-to-perform direct particle tracking. PMID:25625504

Understanding the transformation, speciation, and hazard potential of copper particles in a model septic tank system using zebrafish to monitor the effluent.

PubMed

Lin, Sijie; Taylor, Alicia A; Ji, Zhaoxia; Chang, Chong Hyun; Kinsinger, Nichola M; Ueng, William; Walker, Sharon L; Nel, André E

2015-02-24

Although copper-containing nanoparticles are used in commercial products such as fungicides and bactericides, we presently do not understand the environmental impact on other organisms that may be inadvertently exposed. In this study, we used the zebrafish embryo as a screening tool to study the potential impact of two nano Cu-based materials, CuPRO and Kocide, in comparison to nanosized and micron-sized Cu and CuO particles in their pristine form (0-10 ppm) as well as following their transformation in an experimental wastewater treatment system. This was accomplished by construction of a modeled domestic septic tank system from which effluents could be retrieved at different stages following particle introduction (10 ppm). The Cu speciation in the effluent was identified as nondissolvable inorganic Cu(H2PO2)2 and nondiffusible organic Cu by X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), diffusive gradients in thin-films (DGT), and Visual MINTEQ software. While the nanoscale materials, including the commercial particles, were clearly more potent (showing 50% hatching interference above 0.5 ppm) than the micron-scale particulates with no effect on hatching up to 10 ppm, the Cu released from the particles in the septic tank underwent transformation into nonbioavailable species that failed to interfere with the function of the zebrafish embryo hatching enzyme. Moreover, we demonstrate that the addition of humic acid, as an organic carbon component, could lead to a dose-dependent decrease in Cu toxicity in our high content zebrafish embryo screening assay. Thus, the use of zebrafish embryo screening, in combination with the effluents obtained from a modeled exposure environment, enables a bioassay approach to follow the change in the speciation and hazard potential of Cu particles instead of difficult-to-perform direct particle tracking.

Role of organic aerosols in CCN activation and closure over a rural background site in Western Ghats, India

NASA Astrophysics Data System (ADS)

Singla, V.; Mukherjee, S.; Safai, P. D.; Meena, G. S.; Dani, K. K.; Pandithurai, G.

2017-06-01

The cloud condensation nuclei (CCN) closure study was performed to exemplify the effect of aerosol chemical composition on the CCN activity of aerosols at Mahabaleshwar, a high altitude background site in the Western Ghats, India. For this, collocated aerosol, CCN, Elemental Carbon (EC), Organic Carbon (OC), sub-micron aerosol chemical speciation for the period from 3rd June to 19th June 2015 was used. The chemical composition of non-refractory particulate matter (<1 μm) as measured by Time of Flight - Aerosol Chemical Speciation Monitor (ToF-ACSM) was dominated by organics with average concentration of 3.81 ± 1.6, 0.32 ± 0.06, 0.15 ± 0.02, 0.13 ± 0.03 and 0.95 ± 0.12 μg m-3 for organics, ammonium, chloride, nitrate and sulphate, respectively. The PM1 number concentration as obtained by Wide Range Aerosol Spectrometer (WRAS) varied from 750 to 6480 cm-3. The average mass concentration of elemental carbon (EC) as measured by OC-EC analyzer was 1.16 ± 0.4 μg m-3. The average CCN concentrations obtained from CCN counter (CCNC) at five super-saturations (SS's) was 118 ± 58 cm-3 (0.1% SS), 873 ± 448 cm-3 (0.31% SS), 1308 ± 603 cm-3 (0.52% SS), 1610 ± 838 cm-3 (0.73% SS) and 1826 ± 985 cm-3 (0.94% SS). The CCN concentrations were predicted using Köhler theory on the basis of measured aerosol particle number size distribution, size independent NR-PM1 chemical composition and calculated hygroscopicity. The CCN closure study was evaluated for 3 scenarios, B-I (all soluble inorganics), B-IO (all soluble organics and inorganics) and B-IOOA (all soluble inorganic and soluble oxygenated organic aerosol, OOA). OOA component was derived from the positive matrix factorization (PMF) analysis of organic aerosol mass spectra. Considering the bulk composition as internal mixture, CCN closure study was underestimated by 16-39% for B-I and overestimated by 47-62% for B-IO. The CCN closure result was appreciably improved for B-IOOA where the knowledge of OOA fraction was introduced and uncertainty reduced to within 8-10%.

Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

PubMed

Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

2010-06-28

With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

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

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.

Linking patterns and processes of species diversification in the cone flies Strobilomyia (Diptera: Anthomyiidae).

PubMed

Sachet, Jean-Marie; Roques, Alain; Després, Laurence

2006-12-01

Phytophagous insects provide useful models for the study of ecological speciation. Much attention has been paid to host shifts, whereas situations where closely related lineages of insects use the same plant during different time periods have been relatively neglected in previous studies of insect diversification. Flies of the genus Strobilomyia are major pests of conifers in Eurasia and North America. They are specialized feeders in cones and seeds of Abies (fir), Larix (larch) ,and Picea (spruce). This close association is accompanied by a large number of sympatric Strobilomyia species coexisting within each tree genus. We constructed a molecular phylogeny with a 1320 base-pair fragment of mitochondrial DNA that demonstrated contrasting patterns of speciation in larch cone flies, as opposed to spruce and fir cone flies; this despite their comparable geographic distributions and similar resource quality of the host. Species diversity is the highest on larch, and speciation is primarily driven by within-host phenological shifts, followed by allopatric speciation during geographical expansion. By contrast, fewer species exploit spruce and fir, and within-host phenological shifts did not occur. This study illustrates within-host adaptive radiation through phenological shifts, a neglected mode of sympatric speciation.

PARTICLE SPECIATION AND EMISSION PROFILES OF SMALL 2-STROKE ENGINES

EPA Science Inventory

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

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

PM10 and PM2.5 chemical source profiles with optical attenuation and health risk indicators of paved and unpaved road dust in Bhopal, India.

PubMed

Samiksha, Shilpi; Sunder Raman, Ramya; Nirmalkar, Jayant; Kumar, Samresh; Sirvaiya, Rohit

2017-03-01

Size classified (PM 10 and PM 2.5 ) paved and unpaved road dust chemical source profiles, optical attenuation and potential health risk from exposure to these sources are reported in this study. A total of 45 samples from 9 paved road and 6 unpaved road sites located in and around Bhopal were re-suspended in the laboratory, collected onto filter substrates and subjected to a variety of chemical analyses. In general, road dust was enriched (compared to upper continental crustal abundance) in anthropogenic pollutants including Sb, Cu, Zn, Co, and Pb. Organic and elemental carbon (OC/EC) in PM 10 and PM 2.5 size fractions were 50-75% higher in paved road dust compared to their counterparts in unpaved road dust. Further, the results suggest that when it is not possible to include carbon fractions in source profiles, the inclusion of optical attenuation is likely to enhance the source resolution of receptor models. Additionally, profiles obtained in this study were not very similar to the US EPA SPECIATE composite profiles for PM 10 and PM 2.5 , for both sources. Specifically, the mass fractions of Si, Fe, OC, and EC were most different between SPECIATE composite profiles and Bhopal composite profiles. An estimate of health indicators for Bhopal road dust revealed that although Cr was only marginally enriched, its inhalation may pose a health risk. The estimates of potential lifetime incremental cancer risk induced by the inhalation of Cr in paved and unpaved road dust (PM 10 and PM 2.5 ) for both adults and children were higher than the baseline values of acceptable risk. These results suggest that road dust Cr induced carcinogenic risk should be further investigated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental study of carbonate formation in oceanic peridotite

NASA Astrophysics Data System (ADS)

Grozeva, Niya G.; Klein, Frieder; Seewald, Jeffrey S.; Sylva, Sean P.

2017-02-01

Interactions of CO2-rich aqueous fluids with mantle peridotite have major implications for geochemical budgets and microbial life in the shallow oceanic lithosphere through the formation of carbonate minerals and reduced carbon species. However, the underlying mechanisms controlling the transformation of CO2 to carbonates in ultramafic-hosted hydrothermal systems remain incompletely understood. A long-term laboratory experiment was conducted at 300 °C and 35 MPa to investigate serpentinization and carbonate formation pathways during hydrothermal alteration of peridotite. Powdered harzburgite was initially reacted with a Ca-rich aqueous fluid for 14,592 h (608 days) and changes in fluid composition were monitored with time. Once the system reached a steady state, a CO2(aq)-rich fluid was injected and allowed to react with the system for 5907 h (246 days). Fluid speciation and mineral analyses suggest that serpentinization of harzburgite in the CO2-poor system led to the precipitation of serpentine, brucite, magnetite, and minor calcite, in addition to other minor phases including chlorite and sulfur-poor Ni sulfides. The addition of the CO2(aq)-rich fluid caused dolomite, Ca-rich dolomite, and high-Mg calcite to form at the expense of olivine, calcite, and brucite, while serpentine remained unreactive. Replacement textures and mineral assemblages mimic those documented in carbonate-altered seafloor serpentinites, particularly those from the Mid-Atlantic Ridge and the Iberia Margin. In contrast to thermodynamic predictions, magnesite did not form in the experiment because the dissolution of clinopyroxene, in combination with the lack of serpentine reactivity, maintained low Mg/Ca ratios in solution. Clinopyroxene dissolution and unreactive serpentine may similarly maintain low Mg/Ca ratios in submarine serpentinization systems and limit magnesite formation in subseafloor environments. Results of this study suggest that the formation of Ca-Mg carbonates by mineral carbonation is favorable in subseafloor serpentinization systems and likely represents a significant, but poorly quantified, carbon sink in hydrothermally altered oceanic lithosphere at slow-spreading mid-ocean ridges.

Application of ESI-HRMS for molybdenum speciation in natural waters: An investigation of molybdate-halide reactions.

PubMed

Dang, Duc Huy; Evans, R Douglas

2018-03-01

High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO 3 Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO 4 2- to HMoO 4 - ) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Use of Mössbauer spectroscopy to determine the effect of salinity on the speciation of triorganotins in Anacostia River sediments

NASA Astrophysics Data System (ADS)

Eng, George; Song, Xueqing; May, Leopold

2006-06-01

The speciation of several tributyltin and triphenyltin compounds under varying salinity conditions (0, 20, 40 and 60%) was studied by Mössbauer spectroscopy in both anaerobic and aerobic Anacostia River sediments. The Mössbauer spectral parameters of the spiked sediments indicated that changes in the salinity did not affect the speciation of the tin compounds in either aerobic or anaerobic sediments.

Use of Mössbauer spectroscopy to determine the effect of salinity on the speciation of triorganotins in Anacostia River sediments

NASA Astrophysics Data System (ADS)

Eng, George; Song, Xueqing; May, Leopold

The speciation of several tributyltin and triphenyltin compounds under varying salinity conditions (0, 20, 40 and 60%) was studied by Mössbauer spectroscopy in both anaerobic and aerobic Anacostia River sediments. The Mössbauer spectral parameters of the spiked sediments indicated that changes in the salinity did not affect the speciation of the tin compounds in either aerobic or anaerobic sediments.

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.

Reduction of disinfection by-product precursors in reservoir water by coagulation and ultrafiltration.

PubMed

Wang, Feng; Gao, Baoyu; Ma, Defang; Yue, Qinyan; Li, Ruihua; Wang, Qianwen

2016-11-01

In this study, reservoir water intended for drinking water supply was treated by (i) ultrafiltration (UF) (ii) coagulation (CW) (iii) coagulation combined with ultrafiltration (CW-UF). To probe the influences of three treatment processes on disinfection byproduct (DBP) precursors in source water, the changes of dissolved organic matter (DOM) amounts and physicochemical properties, and disinfection byproduct (DBP) formation characteristics during chlorine disinfection were investigated. Both carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) formation and speciation were analyzed. The influence of chlorine dose, contact time on DBP formation and speciation were also studied to optimize the disinfection conditions to minimize the DBP formation. Compared with UF and CW alone, CW-UF improved the dissolved organic carbon (DOC) removal from about 20 % to 59 %. The three-dimensional excitation and emission matrix (3DEEM) fluorescence spectroscopy analysis showed that CW-UF had high removal efficiency in microbial products (Region IV), fulvic acid-like (Region III) and humic acid-like (Region V). The total C-DBP was determined by the formation of trihalomethanes and trichloromethane was the most abundant species (40 %). The most abundant N-DBP species was dichloroacetonitrile (32.5 %), followed by trichloroactetonitrile. CW-UF effectively reduced the risk of DBPs in drinking water supply by reducing 30.8 % and 16.9 % DBPs formation potential compared with UF and CW alone. Increasing contact time improved the yields of both C-DBPs and N-DBPs. Chlorine dosage had slight influence on DBP yield in this study.

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 does organic matter occurrence set limit onto the use of Ce anomaly as a reliable proxy of redox conditions in shallow groundwaters?

NASA Astrophysics Data System (ADS)

Dia, A.; Gruau, G.; Davranche, M.; Vidy, A.; Henin, O.; Petitjean, P.; Le Coz-Bouhnik, M.

2003-04-01

This study is dedicated to the effects of organic matter on the hydrochemistry of Rare Earth Elements (REE) and the ability of using the Ce anomaly as a reliable proxy of redox conditions in surface waters when organic matter occurs. The data include a : i) two-year survey of SREE and Ce anomalies in organic-rich waters recovered from a catchment located in Brittany (western Europe) and (ii) experimental incubation of organic soils from this catchment set under controlled conditions, as well as, (iii) a REE speciation calculation in both the natural organic-rich waters from the wetlands and the experimental solutions. Field and experimental data appear to be extremely coherent, displaying good correlation between the SREE, the Dissolved Organic Carbon (DOC) contents and the redox state. The field data show a strong increase of the SREE and DOC concentrations in soil waters when the environment becomes more reducing. The onset of DOC and SREE contents is seen to be in phase with the increase of dissolved Fe and Mn. The role of Fe-, Mn-oxyhydroxides is confirmed by the experimental data as the maximum of DOC and SREE content is reached when Fe2+ reaches a maximum in the soil solution, suggesting that reductive dissolution of Fe, Mn-oxyhydroxides happens. Despite the strong redox changes and the known redox sensitive behaviour of Ce as compared to other REE, none Ce anomaly variation is observed during either, the experimental procedure, or the field survey through time. Speciation calculations were performed showing that in both such pH range and moderately oxidizing waters in DOC-rich waters, REE should have an organic speciation. Such an organic speciation prevents the formation of Ce(IV) and therefore the development of any Ce anomaly. However, since the studied waters are highly oxidizing (high nitrate contents), the nitrates impose the redox formation of Ce(IV) and a Ce anomaly should appear. Therefore, Ce(IV) is not formed in these waters either because (i) the reaction kinetic might be so slow that the anomaly has no time to ever happen in the field, or (ii) Ce(IV) might be linked to the organic colloidal fraction. Since the thermodynamic modelling does not help getting information, further experimental kinetics or ultrafiltration studies will be required to clarify these latter points. This has to be fixed to be able to use the Ce anomaly as a reliable proxy of redox conditions in organic-rich environment.

The inorganic speciation of tin(II) in aqueous solution

NASA Astrophysics Data System (ADS)

Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

2012-06-01

This paper reports new voltammetric measurements on the interactions between tin(II) and the most important natural inorganic ligands, OH-, Cl-, F-, CO32-, SO42- and PO43-. For a better understanding of tin(II) speciation, an analysis is also given of prior data on the same systems from the literature. The formation constants were determined at t = 25 °C in different ionic media and at different ionic strengths, specifically the following: Sn(OH)q (0.1 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), SnClr and Sn(OH)Cl (0.1 ⩽ I/mol L-1 ⩽ 2.3 in Na(NO3, Cl)), Sn(SO4)r (0.1 ⩽ I/mol L-1 ⩽ 1.6 in Na(NO3, SO4)), SnHqCO3 and SnHqPO4 (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaNO3), where the subscripts r and q represent the stoichiometric coefficients. Concerning the SnFr species, reliable literature values were considered (0.15 ⩽ I/mol L-1 ⩽ 1.0 in NaClO4). Fifteen voltammetric measurements were performed in synthetic seawater; the total seawater binding ability was evaluated by a model in which synthetic seawater is expressed as a single salt, BA. The formation of species between tin(II) and the anion of the marine salt (A) was also proposed, and the corresponding stability constants at different salinities (5 ⩽ S ⩽ 50) were reported. In addition, studies on the solubility of Sn(OH)2(s) were carried out using voltammetry and light scattering measurements. The "extra-stability" of the mixed species with respect to the parent species was evaluated, in particular for Sn(OH)Cl and the corresponding species involving the anion of the marine salt (A). The dependence of the formation constants on ionic strength was analysed using extended Debye-Hückel and Specific ion Interaction Theory (SIT) type equations. Tin(II) speciation was also evaluated in different natural fluid conditions, where, in all cases, carbonate complexation was predominant, hampering the formation of hydrolytic species throughout the investigated pH range. Moreover, some formation enthalpy changes were calculated for the Sn(OH)+, Sn(OH)2(aq), Sn(OH)2(s), Sn(OH)3-, Sn(OH)22+, Sn(OH)42+, Sn(OH)Cl, SnCl+, SnCl2 and SnCl3- species on the basis of the available literature stability constant values at different temperatures and using the empirical relationships reported in the literature. The ΔH values at t = 25 °C were positive in all cases except for the Sn(OH)2(s) and Sn(OH)3- species, indicating an increase in the stability constant values with increasing temperature. This work represents an advance in the knowledge, understanding and modelling of the inorganic speciation of tin(II) in natural fluids, particularly for solutions containing chloride, fluoride, sulphate, carbonate and phosphate anions.

Pb(II) adsorption by a novel activated carbon - alginate composite material. A kinetic and equilibrium study.

PubMed

Cataldo, Salvatore; Gianguzza, Antonio; Milea, Demetrio; Muratore, Nicola; Pettignano, Alberto

2016-11-01

The adsorption capacity of an activated carbon - calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH=5, in NaCl medium and in the ionic strength range 0.1-0.75molL -1 . Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate (AA-Ca) improves the adsorption capacity (q m ) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., q m =15.7 and 10.5mgg -1 at I=0.25molL -1 , for ACAA-Ca and AC, respectively). SEM-EDX and thermogravimetric (TGA) measurements were carried out in order to characterize the composite material. The results of the speciation study on the Pb(II) solution and of the characterization of the ACAA-Ca and of the pristine AA-Ca and AC were evaluated in order to explain the specific contribution of AC and AA-Ca to the adsorption of the metal ion. Copyright © 2016 Elsevier B.V. All rights reserved.

The Lake Ohrid Drilling Project: initial interpretations of stable isotope data over the last 640 ka

NASA Astrophysics Data System (ADS)

Lacey, J. H.; Leng, M. J.; Francke, A.; Sloane, H. J.; Milodowski, A. E.; Vogel, H.; Baumgarten, H.; Wagner, B.

2015-12-01

Lake Ohrid (Macedonia/Albania) is an ancient European lake with a unique biodiversity and a site of global significance to study the influence of climate, geological and tectonic events on the biological evolution of taxa. Here, we present oxygen (δ18O) and carbon (δ13C) isotope data on carbonate from sediment cores spanning 640 ka recovered as part of the Scientific Collaboration on Past Speciation Conditions in Lake Ohrid (SCOPSCO) project. Previous work on cores from the lake (up to 15 m, <140 ka) indicated that the Total Inorganic Carbon (TIC) content of sediments was highly sensitive to climate change during the last glacial-interglacial cycle, comprising abundant endogenic calcite through interglacials and being almost absent in glacials, apart from discrete bands of early diagenetic authigenic siderite. Isotope measurements on calcite (δ18Oc and δ13Cc) reveal variations both between and within interglacials that suggest the lake has been subject to hydroclimate fluctuations on orbital and millennial timescales. We also measured isotopes on authigenic siderite (δ18Os and δ13Cs) and, with the δ18Oc and δ18Os, reconstruct δ18O of lakewater (δ18Olw). Glacials are observed to have lower δ18Olw when compared to interglacials, most likely due to cooler summer temperatures, a higher proportion of winter precipitation (snowfall), and a reduced inflow from neighbouring Lake Prespa. The isotope data suggest Lake Ohrid experienced a period of overall stability through Marine Isotope Stage (MIS) 15 to 13, highlighting MIS 14 as a particularly warm glacial, and MIS 9 was isotopically freshest. Following MIS 9, the variability between glacial and interglacial δ18Olw is enhanced and the lake became increasingly evaporated through to present day with MIS 5 having the highest average δ18Olw. These findings provide new evidence for long-term climate change in the northern Mediterranean region, which will form the basis to better understand the influence of major environmental events on endemic speciation within the lake.

Visualizing speciation in artificial cichlid fish.

PubMed

Clement, Ross

2006-01-01

The Cichlid Speciation Project (CSP) is an ALife simulation system for investigating open problems in the speciation of African cichlid fish. The CSP can be used to perform a wide range of experiments that show that speciation is a natural consequence of certain biological systems. A visualization system capable of extracting the history of speciation from low-level trace data and creating a phylogenetic tree has been implemented. Unlike previous approaches, this visualization system presents a concrete trace of speciation, rather than a summary of low-level information from which the viewer can make subjective decisions on how speciation progressed. The phylogenetic trees are a more objective visualization of speciation, and enable automated collection and summarization of the results of experiments. The visualization system is used to create a phylogenetic tree from an experiment that models sympatric speciation.

Chemical Speciation and Metallomics.

PubMed

de Jesus, Jemmyson Romário; da Costa, Luana Ferreira; Lehmann, Eraldo Luiz; Galazzi, Rodrigo Moretto; Madrid, Katherine Chacón; Arruda, Marco Aurélio Zezzi

2018-01-01

Chemical speciation approaches is an inherent part of metallomics, once metals/metalloids and organic structures need to be currently evaluated for attaining metallomics studies. Then, this chapter focuses on the applications of the chemical speciation applied to the human health risk, food and human diet, drugs, forensic, nanoscience, and geological metallomics, also pointing out the advances in such area. Some aspects regarding sample preparation is commented along this chapter, and some strategies for maintaining the integrity of the metallomics information are also emphasized.

Hybrid Speciation in a Marine Mammal: The Clymene Dolphin (Stenella clymene)

PubMed Central

Amaral, Ana R.; Lovewell, Gretchen; Coelho, Maria M.; Amato, George; Rosenbaum, Howard C.

2014-01-01

Natural hybridization may result in the exchange of genetic material between divergent lineages and even the formation of new taxa. Many of the Neo-Darwinian architects argued that, particularly for animal clades, natural hybridization was maladaptive. Recent evidence, however, has falsified this hypothesis, instead indicating that this process may lead to increased biodiversity through the formation of new species. Although such cases of hybrid speciation have been described in plants, fish and insects, they are considered exceptionally rare in mammals. Here we present evidence for a marine mammal, Stenella clymene, arising through natural hybridization. We found phylogenetic discordance between mitochondrial and nuclear markers, which, coupled with a pattern of transgressive segregation seen in the morphometric variation of some characters, support a case of hybrid speciation. S. clymene is currently genetically differentiated from its putative parental species, Stenella coerueloalba and Stenella longisrostris, although low levels of introgressive hybridization may be occurring. Although non-reticulate forms of evolution, such as incomplete lineage sorting, could explain our genetic results, we consider that the genetic and morphological evidence taken together argue more convincingly towards a case of hybrid speciation. We anticipate that our study will bring attention to this important aspect of reticulate evolution in non-model mammal species. The study of speciation through hybridization is an excellent opportunity to understand the mechanisms leading to speciation in the context of gene flow. PMID:24421898

Hybrid speciation in a marine mammal: the clymene dolphin (Stenella clymene).

PubMed

Amaral, Ana R; Lovewell, Gretchen; Coelho, Maria M; Amato, George; Rosenbaum, Howard C

2014-01-01

Natural hybridization may result in the exchange of genetic material between divergent lineages and even the formation of new taxa. Many of the Neo-Darwinian architects argued that, particularly for animal clades, natural hybridization was maladaptive. Recent evidence, however, has falsified this hypothesis, instead indicating that this process may lead to increased biodiversity through the formation of new species. Although such cases of hybrid speciation have been described in plants, fish and insects, they are considered exceptionally rare in mammals. Here we present evidence for a marine mammal, Stenella clymene, arising through natural hybridization. We found phylogenetic discordance between mitochondrial and nuclear markers, which, coupled with a pattern of transgressive segregation seen in the morphometric variation of some characters, support a case of hybrid speciation. S. clymene is currently genetically differentiated from its putative parental species, Stenella coerueloalba and Stenella longisrostris, although low levels of introgressive hybridization may be occurring. Although non-reticulate forms of evolution, such as incomplete lineage sorting, could explain our genetic results, we consider that the genetic and morphological evidence taken together argue more convincingly towards a case of hybrid speciation. We anticipate that our study will bring attention to this important aspect of reticulate evolution in non-model mammal species. The study of speciation through hybridization is an excellent opportunity to understand the mechanisms leading to speciation in the context of gene flow.

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

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...

Metal Ion Speciation and Dissolved Organic Matter Composition in Soil Solutions

NASA Astrophysics Data System (ADS)

Benedetti, M. F.; Ren, Z. L.; Bravin, M.; Tella, M.; Dai, J.

2014-12-01

Knowledge of the speciation of heavy metals and the role of dissolved organic matter (DOM) in soil solution is a key to understand metal mobility and ecotoxicity. In this study, soil column-Donnan membrane technique (SC-DMT) was used to measure metal speciation of Cd, Cu, Ni, Pb, and Zn in eighteen soil solutions, covering a wide range of metal sources and concentrations. DOM composition in these soil solutions was also determined. Our results show that in soil solution Pb and Cu are dominant in complex form, whereas Cd, Ni and Zn mainly exist as free ions; for the whole range of soil solutions, only 26.2% of DOM is reactive and consists mainly of fulvic acid (FA). The metal speciation measured by SC-DMT was compared to the predicted ones obtained via the NICA-Donnan model using the measured FA concentrations. The free ion concentrations predicted by speciation modelling were in good agreement with the measurements. Diffusive gradients in thin-films gels (DGT) were also performed to quantify the labile metal species in the fluxes from solid phase to solution in fourteen soils. The concentrations of metal species detected by DGT were compared with the free ion concentrations measured by DMT and the maximum concentrations calculated based on the predicted metal speciation in SC-DMT soil solutions. It is concluded that both inorganic species and a fraction of FA bound species account for the amount of labile metals measured by DGT, consistent with the dynamic features of this technique. The comparisons between measurements using analytical techniques and mechanistic model predictions provided mutual validation in their performance. Moreover, we show that to make accurate modelling of metal speciation in soil solutions, the knowledge of DOM composition is the crucial information, especially for Cu; like in previous studies the modelling of Pb speciation is not optimal and an updated of Pb generic binding parameters is required to reduce model prediction uncertainties.

Rapid radiation in spiny lobsters (Palinurus spp) as revealed by classic and ABC methods using mtDNA and microsatellite data.

PubMed

Palero, Ferran; Lopes, Joao; Abelló, Pere; Macpherson, Enrique; Pascual, Marta; Beaumont, Mark A

2009-11-09

Molecular tools may help to uncover closely related and still diverging species from a wide variety of taxa and provide insight into the mechanisms, pace and geography of marine speciation. There is a certain controversy on the phylogeography and speciation modes of species-groups with an Eastern Atlantic-Western Indian Ocean distribution, with previous studies suggesting that older events (Miocene) and/or more recent (Pleistocene) oceanographic processes could have influenced the phylogeny of marine taxa. The spiny lobster genus Palinurus allows for testing among speciation hypotheses, since it has a particular distribution with two groups of three species each in the Northeastern Atlantic (P. elephas, P. mauritanicus and P. charlestoni) and Southeastern Atlantic and Southwestern Indian Oceans (P. gilchristi, P. delagoae and P. barbarae). In the present study, we obtain a more complete understanding of the phylogenetic relationships among these species through a combined dataset with both nuclear and mitochondrial markers, by testing alternative hypotheses on both the mutation rate and tree topology under the recently developed approximate Bayesian computation (ABC) methods. Our analyses support a North-to-South speciation pattern in Palinurus with all the South-African species forming a monophyletic clade nested within the Northern Hemisphere species. Coalescent-based ABC methods allowed us to reject the previously proposed hypothesis of a Middle Miocene speciation event related with the closure of the Tethyan Seaway. Instead, divergence times obtained for Palinurus species using the combined mtDNA-microsatellite dataset and standard mutation rates for mtDNA agree with known glaciation-related processes occurring during the last 2 my. The Palinurus speciation pattern is a typical example of a series of rapid speciation events occurring within a group, with very short branches separating different species. Our results support the hypothesis that recent climate change-related oceanographic processes have influenced the phylogeny of marine taxa, with most Palinurus species originating during the last two million years. The present study highlights the value of new coalescent-based statistical methods such as ABC for testing different speciation hypotheses using molecular data.

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

EPA Science Inventory

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

A COMPUTATIONAL AND EXPERIMENTAL STUDY OF MERCURY SPECIATION AS FACILITATED BY THE DEACON PROCESS

EPA Science Inventory

The paper gives results of a computational and experimental study of mercury (Hg) speciation as facilitated by the Deacon process. Fly ashes that contain trace cupric or ferric oxide are effective catalysts for elemental mercury (Hg) conversion to mercuric chloride in the presenc...

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...

Arsenic speciation in rice and risk assessment of inorganic arsenic in Taiwan population.

PubMed

Chen, Hsiu-Ling; Lee, Ching-Chang; Huang, Winn-Jung; Huang, Han-Ting; Wu, Yi-Chen; Hsu, Ya-Chen; Kao, Yi-Ting

2016-03-01

This study assessed the total arsenic content and arsenic speciation in rice to determine the health risks associated with rice consumption in various age-gender subgroups in Taiwan. The average total arsenic levels in white rice and brown rice were 116.6 ± 39.2 and 215.5 ± 63.5 ng/g weight (n = 51 and 13), respectively. The cumulative cancer risk among males was 10.4/100,000. The highest fraction of inorganic/total arsenic content in white rice ranged from 76.9 to 88.2 % and from 81.0 to 96.5 % in brown rice. The current study found different arsenic speciation of rice in southern Taiwan, where the famous blackfoot disease has been reported compared with arsenic speciation from other Taiwan areas. Therefore, rice and other grains should be further monitored in southern Taiwan to evaluate whether arsenic contamination is well controlled in this area.

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.

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

Neu, Mary Patricia

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

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

Storey, John Morse; Lewis Sr, Samuel Arthur; Szybist, James P

Gasoline direct injection (GDI) engines can offer improved fuel economy and higher performance over their port fuel-injected (PFI) counterparts, and are now appearing in increasingly more U.S. and European vehicles. Small displacement, turbocharged GDI engines are replacing large displacement engines, particularly in light-duty trucks and sport utility vehicles, in order for manufacturers to meet more stringent fuel economy standards. GDI engines typically emit the most particulate matter (PM) during periods of rich operation such as start-up and acceleration, and emissions of air toxics are also more likely during this condition. A 2.0 L GDI engine was operated at lambda ofmore » 0.91 at typical loads for acceleration (2600 rpm, 8 bar BMEP) on three different fuels; an 87 anti-knock index (AKI) gasoline (E0), 30% ethanol blended with the 87 AKI fuel (E30), and 48% isobutanol blended with the 87 AKI fuel. E30 was chosen to maximize octane enhancement while minimizing ethanol-blend level and iBu48 was chosen to match the same fuel oxygen level as E30. Particle size and number, organic carbon and elemental carbon (OC/EC), soot HC speciation, and aldehydes and ketones were all analyzed during the experiment. A new method for soot HC speciation is introduced using a direct, thermal desorption/pyrolysis inlet for the gas chromatograph (GC). Results showed high levels of aromatic compounds were present in the PM, including downstream of the catalyst, and the aldehydes were dominated by the alcohol blending.« less

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

NASA Astrophysics Data System (ADS)

Ding, Luyi C.; Ke, Fu; Wang, Daniel K. W.; Dann, Tom; Austin, Claire C.

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33-98% by mass of the organic compounds identified. PAHs accounted for 1-65% and biomarkers (hopanes and steranes) 1-8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07-1.55 ng m -3), 16 PAHs (0.02-1.83 ng m -3), and biomarkers (0.02-0.18 ng m -3). Daily levels of these organics were 4.89-74.38 ng m -3, 0.27-100.24 ng m -3, 0.14-4.39 ng m -3, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source - most likely motor vehicles and space heating.

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

PubMed

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

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.

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.

Formation of CO2, H2 and condensed carbon from siderite dissolution in the 200-300 °C range and at 50 MPa

NASA Astrophysics Data System (ADS)

Milesi, Vincent; Guyot, François; Brunet, Fabrice; Richard, Laurent; Recham, Nadir; Benedetti, Marc; Dairou, Julien; Prinzhofer, Alain

2015-04-01

Laboratory experiments were conducted to investigate the chemical processes governing the carbon speciation associated to hydrothermal decomposition of siderite. Experiments were carried out in sealed gold capsules using synthetic siderite and deionised water. The samples were reacted at 200 and 300 °C, under a pressure of 50 MPa. Siderite dissolved to reach the 3FeCO3 + H2O = Fe3O4 + 3CO2 + H2 equilibrium and magnetite, Fe3O4, was produced accordingly. The gas phase was dominated by CO2, H2 and CH4, the latter being in strong thermodynamic disequilibrium with CO2. Contrary to the other gas products, H2 concentration was found to decrease with run duration. TEM observations showed the occurrence of condensed carbon phases at the surfaces of magnetite and residual siderite grains. Thermodynamic calculations predict the formation of condensed carbon in the experiments according to the reaction: CO2 + 2H2 ⇒ C + 2H2O, which accounted for the observed H2 concentration decrease up to the point where H2 and CO2 activities were buffered by the graphite-siderite-magnetite assemblage. The well-organized structure of the carbon coating around magnetite emphasizes the high catalytic potential of magnetite surface for carbon reduction and polymerization. The formation of such C-rich phases may represent a potential source of CH4 by hydrogenation. On the other hand, the catalysis of Fischer-Tropsch type reactions may be poisoned by the presence of carbon coating on mineral surfaces. In any case, this study also demonstrates that abiotic H2 generation by water reduction, widely studied in recent years in ultrabasic contexts, can also occur in sedimentary contexts where siderite is present. We show that, in the latter case, natural H2 concentration will be buffered by a condensed carbon phase associated with magnetite.

Nitrogen enrichment and speciation in a coral reef lagoon driven by groundwater inputs of bird guano

NASA Astrophysics Data System (ADS)

McMahon, Ashly; Santos, Isaac R.

2017-09-01

While the influence of river inputs on coral reef biogeochemistry has been investigated, there is limited information on nutrient fluxes related to submarine groundwater discharge (SGD). Here, we investigate whether significant saline groundwater-derived nutrient inputs from bird guano drive coral reef photosynthesis and calcification off Heron Island (Great Barrier Reef, Australia). We used multiple experimental approaches including groundwater sampling, beach face transects, and detailed time series observations to assess the dynamics and speciation of groundwater nutrients as they travel across the island and discharge into the coral reef lagoon. Nitrogen speciation shifted from nitrate-dominated groundwater (>90% of total dissolved nitrogen) to a coral reef lagoon dominated by dissolved organic nitrogen (DON; ˜86%). There was a minimum input of nitrate of 2.1 mmol m-2 d-1 into the lagoon from tidally driven submarine groundwater discharge estimated from a radon mass balance model. An independent approach based on the enrichment of dissolved nutrients during isolation at low tide implied nitrate fluxes of 5.4 mmol m-2 d-1. A correlation was observed between nitrate and daytime net ecosystem production and calcification. We suggest that groundwater nutrients derived from bird guano may offer a significant addition to oligotrophic coral reef lagoons and fuel ecosystem productivity and the coastal carbon cycle near Heron Island. The large input of groundwater nutrients in Heron Island may serve as a natural ecological analogue to other coral reefs subject to large nutrient inputs from anthropogenic sources.

Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

PubMed

Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel

2015-06-01

Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. Copyright © 2015 Elsevier Inc. All rights reserved.

STUDY OF THE FUNDAMENTALS OF MERCURY SPECIATION IN COAL-FIRED BOILERS UNDER SIMULATED POST-COMBUSTION CONDITIONS

EPA Science Inventory

The report discusses a continuation of the study on mercury speciation initiated in the fiscal year 1997 (FY97). The previous study found that cupric oxide (CuO) and ferric oxide (Fe2O3) in the presence of hydrogen chloride (HCl) promote elemental mercury oxidation in simulated f...

ARSENIC SPECIATION ANALYSIS IN HUMAN SALIVA

EPA Science Inventory

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

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

Photochemical Oxidation of Dissolved Elemental Mercury by Carbonate Radicals in Water

DOE PAGES

He, Feng; Zhao, Weirong; Liang, Liyuan; ...

2014-11-11

Photochemical oxidation of dissolved elemental mercury [Hg(0)] affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially in natural freshwaters containing dissolved organic matter (DOM) and carbonate. Here, we evaluate Hg(0) photooxidation rates affected by various reactive ionic species [e.g., DOM, CO 3 2-, NO 3 -] and free radicals in a creek water and a phosphate buffer solution (pH=8) under simulated solar irradiation. We report a high Hg(0) photooxidation rate (k = 1.44 h -1) in the presence of bothmore » HCO 3 2- and NO 3 -, whereas HCO 3 2-, NO 3 -, or DOM alone increased the oxidation rate slightly (k = 0.1 0.17 h -1). Using scavengers and enhancers for singlet oxygen ( 1O 2) and hydroxyl (HO ∙ ) radicals, as well as electron paramagnetic resonance spectroscopy, we identify that carbonate radicals (CO 3 ∙-) primarily drive the Hg(0) photooxidation, whereas addition of DOM resulted in a 2-fold decrease in Hg(0) oxidation. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO 3 ∙- radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and fate in water containing carbonate such as hard water and seawater.« less

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

PubMed Central

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-01

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

PubMed

Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

2016-01-27

Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

The Influence of Polyploidy on the Evolution of Yeast Grown in a Sub-Optimal Carbon Source

PubMed Central

Scott, Amber L.; Richmond, Phillip A.; Dowell, Robin D.; Selmecki, Anna M.

2017-01-01

Abstract Polyploidization events have occurred during the evolution of many fungi, plant, and animal species and are thought to contribute to speciation and tumorigenesis, however little is known about how ploidy level contributes to adaptation at the molecular level. Here we integrate whole genome sequencing, RNA expression analysis, and relative fitness of ∼100 evolved clones at three ploidy levels. Independent haploid, diploid, and tetraploid populations were grown in a low carbon environment for 250 generations. We demonstrate that the key adaptive mutation in the evolved clones is predicted by a gene expression signature of just five genes. All of the adaptive mutations identified encompass a narrow set of genes, however the tetraploid clones gain a broader spectrum of adaptive mutations than haploid or diploid clones. While many of the adaptive mutations occur in genes that encode proteins with known roles in glucose sensing and transport, we discover mutations in genes with no canonical role in carbon utilization (IPT1 and MOT3), as well as identify novel dominant mutations in glucose signal transducers thought to only accumulate recessive mutations in carbon limited environments (MTH1 and RGT1). We conclude that polyploid cells explore more genotypic and phenotypic space than lower ploidy cells. Our study provides strong evidence for the beneficial role of polyploidization events that occur during the evolution of many species and during tumorigenesis. PMID:28957510

Measuring ocean acidification: new technology for a new era of ocean chemistry.

PubMed

Byrne, Robert H

2014-05-20

Human additions of carbon dioxide to the atmosphere are creating a cascade of chemical consequences that will eventually extend to the bottom of all the world's oceans. Among the best-documented seawater effects are a worldwide increase in open-ocean acidity and large-scale declines in calcium carbonate saturation states. The susceptibility of some young, fast-growing calcareous organisms to adverse impacts highlights the potential for biological and economic consequences. Many important aspects of seawater CO2 chemistry can be only indirectly observed at present, and important but difficult-to-observe changes can include shifts in the speciation and possibly bioavailability of some life-essential elements. Innovation and invention are urgently needed to develop the in situ instrumentation required to document this era of rapid ocean evolution.

Speciation of heavy metals in landfill leachate: a review.

PubMed

Baun, Dorthe L; Christensen, Thomas H

2004-02-01

The literature was reviewed with respect to metal speciation methods in aquatic samples specifically emphasizing speciation of heavy metals in landfill leachate. Speciation here refers to physical fractionation (particulate, colloidal, dissolved), chemical fractionation (organic complexes, inorganic complexes, free metal ions), as well as computer-based thermodynamic models. Relatively few landfill leachate samples have been speciated in detail (less than 30) representing only a few landfills (less than 15). This suggests that our knowledge about metal species in landfill leachate still is indicative. In spite of the limited database and the different definitions of the dissolved fraction (< 0.45 microm or < 0.001 microm) the studies consistently show that colloids as well as organic and inorganic complexes are important for all heavy metals in landfill leachate. The free metal ion constitutes less than 30%, typically less than 10%, of the total metal concentration. This has significant implications for sampling, since no standardized procedures exist, and for assessing the content of metals in leachate in the context of its treatment, toxicity and migration in aquifers.

Parapatric speciation in three islands: dynamics of geographical configuration of allele sharing

PubMed Central

Iwasa, Yoh

2017-01-01

We studied the time to speciation by geographical isolation for a species living on three islands connected by rare migration. We assumed that incompatibility was controlled by a number of quantitative loci and that individuals differing in loci by more than a threshold did not mix genetically with each other. For each locus, we defined the geographical configuration (GC), which specifies islands with common alleles, and traced the stochastic transitions between different GCs. From these results, we calculated the changes in genetic distances. As a single migration event provides an opportunity for transitions in multiple loci, the GCs of different loci are correlated, which can be evaluated by constructing the stochastic differential equations of the number of loci with different GCs. Our model showed that the low number of incompatibility loci facilitates parapatric speciation and that migrants arriving as a group shorten the waiting time to speciation compared with the same number of migrants arriving individually. We also discuss how speciation rate changes with geographical structure. PMID:28386439

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

PubMed

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

2015-02-01

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

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

ERIC Educational Resources Information Center

Sharp, Joan

2002-01-01

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

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano.

PubMed

Floor, Geerke H; Iglesías, Mònica; Román-Ross, Gabriela; Corvini, Philippe F X; Lenz, Markus

2011-09-01

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH<4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L(-1) using (78)Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H(2)SO(4) and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

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...

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.

Comparative Transcriptomics of Strawberries (Fragaria spp.) Provides Insights into Evolutionary Patterns

PubMed Central

Qiao, Qin; Xue, Li; Wang, Qia; Sun, Hang; Zhong, Yang; Huang, Jinling; Lei, Jiajun; Zhang, Ticao

2016-01-01

Multiple closely related species with genomic sequences provide an ideal system for studies on comparative and evolutionary genomics, as well as the mechanism of speciation. The whole genome sequences of six strawberry species (Fragaria spp.) have been released, which provide one of the richest genomic resources of any plant genus. In this study, we first generated seven transcriptome sequences of Fragaria species de novo, with a total of 48,557–82,537 unigenes per species. Combined with 13 other species genomes in Rosales, we reconstructed a phylogenetic tree at the genomic level. The phylogenic tree shows that Fragaria closed grouped with Rubus and the Fragaria clade is divided into three subclades. East Asian species appeared in every subclade, suggesting that the genus originated in this area at ∼7.99 Mya. Four species found in mountains of Southwest China originated at ∼3.98 Mya, suggesting that rapid speciation occurred to adapt to changing environments following the uplift of the Qinghai–Tibet Plateau. Moreover, we identified 510 very significantly positively selected genes in the cultivated species F. × ananassa genome. This set of genes was enriched in functions related to specific agronomic traits, such as carbon metabolism and plant hormone signal transduction processes, which are directly related to fruit quality and flavor. These findings illustrate comprehensive evolutionary patterns in Fragaria and the genetic basis of fruit domestication of cultivated strawberry at the genomic/transcriptomic level. PMID:28018379

Observations and regional modeling of aerosol optical properties, speciation and size distribution over Northern Africa and western Europe

NASA Astrophysics Data System (ADS)

Menut, Laurent; Siour, Guillaume; Mailler, Sylvain; Couvidat, Florian; Bessagnet, Bertrand

2016-10-01

The aerosol speciation and size distribution is modeled during the summer 2013 and over a large area encompassing Africa, Mediterranean and western Europe. The modeled aerosol is compared to available measurements such as the AERONET aerosol optical depth (AOD) and aerosol size distribution (ASD) and the EMEP network for surface concentrations of particulate matter PM2.5, PM10 and inorganic species (nitrate, sulfate and ammonium). The main goal of this study is to quantify the model ability to realistically model the speciation and size distribution of the aerosol. Results first showed that the long-range transport pathways are well reproduced and mainly constituted by mineral dust: spatial correlation is ≈ 0.9 for AOD and Ångström exponent, when temporal correlations show that the day-to-day variability is more difficult to reproduce. Over Europe, PM2.5 and PM10 have a mean temporal correlation of ≈ 0.4 but the lowest spatial correlation ( ≈ 0.25 and 0.62, respectively), showing that the fine particles are not well localized or transported. Being short-lived species, the uncertainties on meteorology and emissions induce these lowest scores. However, time series of PM2.5 with the speciation show a good agreement between model and measurements and are useful for discriminating the aerosol composition. Using a classification from the south (Africa) to the north (northern Europe), it is shown that mineral dust relative mass contribution decreases from 50 to 10 % when nitrate increases from 0 to 20 % and all other species, sulfate, sea salt, ammonium, elemental carbon, primary organic matter, are constant. The secondary organic aerosol contribution is between 10 and 20 % with a maximum at the latitude of the Mediterranean Sea (Spanish stations). For inorganic species, it is shown that nitrate, sulfate and ammonium have a mean temporal correlation of 0.25, 0.37 and 0.17, respectively. The spatial correlation is better (0.25, 0.5 and 0.87), showing that the mean values may be biased but the spatial localization of sulfate and ammonium is well reproduced. The size distribution is compared to the AERONET product and it is shown that the model fairly reproduces the main values for the fine and coarse mode. In particular, for the fine mode, the model overestimates the aerosol mass in Africa and underestimates it in Europe.

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.

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.

Anaerobic Digestion Alters Copper and Zinc Speciation.

PubMed

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

2017-09-19

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

Direct determination and speciation of mercury compounds in environmental and biological samples by carbon bed atomic absorption spectroscopy

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

Skelly, E.M.

A method was developed for the direct determination of mercury in water and biological samples using a unique carbon bed atomizer for atomic absorption spectroscopy. The method avoided sources of error such as loss of volatile mercury during sample digestion and contamination of samples through added reagents by eliminating sample pretreatment steps. The design of the atomizer allowed use of the 184.9 nm mercury resonance line in the vacuum ultraviolet region, which increased sensitivity over the commonly used spin-forbidden 253.7 nm line. The carbon bed atomizer method was applied to a study of mercury concentrations in water, hair, sweat, urine,more » blood, breath and saliva samples from a non-occupationally exposed population. Data were collected on the average concentration, the range and distribution of mercury in the samples. Data were also collected illustrating individual variations in mercury concentrations with time. Concentrations of mercury found were significantly higher than values reported in the literature for a ''normal'' population. This is attributed to the increased accuracy gained by eliminating pretreatment steps and increasing atomization efficiency. Absorption traces were obtained for various solutions of pure and complexed mercury compounds. Absorption traces of biological fluids were also obtained. Differences were observed in the absorption-temperatures traces of various compounds. The utility of this technique for studying complexation was demonstrated.« less

Capillary electrophoresis application in metal speciation and complexation characterization

USDA-ARS?s Scientific Manuscript database

Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

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.

Overview of the Manitou Experimental Forest Observatory: site description and selected science results from 2008 to 2013

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

Ortega, John; Turnipseed, A.; Guenther, Alex B.

2014-01-01

The Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen (BEACHON) project seeks to understand the feedbacks and interrelationships between hydrology, biogenic emissions, carbon assimilation, aerosol properties, clouds and associated feedbacks within water-limited ecosystems. The Manitou Experimental Forest Observatory (MEFO) was established in 2008 by the National Center for Atmospheric Research to address many of the BEACHON research objectives, and it now provides a fixed field site with significant infrastructure. MEFO is a mountainous, semi-arid ponderosa pine-dominated forest site that is normally dominated by clean continental air but is periodically influenced by anthropogenic sources from Colorado Front Range cities.more » This article summarizes the past and ongoing research activities at the site, and highlights some of the significant findings that have resulted from these measurements. These activities include – soil property measurements; – hydrological studies; – measurements of high-frequency turbulence parameters; – eddy covariance flux measurements of water, energy, aerosols and carbon dioxide through the canopy; – determination of biogenic and anthropogenic volatile organic compound emissions and their influence on regional atmospheric chemistry; – aerosol number and mass distributions; – chemical speciation of aerosol particles; – characterization of ice and cloud condensation nuclei; – trace gas measurements; and – model simulations using coupled chemistry and meteorology. In addition to various long-term continuous measurements, three focused measurement campaigns with state-of-the-art instrumentation have taken place since the site was established, and two of these studies are the subjects of this special issue: BEACHON-ROCS (Rocky Mountain Organic Carbon Study, 2010) and BEACHON-RoMBAS (Rocky Mountain Biogenic Aerosol Study, 2011).« less

Influences of organic carbon speciation on hyporheic corridor biogeochemistry and microbial ecology.

PubMed

Stegen, James C; Johnson, Tim; Fredrickson, James K; Wilkins, Michael J; Konopka, Allan E; Nelson, William C; Arntzen, Evan V; Chrisler, William B; Chu, Rosalie K; Fansler, Sarah J; Graham, Emily B; Kennedy, David W; Resch, Charles T; Tfaily, Malak; Zachara, John

2018-02-08

The hyporheic corridor (HC) encompasses the river-groundwater continuum, where the mixing of groundwater (GW) with river water (RW) in the HC can stimulate biogeochemical activity. Here we propose a novel thermodynamic mechanism underlying this phenomenon and reveal broader impacts on dissolved organic carbon (DOC) and microbial ecology. We show that thermodynamically favorable DOC accumulates in GW despite lower DOC concentration, and that RW contains thermodynamically less-favorable DOC, but at higher concentrations. This indicates that GW DOC is protected from microbial oxidation by low total energy within the DOC pool, whereas RW DOC is protected by lower thermodynamic favorability of carbon species. We propose that GW-RW mixing overcomes these protections and stimulates respiration. Mixing models coupled with geophysical and molecular analyses further reveal tipping points in spatiotemporal dynamics of DOC and indicate important hydrology-biochemistry-microbial feedbacks. Previously unrecognized thermodynamic mechanisms regulated by GW-RW mixing may therefore strongly influence biogeochemical and microbial dynamics in riverine ecosystems.

Modeling the two-locus architecture of divergent pollinator adaptation: how variation in SAD paralogs affects fitness and evolutionary divergence in sexually deceptive orchids.

PubMed

Xu, Shuqing; Schlüter, Philipp M

2015-01-01

Divergent selection by pollinators can bring about strong reproductive isolation via changes at few genes of large effect. This has recently been demonstrated in sexually deceptive orchids, where studies (1) quantified the strength of reproductive isolation in the field; (2) identified genes that appear to be causal for reproductive isolation; and (3) demonstrated selection by analysis of natural variation in gene sequence and expression. In a group of closely related Ophrys orchids, specific floral scent components, namely n-alkenes, are the key floral traits that control specific pollinator attraction by chemical mimicry of insect sex pheromones. The genetic basis of species-specific differences in alkene production mainly lies in two biosynthetic genes encoding stearoyl-acyl carrier protein desaturases (SAD) that are associated with floral scent variation and reproductive isolation between closely related species, and evolve under pollinator-mediated selection. However, the implications of this genetic architecture of key floral traits on the evolutionary processes of pollinator adaptation and speciation in this plant group remain unclear. Here, we expand on these recent findings to model scenarios of adaptive evolutionary change at SAD2 and SAD5, their effects on plant fitness (i.e., offspring number), and the dynamics of speciation. Our model suggests that the two-locus architecture of reproductive isolation allows for rapid sympatric speciation by pollinator shift; however, the likelihood of such pollinator-mediated speciation is asymmetric between the two orchid species O. sphegodes and O. exaltata due to different fitness effects of their predominant SAD2 and SAD5 alleles. Our study not only provides insight into pollinator adaptation and speciation mechanisms of sexually deceptive orchids but also demonstrates the power of applying a modeling approach to the study of pollinator-driven ecological speciation.

Mid-depth respired carbon storage and oxygenation of the eastern equatorial Pacific over the last 25,000 years

NASA Astrophysics Data System (ADS)

Umling, Natalie E.; Thunell, Robert C.

2018-06-01

A growing body of evidence suggests that respired carbon was stored in mid-depth waters (∼1-3 km) during the last glacial maximum (LGM) and released to the atmosphere from upwelling regions during deglaciation. Decreased ventilation, enhanced productivity, and enhanced carbonate dissolution are among the mechanisms that have been cited as possible drivers of glacial CO2 drawdown. However, the relative importance of each of these mechanisms is poorly understood. New approaches to quantitatively constrain bottom water carbonate chemistry and oxygenation provide methods for estimating historic changes in respired carbon storage. While increased CO2 drawdown during the LGM should have resulted in decreased oxygenation and a shift in dissolved inorganic carbon (DIC) speciation towards lower carbonate ion concentrations, this is complicated by the interplay of carbonate compensation, export productivity, and circulation. To disentangle these processes, we use a multiproxy approach that includes boron to calcium (B/Ca) ratios of the benthic foraminifera Cibicidoides wuellerstorfi to reconstruct deep-water carbonate ion concentrations ([CO32-]) and the uranium to calcium (U/Ca) ratio of foraminiferal coatings in combination with benthic foraminiferal carbon isotopes to reconstruct changes in bottom water oxygen concentrations ([O2]) and organic carbon export. Our records indicate that LGM [CO32-] and [O2] was reduced at mid water depths of the eastern equatorial Pacific (EEP), consistent with increased respired carbon storage. Furthermore, our results suggest enhanced mixing of lower Circumpolar Deep Water (LCDW) to EEP mid water depths and provide evidence for the importance of circulation for oceanic-atmospheric CO2 exchange.

Instrumentation for Aerosol and Gas Speciation

NASA Technical Reports Server (NTRS)

Coggiola, Michael J.

1998-01-01

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

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.

Primate diversification inferred from phylogenies and fossils.

PubMed

Herrera, James P

2017-12-01

Biodiversity arises from the balance between speciation and extinction. Fossils record the origins and disappearance of organisms, and the branching patterns of molecular phylogenies allow estimation of speciation and extinction rates, but the patterns of diversification are frequently incongruent between these two data sources. I tested two hypotheses about the diversification of primates based on ∼600 fossil species and 90% complete phylogenies of living species: (1) diversification rates increased through time; (2) a significant extinction event occurred in the Oligocene. Consistent with the first hypothesis, analyses of phylogenies supported increasing speciation rates and negligible extinction rates. In contrast, fossils showed that while speciation rates increased, speciation and extinction rates tended to be nearly equal, resulting in zero net diversification. Partially supporting the second hypothesis, the fossil data recorded a clear pattern of diversity decline in the Oligocene, although diversification rates were near zero. The phylogeny supported increased extinction ∼34 Ma, but also elevated extinction ∼10 Ma, coinciding with diversity declines in some fossil clades. The results demonstrated that estimates of speciation and extinction ignoring fossils are insufficient to infer diversification and information on extinct lineages should be incorporated into phylogenetic analyses. © 2017 The Author(s). Evolution © 2017 The Society for the Study of Evolution.

Bromine speciation in hydrous haplogranitic melts up to 7 GPa

NASA Astrophysics Data System (ADS)

Cochain, B.; de Grouchy, C.; Crepisson, C.; Kantor, I.; Irifune, T.; Sanloup, C.

2013-12-01

Halogens are minor volatiles in the Earth's mantle and crust, but they have significant and specific influences on magmatic and degassing processes. They also provide insights about subsurface magma movement and eruption likelihood in subduction-related volcanism. Their speciation in silicate melts affects volatile exsolution, rheology, and the thermodynamic properties of the melts but still remains relatively unknown. A few studies have explored halogen speciation at room conditions, i.e. in glasses but no firm conclusion has yet been reached. Furthermore, halogen speciation remains unexplored at high pressures and temperatures. In this work we investigate the speciation of Br in subduction-related melt (hydrous haplogranite melt) up to 1200°C and 7 GPa using X-ray absorption spectroscopy (XANES and EXAFS) at the Br K-edge. High P-T conditions were generated by the Paris-Edinburgh press. The use of nanocrystalline diamond capsules enabled us to avoid glitches in the EXAFS spectra. The results provide valuable information on Br speciation and its evolution with pressure. It gives insights into solubility mechanisms for halogens in magmas at depth and on their degassing from the melt. In addition, we were able to identify quench effects on the atomic environment of Br by comparison of high P-T in-situ spectra and ex-situ spectra recorded on quenched samples.

PILOT-SCALE STUDY OF THE EFFECT OF SELECTIVE CATALYTIC REDUCTION CATALYST ON MERCURY SPECIATION IN ILLINOIS AND POWDER RIVER BASIN COAL COMBUSTION FLUE GASES

EPA Science Inventory

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur and chlorine) and one Po...

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.

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

PubMed

Kozak, Lidia; Niedzielski, Przemyslaw

2017-08-01

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

Early events in speciation: Cryptic species of Drosophila aldrichi.

PubMed

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

2017-06-01

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

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...

Characterization of soluble microbial products as precursors of disinfection byproducts in drinking water supply.

PubMed

Liu, Jin-Lin; Li, Xiao-Yan; Xie, Yue-Feng; Tang, Hao

2014-02-15

Water pollution by wastewater discharge can cause the problem of disinfection byproducts (DBPs) in drinking water supply. In this study, DBP formation characteristics of soluble microbial products (SMPs) as the main products of wastewater organic biodegradation were investigated. The results show that SMPs can act as DBP precursors in simulated wastewater biodegradation process. Under the experimental conditions, stabilized SMPs had DBPFP (DBP formation potential) yield of around 5.6 μmol mmol(-1)-DOC (dissolved organic carbon) and DBP speciation profile different from that of the conventional precursor, natural organic matter (NOM). SMPs contained polysaccharides, proteins, and humic-like substances, and the latter two groups can act as reactive DBP precursors. SMP fraction with molecular weight of <1 kDa accounted for 85% of the organic carbon and 65% of the DBP formation. As small SMP molecules are more difficult to remove by conventional water treatment processes, more efforts are needed to control wastewater-derived DBP problem in water resource management. Copyright © 2013 Elsevier B.V. All rights reserved.

Adsorption behavior and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes.

PubMed

Zhao, Heng; Liu, Xue; Cao, Zhen; Zhan, Yi; Shi, Xiaodong; Yang, Yi; Zhou, Junliang; Xu, Jiang

2016-06-05

The adsorption behavior of different emerging contaminants (3 chloramphenicols, 7 sulfonamides, and 3 non-antibiotic pharmaceuticals) on five types of multi-walled carbon nanotubes (MWCNTs), and the underlying factors were studied. Adsorption equilibriums were reached within 12h for all compounds, and well fitted by the Freundlich isotherm model. The adsorption affinity of pharmaceuticals was positively related to the specific surface area of MWCNTs. The solution pH was an important parameter of pharmaceutical adsorption on MWCNTs, due to its impacts on the chemical speciation of pharmaceuticals and the surface electrical property of MWCNTs. The adsorption of ionizable pharmaceuticals decreased in varying degrees with the increased ionic strength. MWCNT-10 was found to be the strongest adsorbent in this study, and the Freundlich constant (KF) values were 353-2814mmol(1-n)L(n)/kg, 571-618mmol(1-n)L(n)/kg, and 317-1522mmol(1-n)L(n)/kg for sulfonamides, chloramphenicols, and non-antibiotic pharmaceuticals, respectively. The different adsorption affinity of sulfonamides might contribute to the different hydrophobic of heterocyclic substituents, while chloramphenicols adsorption was affected by the charge distribution in aromatic rings via substituent effects. Copyright © 2016 Elsevier B.V. All rights reserved.

A Study of metabolic transformation of organic and inorganic components in PM2.5 and PM10, South Korea

NASA Astrophysics Data System (ADS)

Kim, J.; Yoon, H.; Lee, M.

2012-12-01

The important factors of atmospheric particle matter (PM) are size, concentration, composition and toxicity which can considerably affect the possible human health problem, especially respiratory diseases, visibility reduction and climate change. PM2.5 and PM10 are complex mixture of ammonium sulfate, ammonium nitrate, organic carbon, inorganic carbon and inorganic constituents. Recently, most researches of source attribution and assessments of the relationship between health effects and particle concentrations have not taken advantage of the development in analytical tools measuring the detailed molecular structure and microstructure of particles and of the knowledge of particle formation mechanisms in combustion system. This study will combine variety analytical techniques that can provide structural and compositional information to determine the correlation between sources of hazardous material and physicochemical properties in aerosol particle. Inorganic metal can be rapidly quantifying to filter base using ED-XRF (Energy-dispersive X-ray fluorescence). Speciation and quantification of water soluble components applied HPLC-ICP-MS and LC-MS NMR (nuclear magnetic resonance). Afterward, we investigate metabolic transformations of atmospheric particle matter also using FE-TEM (Field Emission Transmission Electron Microscopy).

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

PubMed

Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

2016-06-01

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Antipredator defenses predict diversification rates

PubMed Central

Arbuckle, Kevin; Speed, Michael P.

2015-01-01

The “escape-and-radiate” hypothesis predicts that antipredator defenses facilitate adaptive radiations by enabling escape from constraints of predation, diversified habitat use, and subsequently speciation. Animals have evolved diverse strategies to reduce the direct costs of predation, including cryptic coloration and behavior, chemical defenses, mimicry, and advertisement of unprofitability (conspicuous warning coloration). Whereas the survival consequences of these alternative defenses for individuals are well-studied, little attention has been given to the macroevolutionary consequences of alternative forms of defense. Here we show, using amphibians as the first, to our knowledge, large-scale empirical test in animals, that there are important macroevolutionary consequences of alternative defenses. However, the escape-and-radiate hypothesis does not adequately describe them, due to its exclusive focus on speciation. We examined how rates of speciation and extinction vary across defensive traits throughout amphibians. Lineages that use chemical defenses show higher rates of speciation as predicted by escape-and-radiate but also show higher rates of extinction compared with those without chemical defense. The effect of chemical defense is a net reduction in diversification compared with lineages without chemical defense. In contrast, acquisition of conspicuous coloration (often used as warning signals or in mimicry) is associated with heightened speciation rates but unchanged extinction rates. We conclude that predictions based on the escape-and-radiate hypothesis must incorporate the effect of traits on both speciation and extinction, which is rarely considered in such studies. Our results also suggest that knowledge of defensive traits could have a bearing on the predictability of extinction, perhaps especially important in globally threatened taxa such as amphibians. PMID:26483488

Effect of thermal maturity on remobilization of molybdenum in black shales

NASA Astrophysics Data System (ADS)

Ardakani, Omid H.; Chappaz, Anthony; Sanei, Hamed; Mayer, Bernhard

2016-09-01

Molybdenum (Mo) concentrations in sedimentary records have been widely used as a method to assess paleo-redox conditions prevailing in the ancient oceans. However, the potential effects of post-depositional processes, such as thermal maturity and burial diagenesis, on Mo concentrations in organic-rich shales have not been addressed, compromising its use as a redox proxy. This study investigates the distribution and speciation of Mo at various thermal maturities in the Upper Ordovician Utica Shale from southern Quebec, Canada. Samples display maturities ranging from the peak oil window (VRo ∼ 1%) to the dry gas zone (VRo ∼ 2%). While our data show a significant correlation between total organic carbon (TOC) and Mo (R2 = 0.40, n = 28, P < 0.0003) at lower thermal maturity, this correlation gradually deteriorates with increasing thermal maturity. Intervals within the thermally overmature section of the Utica Shale that contain elevated Mo levels (20-81 ppm) show petrographic and sulfur isotopic evidence of thermochemical sulfate reduction (TSR) along with formation of recrystallized pyrite. X-ray Absorption Fine Structure spectroscopy (XAFS) was used to determine Mo speciation in samples from intervals with elevated Mo contents (>30 ppm). Our results show the presence of two Mo species: molybdenite Mo(IV)S2 (39 ± 5%) and Mo(VI)-Organic Matter (61 ± 5%). This new evidence suggests that at higher thermal maturities, TSR causes sulfate reduction coupled with oxidation of organic matter (OM). This process is associated with H2S generation and pyrite formation and recrystallization. This in turn leads to the remobilization of Mo and co-precipitation of molybdenite with TSR-derived carbonates in the porous intervals. This could lead to alteration of the initial sedimentary signature of Mo in the affected intervals, hence challenging its use as a paleo-redox proxy in overmature black shales.

Transformation and speciation of typical heavy metals in soil aquifer treatment system during long time recharging with secondary effluent: Depth distribution and combination.

PubMed

Wei, Liangliang; Wang, Kun; Noguera, Daniel R; Jiang, Junqiu; Oyserman, Ben; Zhao, Ningbo; Zhao, Qingliang; Cui, Fuyi

2016-12-01

Soil aquifer treatment (SAT) systems rely on extensive physical and biogeochemical processes in the vadose zone and aquifer for water quality improvement. In this study, the distribution, quantitative changes, as well as the speciation characteristics of heavy metals in different depth of soils of a two-year operated lab-scale SAT was explored. A majority of the heavy metals in the recharged secondary effluent were efficiently trapped by the steady-state operated SAT (removal efficiency ranged from 74.7% to 98.2%). Thus, significant accumulations of 31.7% for Cd, 15.9% for Cu, 15.3% for Zn and 8.6% for Cr were observed for the top soil after 730 d operation, leading to the concentration (in μg g -1 ) of those four heavy metals of the packed soil increased from 0.51, 46.7, 61.0 and 35.7 to 0.66, 54.2, 70.4 and 38.8, respectively. By contrast, the accumulation of Mn and Pb were quite low. The residual species were the predominant fraction of the six heavy metals (ranged for 59.8-82.4%), followed by oxidisable species. Although the Zn, Cr, Cd, Cu and Mn were efficiently bounded onto the oxide components within the soil, the percentage of the labile metal fractions (water-, acid-exchangeable and reducible metal fractions) exhibited a slight increasing after 2 Y operation. Significantly heavy metals accumulation and slightly decreasing of the proportion of the stable fractions indicated a potentially higher environmental hazard for those six heavy metals after long-term SAT operation (especially for Cu, Zn and Cd). Finally, a linear relationship between the accumulation rate of metal species and the variation of soil organic carbon concentration and water extractable organic carbon was demonstrated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Results of a hydrogeological and hydrogeochemical study of a semi-arid karst aquifer in Tezbent plateau, Tebessa region, northeast of Algeria

NASA Astrophysics Data System (ADS)

Belfar, Dalila; Fehdi, Chemseddine; Baali, Fethi; Salameh, Elias

2017-06-01

The Hammamet Plain, situated in the northwest of the Tezbent mountain range, northeast of Algeria, drains carbonate aquifers through some important karst springs. The physical and chemical characteristics of spring and well water samples were studied for 2 years to assess the origin of groundwater and determine the factors driving the geochemical composition. The ionic speciation and mineral dissolution/precipitation was calculated. Water wells, characterizing groundwater circulation at shallow depths, are moderate to high mineralized waters of Na-HCO3 type. In contrast to the shallow environment, the CO2-rich, deeper waters are of the Ca-HCO3-SO4 type and undergo significant changes in the baseline chemistry along flow lines with increasing residence time. The main factors controlling the groundwater composition and its seasonal variations are the geology, because of the presence of carbonate formations, the elevation and the rate of karst development. In both groups, the carbonate chemistry is diagnostic of the effect of karst development. The supersaturation with respect to calcite indicates CO2 degassing, occurring either inside the aquifer in open conduits, or at the outlet in reservoirs. The undersaturation with respect to calcite shows the existence of fast flow and short residence time conditions inside the aquifer. Interaction between groundwater and surrounding host rocks is believed to be the main process responsible for the observed chemical characteristics of groundwater in the study area.

The importance of ligand speciation in environmental research: a case study.

PubMed

Sillanpää, M; Orama, M; Rämö, J; Oikari, A

2001-02-21

The speciations of EDTA and DTPA in process, waste and river waters are modelled and simulated, specifically to the mode of occurrence in the pulp and paper mill effluents and subsequently in receiving waters. Due to relatively short residence times in bleaching process and waste water treatment and slow exchange kinetics, it is expected that the thermodynamic equilibrium is not necessarily reached. Therefore, the initial speciation plays a key role. As such, the simulations have been extended to the process waters of the pulp and paper industry taking into account estimated average conditions. The results reveal that the main species are; Mn and Ca complexes of EDTA and DTPA in pulp mill process waters; Fe(III) and Mn complexes of EDTA and DTPA in waste waters; Fe(III) and Zn complexes of EDTA and DTPA in receiving waters. It is also shown how the increasing concentration of complexing agents effects the speciation. Alkaline earth metal chelation plays a significant role in the speciation of EDTA and DTPA when there is a noticeable molar excess of complexing agents compared with transition metals.

Speciation through the lens of biomechanics: locomotion, prey capture and reproductive isolation.

PubMed

Higham, Timothy E; Rogers, Sean M; Langerhans, R Brian; Jamniczky, Heather A; Lauder, George V; Stewart, William J; Martin, Christopher H; Reznick, David N

2016-09-14

Speciation is a multifaceted process that involves numerous aspects of the biological sciences and occurs for multiple reasons. Ecology plays a major role, including both abiotic and biotic factors. Whether populations experience similar or divergent ecological environments, they often adapt to local conditions through divergence in biomechanical traits. We investigate the role of biomechanics in speciation using fish predator-prey interactions, a primary driver of fitness for both predators and prey. We highlight specific groups of fishes, or specific species, that have been particularly valuable for understanding these dynamic interactions and offer the best opportunities for future studies that link genetic architecture to biomechanics and reproductive isolation (RI). In addition to emphasizing the key biomechanical techniques that will be instrumental, we also propose that the movement towards linking biomechanics and speciation will include (i) establishing the genetic basis of biomechanical traits, (ii) testing whether similar and divergent selection lead to biomechanical divergence, and (iii) testing whether/how biomechanical traits affect RI. Future investigations that examine speciation through the lens of biomechanics will propel our understanding of this key process. © 2016 The Author(s).

250 years of hybridization between two biennial herb species without speciation.

PubMed

Matthews, Andrew; Emelianova, Katie; Hatimy, Abubakar A; Chester, Michael; Pellicer, Jaume; Ahmad, Khawaja Shafique; Guignard, Maité S; Rouhan, Germinal; Soltis, Douglas E; Soltis, Pamela S; Leitch, Ilia J; Leitch, Andrew R; Mavrodiev, Evgeny V; Buggs, Richard J A

2015-07-17

Hybridization between plant species can generate novel morphological diversity and lead to speciation at homoploid or polyploid levels. Hybrids between biennial herbs Tragopogon pratensis and T. porrifolius have been studied in experimental and natural populations for over 250 years. Here we examine their current status in natural populations in southeast England. All hybrids found were diploid; they tended to grow taller and with more buds than their parental species; many showed partial fertility; a few showed evidence of backcrossing. However, we found no evidence to suggest that the hybrids are establishing as a new species, nor can we find literature documenting speciation of these hybrids elsewhere. This lack of speciation despite at least 250 years of hybridization contrasts with the fact that both parental species have formed new allopolyploid species through hybridization with another diploid, T. dubius. Understanding why hybrids often do not speciate, despite repeated opportunities, would enhance our understanding of both the evolutionary process and risk assessments of invasive species. Published by Oxford University Press on behalf of the Annals of Botany Company.

Complete genomes of Hairstreak butterflies, their speciation, and nucleo-mitochondrial incongruence

PubMed Central

Cong, Qian; Shen, Jinhui; Borek, Dominika; Robbins, Robert K.; Otwinowski, Zbyszek; Grishin, Nick V.

2016-01-01

Comparison of complete genomes of closely related species enables research on speciation and how phenotype is determined by genotype. Lepidoptera, an insect order of 150,000 species with diverse phenotypes, is well-suited for such comparative genomics studies if new genomes, which cover additional Lepidoptera families are acquired. We report a 729 Mbp genome assembly of the Calycopis cecrops, the first genome from the family Lycaenidae and the largest available Lepidoptera genome. As detritivore, Calycopis shows expansion in detoxification and digestion enzymes. We further obtained complete genomes of 8 Calycopis specimens: 3 C. cecrops and 5 C. isobeon, including a dry specimen stored in the museum for 30 years. The two species differ subtly in phenotype and cannot be differentiated by mitochondrial DNA. However, nuclear genomes revealed a deep split between them. Genes that can clearly separate the two species (speciation hotspots) mostly pertain to circadian clock, mating behavior, transcription regulation, development and cytoskeleton. The speciation hotspots and their function significantly overlap with those we previously found in Pterourus, suggesting common speciation mechanisms in these butterflies. PMID:27120974

A review of recent developments in the speciation and location of arsenic and selenium in rice grain

PubMed Central

Carey, Anne-Marie; Lombi, Enzo; Donner, Erica; de Jonge, Martin D.; Punshon, Tracy; Jackson, Brian P.; Guerinot, Mary Lou; Price, Adam H.; Meharg, Andrew A.

2014-01-01

Rice is a staple food yet is a significant dietary source of inorganic arsenic, a class 1, nonthreshold carcinogen. Establishing the location and speciation of arsenic within the edible rice grain is essential for understanding the risk and for developing effective strategies to reduce grain arsenic concentrations. Conversely, selenium is an essential micronutrient and up to 1 billion people worldwide are selenium-deficient. Several studies have suggested that selenium supplementation can reduce the risk of some cancers, generating substantial interest in biofortifying rice. Knowledge of selenium location and speciation is important, because the anti-cancer effects of selenium depend on its speciation. Germanic acid is an arsenite/silicic acid analogue, and location of germanium may help elucidate the mechanisms of arsenite transport into grain. This review summarises recent discoveries in the location and speciation of arsenic, germanium, and selenium in rice grain using state-of-the-art mass spectrometry and synchrotron techniques, and illustrates both the importance of high-sensitivity and high-resolution techniques and the advantages of combining techniques in an integrated quantitative and spatial approach. PMID:22159463

Complete genomes of Hairstreak butterflies, their speciation, and nucleo-mitochondrial incongruence.

PubMed

Cong, Qian; Shen, Jinhui; Borek, Dominika; Robbins, Robert K; Otwinowski, Zbyszek; Grishin, Nick V

2016-04-28

Comparison of complete genomes of closely related species enables research on speciation and how phenotype is determined by genotype. Lepidoptera, an insect order of 150,000 species with diverse phenotypes, is well-suited for such comparative genomics studies if new genomes, which cover additional Lepidoptera families are acquired. We report a 729 Mbp genome assembly of the Calycopis cecrops, the first genome from the family Lycaenidae and the largest available Lepidoptera genome. As detritivore, Calycopis shows expansion in detoxification and digestion enzymes. We further obtained complete genomes of 8 Calycopis specimens: 3 C. cecrops and 5 C. isobeon, including a dry specimen stored in the museum for 30 years. The two species differ subtly in phenotype and cannot be differentiated by mitochondrial DNA. However, nuclear genomes revealed a deep split between them. Genes that can clearly separate the two species (speciation hotspots) mostly pertain to circadian clock, mating behavior, transcription regulation, development and cytoskeleton. The speciation hotspots and their function significantly overlap with those we previously found in Pterourus, suggesting common speciation mechanisms in these butterflies.

Speciation through the lens of biomechanics: locomotion, prey capture and reproductive isolation

PubMed Central

Rogers, Sean M.; Langerhans, R. Brian; Jamniczky, Heather A.; Lauder, George V.; Stewart, William J.; Martin, Christopher H.; Reznick, David N.

2016-01-01

Speciation is a multifaceted process that involves numerous aspects of the biological sciences and occurs for multiple reasons. Ecology plays a major role, including both abiotic and biotic factors. Whether populations experience similar or divergent ecological environments, they often adapt to local conditions through divergence in biomechanical traits. We investigate the role of biomechanics in speciation using fish predator–prey interactions, a primary driver of fitness for both predators and prey. We highlight specific groups of fishes, or specific species, that have been particularly valuable for understanding these dynamic interactions and offer the best opportunities for future studies that link genetic architecture to biomechanics and reproductive isolation (RI). In addition to emphasizing the key biomechanical techniques that will be instrumental, we also propose that the movement towards linking biomechanics and speciation will include (i) establishing the genetic basis of biomechanical traits, (ii) testing whether similar and divergent selection lead to biomechanical divergence, and (iii) testing whether/how biomechanical traits affect RI. Future investigations that examine speciation through the lens of biomechanics will propel our understanding of this key process. PMID:27629033

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...

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...

Heavy metal speciation, leaching and toxicity status of a tropical rain-fed river Damodar, India.

PubMed

Pal, Divya; Maiti, Subodh Kumar

2018-03-26

Speciations of metals were assessed in a tropical rain-fed river, flowing through the highly economically important part of the India. The pattern of distribution of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) were evaluated in water and sediment along with mineralogical characterization, changes with different water quality parameters and their respective health hazard to the local population along the Damodar River basin during pre-monsoon and post-monsoon seasons. The outcome of the speciation analysis using MINTEQ indicated that free metal ions, carbonate, chloride and sulfate ions were predominantly in anionic inorganic fractions, while in cationic inorganic fractions metal loads were negligible. Metals loads were higher in sediment phase than in the aqueous phase. The estimated values of I geo in river sediment during both the seasons showed that most of the metals were found in the I geo class 0-1 which represents unpolluted to moderately polluted sediment status. The result of partition coefficient indicated the strong retention capability of Cr, Pb, Co and Mn, while Cd, Zn, Cu and Ni have resilient mobility capacity. The mineralogical analysis of sediment samples indicated that in Damodar River, quartz, kaolinite and calcite minerals were dominantly present. The hazard index values of Cd, Co and Cr were > 1 in river water, which suggested potential health risk for the children. A combination of pragmatic, computational and statistical relationship between ionic species and fractions of metals represented a strong persuasion for identifying the alikeness among the different sites of the river.

Identification of the typical metal particles among haze, fog, and clear episodes in the Beijing atmosphere.

PubMed

Hu, Yunjie; Lin, Jun; Zhang, Suanqin; Kong, Lingdong; Fu, Hongbo; Chen, Jianmin

2015-04-01

For a better understanding of metal particle morphology and behaviors in China, atmospheric aerosols were sampled in the summer of 2012 in Beijing. The single-particle analysis shows various metal-bearing speciations, dominated by oxides, sulfates and nitrates. A large fraction of particles is soluble. Sources of Fe-bearing particles are mainly steel industries and oil fuel combustion, whereas Zn- and Pb-bearing particles are primarily contributed by waste incineration, besides industrial combustion. Other trace metal particles play a minor rule, and may come from diverse origins. Mineral dust and anthropogenic source like vehicles and construction activities are of less importance to metal-rich particles. Statistics of 1173 analyzed particles show that Fe-rich particles (48.5%) dominate the metal particles, followed by Zn-rich particles (34.9%) and Pb-rich particles (15.6%). Compared with the abundances among clear, haze and fog conditions, a severe metal pollution is identified in haze and fog episodes. Particle composition and elemental correlation suggest that the haze episodes are affected by the biomass burning in the southern regions, and the fog episodes by the local emission with manifold particle speciation. Our results show the heterogeneous reaction accelerated in the fog and haze episodes indicated by more zinc nitrate or zinc sulfate instead of zinc oxide or carbonate. Such information is useful in improving our knowledge of fine airborne metal particles on their morphology, speciation, and solubility, all of which will help the government introduce certain control to alleviate metal pollution. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

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

The spread of marine anoxia on the northern Tethys margin during the Paleocene-Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Dickson, Alexander J.; Rees-Owen, Rhian L.; März, Christian; Coe, Angela L.; Cohen, Anthony S.; Pancost, Richard D.; Taylor, Kyle; Shcherbinina, Ekaterina

2014-06-01

Records of the paleoenvironmental changes that occurred during the Paleocene-Eocene Thermal Maximum (PETM) are preserved in sedimentary rocks along the margins of the former Tethys Ocean and Peri-Tethys. This paper presents new geochemical data that constrain paleoproductivity, sediment delivery, and seawater redox conditions, from three sites that were located in the Peri-Tethys region. Trace and major element, iron speciation, and biomarker data indicate that water column anoxia was established during episodes when inputs of land-derived higher plant organic carbon and highly weathered detrital clays and silts became relatively higher. Anoxic conditions are likely to have been initially caused by two primary processes: (i) oxygen consumption by high rates of marine productivity, initially stimulated by the rapid delivery of terrestrially derived organic matter and nutrients, and (ii) phosphorus regeneration from seafloor sediments. The role of the latter process requires further investigation before its influence on the spread of deoxygenated seawater during the PETM can be properly discerned. Other oxygen-forcing processes, such as temperature/salinity-driven water column stratification and/or methane oxidation, are considered to have been relatively less important in the study region. Organic carbon enrichments occur only during the initial stages of the PETM as defined by the negative carbon isotope excursions at each site. The lack of observed terminal stage organic carbon enrichment does not support a link between PETM climate recovery and the sequestration of excess atmospheric CO2 as organic carbon in this region; such a feedback may, however, have been important in the early stages of the PETM.

Association of Soil Aggregation with the Distribution and Quality of Organic Carbon in Soil along an Elevation Gradient on Wuyi Mountain in China.

PubMed

Li, Liguang; Vogel, Jason; He, Zhenli; Zou, Xiaoming; Ruan, Honghua; Huang, Wei; Wang, Jiashe; Bianchi, Thomas S

2016-01-01

Forest soils play a critical role in the sequestration of atmospheric CO2 and subsequent attenuation of global warming. The nature and properties of organic matter in soils have an influence on the sequestration of carbon. In this study, soils were collected from representative forestlands, including a subtropical evergreen broad-leaved forest (EBF), a coniferous forest (CF), a subalpine dwarf forest (DF), and alpine meadow (AM) along an elevation gradient on Wuyi Mountain, which is located in a subtropical area of southeastern China. These soil samples were analyzed in the laboratory to examine the distribution and speciation of organic carbon (OC) within different size fractions of water-stable soil aggregates, and subsequently to determine effects on carbon sequestration. Soil aggregation rate increased with increasing elevation. Soil aggregation rate, rather than soil temperature, moisture or clay content, showed the strongest correlation with OC in bulk soil, indicating soil structure was the critical factor in carbon sequestration of Wuyi Mountain. The content of coarse particulate organic matter fraction, rather than the silt and clay particles, represented OC stock in bulk soil and different soil aggregate fractions. With increasing soil aggregation rate, more carbon was accumulated within the macroaggregates, particularly within the coarse particulate organic matter fraction (250-2000 μm), rather than within the microaggregates (53-250μm) or silt and clay particles (< 53μm). In consideration of the high instability of macroaggregates and the liability of SOC within them, further research is needed to verify whether highly-aggregated soils at higher altitudes are more likely to lose SOC under warmer conditions.

Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

NASA Astrophysics Data System (ADS)

Ulevicius, Vidmantas; Byčenkienė, Steigvilė; Bozzetti, Carlo; Vlachou, Athanasia; Plauškaitė, Kristina; Mordas, Genrik; Dudoitis, Vadimas; Abbaszade, Gülcin; Remeikis, Vidmantas; Garbaras, Andrius; Masalaite, Agne; Blees, Jan; Fröhlich, Roman; Dällenbach, Kaspar R.; Canonaco, Francesco; Slowik, Jay G.; Dommen, Josef; Zimmermann, Ralf; Schnelle-Kreis, Jürgen; Salazar, Gary A.; Agrios, Konstantinos; Szidat, Sönke; El Haddad, Imad; Prévôt, André S. H.

2016-05-01

In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m-3 and black carbon (BC) up to 17 µg m-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf) was the dominant fraction of PM1, with the primary (POCnf) and secondary (SOCnf) fractions contributing 26-44 % and 13-23 % to the total carbon (TC), respectively. 5-8 % of the TC had a primary fossil origin (POCf), whereas the contribution of fossil secondary organic carbon (SOCf) was 4-13 %. Non-fossil EC (ECnf) and fossil EC (ECf) ranged from 13-24 and 7-13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

Association of Soil Aggregation with the Distribution and Quality of Organic Carbon in Soil along an Elevation Gradient on Wuyi Mountain in China

PubMed Central

Li, Liguang; Vogel, Jason; He, Zhenli; Zou, Xiaoming; Ruan, Honghua; Huang, Wei; Wang, Jiashe; Bianchi, Thomas S.

2016-01-01

Forest soils play a critical role in the sequestration of atmospheric CO2 and subsequent attenuation of global warming. The nature and properties of organic matter in soils have an influence on the sequestration of carbon. In this study, soils were collected from representative forestlands, including a subtropical evergreen broad-leaved forest (EBF), a coniferous forest (CF), a subalpine dwarf forest (DF), and alpine meadow (AM) along an elevation gradient on Wuyi Mountain, which is located in a subtropical area of southeastern China. These soil samples were analyzed in the laboratory to examine the distribution and speciation of organic carbon (OC) within different size fractions of water-stable soil aggregates, and subsequently to determine effects on carbon sequestration. Soil aggregation rate increased with increasing elevation. Soil aggregation rate, rather than soil temperature, moisture or clay content, showed the strongest correlation with OC in bulk soil, indicating soil structure was the critical factor in carbon sequestration of Wuyi Mountain. The content of coarse particulate organic matter fraction, rather than the silt and clay particles, represented OC stock in bulk soil and different soil aggregate fractions. With increasing soil aggregation rate, more carbon was accumulated within the macroaggregates, particularly within the coarse particulate organic matter fraction (250–2000 μm), rather than within the microaggregates (53–250μm) or silt and clay particles (< 53μm). In consideration of the high instability of macroaggregates and the liability of SOC within them, further research is needed to verify whether highly-aggregated soils at higher altitudes are more likely to lose SOC under warmer conditions. PMID:26964101

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

Assessing element distribution and speciation in a stream at abandoned Pb-Zn mining site by combining classical, in-situ DGT and modelling approaches.

PubMed

Omanović, Dario; Pižeta, Ivanka; Vukosav, Petra; Kovács, Elza; Frančišković-Bilinski, Stanislav; Tamás, János

2015-04-01

The distribution and speciation of elements along a stream subjected to neutralised acid mine drainage (NAMD) effluent waters (Mátra Mountain, Hungary; Toka stream) were studied by a multi-methodological approach: dissolved and particulate fractions of elements were determined by HR-ICPMS, whereas speciation was carried out by DGT, supported by speciation modelling performed by Visual MINTEQ. Before the NAMD discharge, the Toka is considered as a pristine stream, with averages of dissolved concentrations of elements lower than world averages. A considerable increase of element concentrations caused by effluent water inflow is followed by a sharp or gradual concentration decrease. A large difference between total and dissolved concentrations was found for Fe, Al, Pb, Cu, Zn and As in effluent water and at the first downstream site, with high correlation factors between elements in particulate fraction, indicating their common behaviour, governed by the formation of ferri(hydr)oxides (co)precipitates. In-situ speciation by the DGT technique revealed that Zn, Cd, Ni, Co, Mn and U were predominantly present as a labile, potentially bioavailable fraction (>90%). The formation of strong complexes with dissolved organic matter (DOM) resulted in a relatively low DGT-labile concentration of Cu (42%), while low DGT-labile concentrations of Fe (5%) and Pb (12%) were presumably caused by their existence in colloidal (particulate) fraction which is not accessible to DGT. Except for Fe and Pb, a very good agreement between DGT-labile concentrations and those predicted by the applied speciation model was obtained, with an average correlation factor of 0.96. This study showed that the in-situ DGT technique in combination with model-predicted speciation and classical analysis of samples could provide a reasonable set of data for the assessment of the water quality status (WQS), as well as for the more general study of overall behaviour of the elements in natural waters subjected to high element loads. Copyright © 2014 Elsevier B.V. All rights reserved.

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

EPA Science Inventory

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

Cobalt Distribution and Speciation: Effect of Aging, Intermittent Submergence, In situ Rice Roots

EPA Science Inventory

The speciation and distribution of cobalt (Co) in soils is poorly understood. This study was conducted using X-ray absorption spectroscopy (XAS) techniques to examine the influence of soluble Co(II) aging, submergence-dried cycling, and the presence of in vivo rice roots on the...

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...

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

EPA Science Inventory

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

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

PubMed

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

2015-09-01

Present study deals with the river Ganga water quality and its impact on metal speciation in its sediments. Concentration of physico-chemical parameters was highest in summer season followed by winter and lowest in rainy season. Metal speciation study in river sediments revealed that exchangeable, reducible and oxidizable fractions were dominant in all the studied metals (Cr, Ni, Cu, Zn, Cd, Pb) except Mn and Fe. High pollution load index (1.64-3.89) recommends urgent need of mitigation measures. Self-organizing Map-Artificial Neural Network (SOM-ANN) was applied to the data set for the prediction of major point sources of pollution in the river Ganga. Copyright © 2015 Elsevier Ltd. All rights reserved.

Adsorption of mercury by activated carbon prepared from dried sewage sludge in simulated flue gas.

PubMed

Park, Jeongmin; Lee, Sang-Sup

2018-04-25

Conversion of sewage sludge to activated carbon is attractive as an alternative method to ocean dumping for the disposal of sewage sludge. Injection of activated carbon upstream of particulate matter control devices has been suggested as a method to remove elemental mercury from flue gas. Activated carbon was prepared using various activation temperatures and times and was tested for their mercury adsorption efficiency using lab-scale systems. To understand the effect of the physical property of the activated carbon, its mercury adsorption efficiency was investigated as a function of their Brunauer-Emmett-Teller (BET) surface area. Two simulated flue gas conditions: (1) without hydrogen chloride (HCl) and (2) with 20 ppm HCl, were used to investigate the effect of flue gas composition on the mercury adsorption capacity of activated carbon. Despite very low BET surface area of the prepared sewage sludge activated carbons, their mercury adsorption efficiencies were comparable under both simulated flue gas conditions to those of pinewood and coal activated carbons. After injecting HCl into the simulated flue gas, all sewage sludge activated carbons demonstrated high adsorption efficiencies, i.e., more than 87%, regardless of their BET surface area. IMPLICATIONS We tested activated carbons prepared from dried sewage sludge to investigate the effect of their physical properties on their mercury adsorption efficiency. Using two simulated flue gas conditions, we conducted mercury speciation for the outlet gas. We found that the sewage sludge activated carbon had comparable mercury adsorption efficiency to pinewood and coal activated carbons, and the presence of HCl minimized the effect of physical property of the activated carbon on its mercury adsorption efficiency.

Bioconcentration and arsenic speciation analysis in ragworm, Hediste diversicolor (Muller 1776).

PubMed

Gaion, Andrea; Scuderi, Alice; Pellegrini, David; Sartori, Davide

2013-01-01

This study focused on bioconcentrations of arsenic in Hediste diversicolor (Müller 1776) after exposure to three different molecule solutions: arsenate, dimethyl-arsinate and arsenobetaine. Speciation analysis was carried out after exposing the organisms to these solutions in order to investigate their arsenic biotransformation capacity. Arsenic reached to the maximum level in these tissues after 15 days' exposure to a solution of 100 μg L(-1) of arsenobetaine, although a significant increase was obtained in worms exposed to arsenate. Speciation analysis shows that trimethyl-arsine oxide is the slowest detoxification phase recorded in experiment.

Selenium speciation in seleniferous agricultural soils under different cropping systems using sequential extraction and X-ray absorption spectroscopy.

PubMed

Qin, Hai-Bo; Zhu, Jian-Ming; Lin, Zhi-Qing; Xu, Wen-Po; Tan, De-Can; Zheng, Li-Rong; Takahashi, Yoshio

2017-06-01

Selenium (Se) speciation in soil is critically important for understanding the solubility, mobility, bioavailability, and toxicity of Se in the environment. In this study, Se fractionation and chemical speciation in agricultural soils from seleniferous areas were investigated using the elaborate sequential extraction and X-ray absorption near-edge structure (XANES) spectroscopy. The speciation results quantified by XANES technique generally agreed with those obtained by sequential extraction, and the combination of both approaches can reliably characterize Se speciation in soils. Results showed that dominant organic Se (56-81% of the total Se) and lesser Se(IV) (19-44%) were observed in seleniferous agricultural soils. A significant decrease in the proportion of organic Se to the total Se was found in different types of soil, i.e., paddy soil (81%) > uncultivated soil (69-73%) > upland soil (56-63%), while that of Se(IV) presented an inverse tendency. This suggests that Se speciation in agricultural soils can be significantly influenced by different cropping systems. Organic Se in seleniferous agricultural soils was probably derived from plant litter, which provides a significant insight for phytoremediation in Se-laden ecosystems and biofortification in Se-deficient areas. Furthermore, elevated organic Se in soils could result in higher Se accumulation in crops and further potential chronic Se toxicity to local residents in seleniferous areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

[XANES study of lead speciation in duckweed].

PubMed

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

2012-07-01

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

Rates of speciation and morphological evolution are correlated across the largest vertebrate radiation.

PubMed

Rabosky, Daniel L; Santini, Francesco; Eastman, Jonathan; Smith, Stephen A; Sidlauskas, Brian; Chang, Jonathan; Alfaro, Michael E

2013-01-01

Several evolutionary theories predict that rates of morphological change should be positively associated with the rate at which new species arise. For example, the theory of punctuated equilibrium proposes that phenotypic change typically occurs in rapid bursts associated with speciation events. However, recent phylogenetic studies have found little evidence linking these processes in nature. Here we demonstrate that rates of species diversification are highly correlated with the rate of body size evolution across the 30,000+ living species of ray-finned fishes that comprise the majority of vertebrate biological diversity. This coupling is a general feature of fish evolution and transcends vast differences in ecology and body-plan organization. Our results may reflect a widespread speciational mode of character change in living fishes. Alternatively, these findings are consistent with the hypothesis that phenotypic 'evolvability'-the capacity of organisms to evolve-shapes the dynamics of speciation through time at the largest phylogenetic scales.

Global cooling as a driver of diversification in a major marine clade

PubMed Central

Davis, Katie E.; Hill, Jon; Astrop, Tim I.; Wills, Matthew A.

2016-01-01

Climate is a strong driver of global diversity and will become increasingly important as human influences drive temperature changes at unprecedented rates. Here we investigate diversification and speciation trends within a diverse group of aquatic crustaceans, the Anomura. We use a phylogenetic framework to demonstrate that speciation rate is correlated with global cooling across the entire tree, in contrast to previous studies. Additionally, we find that marine clades continue to show evidence of increased speciation rates with cooler global temperatures, while the single freshwater clade shows the opposite trend with speciation rates positively correlated to global warming. Our findings suggest that both global cooling and warming lead to diversification and that habitat plays a role in the responses of species to climate change. These results have important implications for our understanding of how extant biota respond to ongoing climate change and are of particular importance for conservation planning of marine ecosystems. PMID:27701377

Computer simulations of sympatric speciation in a simple food web

NASA Astrophysics Data System (ADS)

Luz-Burgoa, K.; Dell, Tony; de Oliveira, S. Moss

2005-07-01

Galapagos finches, have motivated much theoretical research aimed at understanding the processes associated with the formation of the species. Inspired by them, in this paper we investigate the process of sympatric speciation in a simple food web model. For that we modify the individual-based Penna model that has been widely used to study aging as well as other evolutionary processes. Initially, our web consists of a primary food source and a single herbivore species that feeds on this resource. Subsequently we introduce a predator that feeds on the herbivore. In both instances we manipulate directly a basal resource distribution and monitor the changes in the populations. Sympatric speciation is obtained for the top species in both cases, and our results suggest that the speciation velocity depends on how far up, in the food chain, the focus population is feeding. Simulations are done with three different sexual imprintinglike mechanisms, in order to discuss adaptation by natural selection.

Global cooling as a driver of diversification in a major marine clade

NASA Astrophysics Data System (ADS)

Davis, Katie E.; Hill, Jon; Astrop, Tim I.; Wills, Matthew A.

2016-10-01

Climate is a strong driver of global diversity and will become increasingly important as human influences drive temperature changes at unprecedented rates. Here we investigate diversification and speciation trends within a diverse group of aquatic crustaceans, the Anomura. We use a phylogenetic framework to demonstrate that speciation rate is correlated with global cooling across the entire tree, in contrast to previous studies. Additionally, we find that marine clades continue to show evidence of increased speciation rates with cooler global temperatures, while the single freshwater clade shows the opposite trend with speciation rates positively correlated to global warming. Our findings suggest that both global cooling and warming lead to diversification and that habitat plays a role in the responses of species to climate change. These results have important implications for our understanding of how extant biota respond to ongoing climate change and are of particular importance for conservation planning of marine ecosystems.

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...

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.

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.

Riverscape genetics identifies replicated ecological divergence across an Amazonian ecotone.

PubMed

Cooke, Georgina M; Landguth, Erin L; Beheregaray, Luciano B

2014-07-01

Ecological speciation involves the evolution of reproductive isolation and niche divergence in the absence of a physical barrier to gene flow. The process is one of the most controversial topics of the speciation debate, particularly in tropical regions. Here, we investigate ecologically based divergence across an Amazonian ecotone in the electric fish, Steatogenys elegans. We combine phylogenetics, genome scans, and population genetics with a recently developed individual-based evolutionary landscape genetics approach that incorporates selection. This framework is used to assess the relative contributions of geography and divergent natural selection between environments as biodiversity drivers. We report on two closely related and sympatric lineages that exemplify how divergent selection across a major Amazonian aquatic ecotone (i.e., between rivers with markedly different hydrochemical properties) may result in replicated ecologically mediated speciation. The results link selection across an ecological gradient with reproductive isolation and we propose that assortative mating based on water color may be driving the divergence. Divergence resulting from ecologically driven selection highlights the importance of considering environmental heterogeneity in studies of speciation in tropical regions. Furthermore, we show that framing ecological speciation in a spatially explicit evolutionary landscape genetics framework provides an important first step in exploring a wide range of the potential effects of spatial dependence in natural selection. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

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

PubMed Central

Border, Shana E

2018-01-01

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

A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS.

PubMed

Day, Jason A; Montes-Bayón, María; Vonderheide, Anne P; Caruso, Joseph A

2002-08-01

Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate.

Influence of gene flow on divergence dating - implications for the speciation history of Takydromus grass lizards.

PubMed

Tseng, Shu-Ping; Li, Shou-Hsien; Hsieh, Chia-Hung; Wang, Hurng-Yi; Lin, Si-Min

2014-10-01

Dating the time of divergence and understanding speciation processes are central to the study of the evolutionary history of organisms but are notoriously difficult. The difficulty is largely rooted in variations in the ancestral population size or in the genealogy variation across loci. To depict the speciation processes and divergence histories of three monophyletic Takydromus species endemic to Taiwan, we sequenced 20 nuclear loci and combined with one mitochondrial locus published in GenBank. They were analysed by a multispecies coalescent approach within a Bayesian framework. Divergence dating based on the gene tree approach showed high variation among loci, and the divergence was estimated at an earlier date than when derived by the species-tree approach. To test whether variations in the ancestral population size accounted for the majority of this variation, we conducted computer inferences using isolation-with-migration (IM) and approximate Bayesian computation (ABC) frameworks. The results revealed that gene flow during the early stage of speciation was strongly favoured over the isolation model, and the initiation of the speciation process was far earlier than the dates estimated by gene- and species-based divergence dating. Due to their limited dispersal ability, it is suggested that geographical isolation may have played a major role in the divergence of these Takydromus species. Nevertheless, this study reveals a more complex situation and demonstrates that gene flow during the speciation process cannot be overlooked and may have a great impact on divergence dating. By using multilocus data and incorporating Bayesian coalescence approaches, we provide a more biologically realistic framework for delineating the divergence history of Takydromus. © 2014 John Wiley & Sons Ltd.

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

Cold Temperature Effects on Speciated VOC Emissions from Modern GDI Light-Duty Vehicles 1

EPA Science Inventory

In this study, speciated VOC emissions were characterized from three modern GDI light-duty vehicles. The vehicles were tested on a chassis dynamometer housed in a climate-controlled chamber at two temperatures (20 and 72 °F) using the EPA Federal Test Procedure (FTP) and a portio...

A COMPARISON OF URINARY ARSENIC SPECIATION VIA DIRECT NEBULIZATION AND ON-LINE PHOTOOXIDATION-HYDRIDE GENERATION WITH DETECTION BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

EPA Science Inventory

Arsenic speciation continues to be important in assessing human and environmental exposure risk. Urinary arsenic analysis provides information on recent arsenic exposure. In this study, two sample introduction pathways: direct nebulization (DN) and hydride generation (HG) were ut...

The genomic landscape at a late stage of stickleback speciation: High genomic divergence interspersed by small localized regions of introgression.

PubMed

Ravinet, Mark; Yoshida, Kohta; Shigenobu, Shuji; Toyoda, Atsushi; Fujiyama, Asao; Kitano, Jun

2018-05-01

Speciation is a continuous process and analysis of species pairs at different stages of divergence provides insight into how it unfolds. Previous genomic studies on young species pairs have revealed peaks of divergence and heterogeneous genomic differentiation. Yet less known is how localised peaks of differentiation progress to genome-wide divergence during the later stages of speciation in the presence of persistent gene flow. Spanning the speciation continuum, stickleback species pairs are ideal for investigating how genomic divergence builds up during speciation. However, attention has largely focused on young postglacial species pairs, with little knowledge of the genomic signatures of divergence and introgression in older stickleback systems. The Japanese stickleback species pair, composed of the Pacific Ocean three-spined stickleback (Gasterosteus aculeatus) and the Japan Sea stickleback (G. nipponicus), which co-occur in the Japanese islands, is at a late stage of speciation. Divergence likely started well before the end of the last glacial period and crosses between Japan Sea females and Pacific Ocean males result in hybrid male sterility. Here we use coalescent analyses and Approximate Bayesian Computation to show that the two species split approximately 0.68-1 million years ago but that they have continued to exchange genes at a low rate throughout divergence. Population genomic data revealed that, despite gene flow, a high level of genomic differentiation is maintained across the majority of the genome. However, we identified multiple, small regions of introgression, occurring mainly in areas of low recombination rate. Our results demonstrate that a high level of genome-wide divergence can establish in the face of persistent introgression and that gene flow can be localized to small genomic regions at the later stages of speciation with gene flow.

Chromosomal Speciation in the Genomics Era: Disentangling Phylogenetic Evolution of Rock-wallabies.

PubMed

Potter, Sally; Bragg, Jason G; Blom, Mozes P K; Deakin, Janine E; Kirkpatrick, Mark; Eldridge, Mark D B; Moritz, Craig

2017-01-01

The association of chromosome rearrangements (CRs) with speciation is well established, and there is a long history of theory and evidence relating to "chromosomal speciation." Genomic sequencing has the potential to provide new insights into how reorganization of genome structure promotes divergence, and in model systems has demonstrated reduced gene flow in rearranged segments. However, there are limits to what we can understand from a small number of model systems, which each only tell us about one episode of chromosomal speciation. Progressing from patterns of association between chromosome (and genic) change, to understanding processes of speciation requires both comparative studies across diverse systems and integration of genome-scale sequence comparisons with other lines of evidence. Here, we showcase a promising example of chromosomal speciation in a non-model organism, the endemic Australian marsupial genus Petrogale . We present initial phylogenetic results from exon-capture that resolve a history of divergence associated with extensive and repeated CRs. Yet it remains challenging to disentangle gene tree heterogeneity caused by recent divergence and gene flow in this and other such recent radiations. We outline a way forward for better integration of comparative genomic sequence data with evidence from molecular cytogenetics, and analyses of shifts in the recombination landscape and potential disruption of meiotic segregation and epigenetic programming. In all likelihood, CRs impact multiple cellular processes and these effects need to be considered together, along with effects of genic divergence. Understanding the effects of CRs together with genic divergence will require development of more integrative theory and inference methods. Together, new data and analysis tools will combine to shed light on long standing questions of how chromosome and genic divergence promote speciation.

Gas and aerosol carbon in California: comparison of ...

EPA Pesticide Factsheets

Co-located measurements of fine particulate matter (PM2.5) organic carbon (OC), elemental carbon, radiocarbon (14C), speciated volatile organic compounds (VOCs),and OH radicals during the CalNex field campaign provide a unique opportunity to evaluate the Community Multiscale Air Quality (CMAQ) model's representation of organic species from VOCs to particles. Episode average daily 23 h average 14C analysis indicates PM2.5 carbon at Pasadena and Bakersfield during the CalNex field campaign was evenly split between contemporary and fossil origins. CMAQ predicts a higher contemporary carbon fraction than indicated by the 14C analysis at both locations. The model underestimates measured PM2.5 organic carbon at both sites with very little (7% in Pasadena) of the modeled mass represented by secondary production, which contrasts with the ambient-based SOC/OC fraction of 63% at Pasadena. The National Exposure Research Laboratory’s (NERL’s) Human Exposure and Atmospheric Sciences Division (HEASD) conducts research in support of EPA’s mission to protect human health and the environment. HEASD’s research program supports Goal 1 (Clean Air) and Goal 4 (Healthy People) of EPA’s strategic plan. More specifically, our division conducts research to characterize the movement of pollutants from the source to contact with humans. Our multidisciplinary research program produces Methods, Measurements, and Models to identify relationships between and characterize processe

Remediation of metal-contaminated urban soil using flotation technique.

PubMed

Dermont, G; Bergeron, M; Richer-Laflèche, M; Mercier, G

2010-02-01

A soil washing process using froth flotation technique was evaluated for the removal of arsenic, cadmium, copper, lead, and zinc from a highly contaminated urban soil (brownfield) after crushing of the particle-size fractions >250microm. The metal contaminants were in particulate forms and distributed in all the particle-size fractions. The particle-by-particle study with SEM-EDS showed that Zn was mainly present as sphalerite (ZnS), whereas Cu and Pb were mainly speciated as various oxide/carbonate compounds. The influence of surfactant collector type (non-ionic and anionic), collector dosage, pulp pH, a chemical activation step (sulfidization), particle size, and process time on metal removal efficiency and flotation selectivity was studied. Satisfactory results in metal recovery (42-52%), flotation selectivity (concentration factor>2.5), and volume reduction (>80%) were obtained with anionic collector (potassium amyl xanthate). The transportation mechanisms involved in the separation process (i.e., the true flotation and the mechanical entrainment) were evaluated by the pulp chemistry, the metal speciation, the metal distribution in the particle-size fractions, and the separation selectivity indices of Zn/Ca and Zn/Fe. The investigations showed that a great proportion of metal-containing particles were recovered in the froth layer by entrainment mechanism rather than by true flotation process. The non-selective entrainment mechanism of the fine particles (<20 microm) caused a flotation selectivity drop, especially with a long flotation time (>5 min) and when a high collector dose is used. The intermediate particle-size fraction (20-125 microm) showed the best flotation selectivity. Copyright 2009 Elsevier B.V. All rights reserved.

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment.

PubMed

Dong, Wenming; Ball, William P; Liu, Chongxuan; Wang, Zheming; Stone, Alan T; Bai, Jing; Zachara, John M

2005-10-15

The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.

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

Chen, Chunmei; Kukkadapu, Ravi K.; Lazareva, Olesya

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased themore » crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.« less

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

USGS Publications Warehouse

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

2003-01-01

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

Speciation of adsorbates on surface of solids by infrared spectroscopy and chemometrics.

PubMed

Vilmin, Franck; Bazin, Philippe; Thibault-Starzyk, Frédéric; Travert, Arnaud

2015-09-03

Speciation, i.e. identification and quantification, of surface species on heterogeneous surfaces by infrared spectroscopy is important in many fields but remains a challenging task when facing strongly overlapped spectra of multiple adspecies. Here, we propose a new methodology, combining state of the art instrumental developments for quantitative infrared spectroscopy of adspecies and chemometrics tools, mainly a novel data processing algorithm, called SORB-MCR (SOft modeling by Recursive Based-Multivariate Curve Resolution) and multivariate calibration. After formal transposition of the general linear mixture model to adsorption spectral data, the main issues, i.e. validity of Beer-Lambert law and rank deficiency problems, are theoretically discussed. Then, the methodology is exposed through application to two case studies, each of them characterized by a specific type of rank deficiency: (i) speciation of physisorbed water species over a hydrated silica surface, and (ii) speciation (chemisorption and physisorption) of a silane probe molecule over a dehydrated silica surface. In both cases, we demonstrate the relevance of this approach which leads to a thorough surface speciation based on comprehensive and fully interpretable multivariate quantitative models. Limitations and drawbacks of the methodology are also underlined. Copyright © 2015 Elsevier B.V. All rights reserved.

Speciation of mercury compounds by differential atomization - atomic absorption spectroscopy

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

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

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

Mountain Refugia Play a Role in Soil Arthropod Speciation on Madagascar: A Case Study of the Endemic Giant Fire-Millipede Genus Aphistogoniulus

PubMed Central

Wesener, Thomas; Raupach, Michael J.; Decker, Peter

2011-01-01

To elucidate the speciation mechanisms prevalent within hotspots of biodiversity, and the evolutionary processes behind the rise of their species-rich and endemic biota, we investigated the phylogeny of the giant fire-millipede genus Aphistogoniulus Silvestri, 1897, a Malagasy endemic. This study is the first comprehensive (molecular and morphological) phylogenetic study focusing on millipede (class Diplopoda) speciation on Madagascar. The morphological analysis is based on 35 morphological characters and incorporates ten described as well as two newly described species (A. rubrodorsalis n. sp. and A. jeekeli n. sp.) of Aphistogoniulus. The molecular analysis is based on both mitochondrial (COI and 16S), and nuclear genes (complete 18S rDNA), together comprised of 3031 base pairs, which were successfully sequenced for 31 individual specimens and eight species of Aphistogoniulus. In addition to the null-model (speciation by distance), two diversification models, mountain refugia and ecotone shift, were discovered to play a role in the speciation of soil arthropods on Madagascar. Mountain refugia were important in the speciation of the A. cowani clade, with three species occurring in the Andringitra and Ranomafana Mountains in the southeast (A. cowani), the Ambohijanahary and Ambohitantely Mountains in the mid-west (A. sanguineus), and the Marojejy Mountain in the northeast (A. rubrodorsalis n. sp.). An ecotone shift from the eastern rainforest to the unique subarid spiny forest of Mahavelo was discovered in the A. vampyrus - A. aridus species-pair. In the monophyletic A. diabolicus clade, evidence for divergent evolution of sexual morphology was detected: species with greatly enlarged gonopods are sister-taxa to species with normal sized gonopods. Among the large-bodied Spirobolida genera of Madagascar, Colossobolus and Sanguinobolus were found to be close sister-genera to Aphistogoniulus. Forest destruction has caused forest corridors between populations to disappear, which might limit the possible resolution of biogeographic analyses on Madagascar. PMID:22162998

Sympatric ecological speciation meets pyrosequencing: sampling the transcriptome of the apple maggot Rhagoletis pomonella

PubMed Central

2009-01-01

Background The full power of modern genetics has been applied to the study of speciation in only a small handful of genetic model species - all of which speciated allopatrically. Here we report the first large expressed sequence tag (EST) study of a candidate for ecological sympatric speciation, the apple maggot Rhagoletis pomonella, using massively parallel pyrosequencing on the Roche 454-FLX platform. To maximize transcript diversity we created and sequenced separate libraries from larvae, pupae, adult heads, and headless adult bodies. Results We obtained 239,531 sequences which assembled into 24,373 contigs. A total of 6810 unique protein coding genes were identified among the contigs and long singletons, corresponding to 48% of all known Drosophila melanogaster protein-coding genes. Their distribution across GO classes suggests that we have obtained a representative sample of the transcriptome. Among these sequences are many candidates for potential R. pomonella "speciation genes" (or "barrier genes") such as those controlling chemosensory and life-history timing processes. Furthermore, we identified important marker loci including more than 40,000 single nucleotide polymorphisms (SNPs) and over 100 microsatellites. An initial search for SNPs at which the apple and hawthorn host races differ suggested at least 75 loci warranting further work. We also determined that developmental expression differences remained even after normalization; transcripts expected to show different expression levels between larvae and pupae in D. melanogaster also did so in R. pomonella. Preliminary comparative analysis of transcript presences and absences revealed evidence of gene loss in Drosophila and gain in the higher dipteran clade Schizophora. Conclusions These data provide a much needed resource for exploring mechanisms of divergence in this important model for sympatric ecological speciation. Our description of ESTs from a substantial portion of the R. pomonella transcriptome will facilitate future functional studies of candidate genes for olfaction and diapause-related life history timing, and will enable large scale expression studies. Similarly, the identification of new SNP and microsatellite markers will facilitate future population and quantitative genetic studies of divergence between the apple and hawthorn-infesting host races. PMID:20035631

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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.

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

USGS Publications Warehouse

Koschinsky, A.; Hein, J.R.

2003-01-01

Marine Fe-Mn oxyhydroxide crusts form by precipitation of dissolved components from seawater. Three hydrogenetic crust samples (one phosphatized) and two hydrothermal Mn-oxide samples were subjected to a sequential-leaching procedure in order to determine the host phases of 40 elements. Those host-phase associations are discussed with respect to element speciation in seawater. The partitioning of elements between the two major phases, Mn oxide and Fe oxyhydroxide, can in a first-order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater, as has been proposed in earlier models. Free and weakly complexed cations, such as alkali and alkaline earth metals, Mn, Co, Ni, Zn, T1(I), and partly Y, are sorbed preferentially on the negatively charged surface of the MnO2 in hydrogenetic crusts. The driving force is a strong coulombic interaction. All neutral or negatively charged chloro (Cd, Hg, T1), carbonate (Cu, Y, Pb, and U), and hydroxide (Be, Sc, Ti, Fe, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, Bi, Th, and T1(III)) complexes and oxyanions (V, Cr, As, Se, Mo, and W) bind to the slightly positively charged surface of the amorphous FeOOH phase. While coulombic interaction can explain the sorption of the negatively charged species, the binding of neutral species is based on specific chemical interaction. Organic complexation of elements in deep-ocean water seems to be at most of minor importance. Surface oxidation can explain some strong metal associations, e.g. of Co and T1 with the MnO2 and Te with the FeOOH. Sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface. Differences in the associations of some metals between the non-phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico-chemical environments of formation and speciations in oxic seawater vs. less-oxic fluids, especially for the redox-sensitive metals such as Mo and V. These environmental-related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth. ?? 2003 Elsevier Science B.V. All rights reserved.

Environmental controls on the activity of aquifer microbial communities in the 300 area of the Hanford site.

PubMed

Konopka, Allan; Plymale, Andrew E; Carvajal, Denny A; Lin, Xueju; McKinley, James P

2013-11-01

Aquifer microbes in the 300 Area of the Hanford Site in southeastern Washington State, USA, are located in an oligotrophic environment and are periodically exposed to U(VI) concentrations that can range up to 10 μM in small sediment fractures. Assays of (3)H-leucine incorporation indicated that both sediment-associated and planktonic microbes were metabolically active, and that organic C was growth-limiting in the sediments. Although bacteria suspended in native groundwater retained high activity when exposed to 100 μM U(VI), they were inhibited by U(VI) <1 μM in synthetic groundwater that lacked added bicarbonate. Chemical speciation modeling suggested that positively charged species and particularly (UO2)3(OH)5 (+) rose in concentration as more U(VI) was added to synthetic groundwater, but that carbonate complexes dominated U(VI) speciation in natural groundwater. U toxicity was relieved when increasing amounts of bicarbonate were added to synthetic groundwater containing 4.5 μM U(VI). Pertechnetate, an oxyanion that is another contaminant of concern at the Hanford Site, was not toxic to groundwater microbes at concentrations up to 125 μM.

Phosphate fertilizer affected rhizospheric soils: speciation of cadmium and phytoremediation by Chlorophytum comosum.

PubMed

Wang, Youbao; Zhu, Chengfeng; Yang, Hongfei; Zhang, Xiaowei

2017-02-01

Experiments were conducted to investigate the effect of phosphate fertilization on chemical speciation of cadmium (Cd) in the rhizospheric soil of Chlorophytum comosum, a potential cadmium hyperaccumulator. The results revealed that when 200 mg kg -1 phosphate was applied into the soil, the Cd contents in the exchangeable fraction (EXC), carbonate-binding fraction (CA), and Fe-Mn oxides-binding fraction (Fe-Mn) were the highest, and the Cd content in the residual fraction (RES) was the lowest. Phosphate fertilization could enhance Cd conversion from RES into CA and weak RES, thereby improving the bioavailability of Cd and enhancing Cd enrichment and adsorption by C. comosum. The total Cd content in the soil was reduced by 10.15 mg kg -1 in the planted group, which was significantly different from the control group (p < 0.01). The highest bioaccumulation coefficient (BC) values in root and aboveground parts appeared when the phosphate rates were 276 and 217 mg kg -1 , whereas the highest translocation factor (TF) occurred with a phosphate rate of 188 mg kg -1 . Phosphate fertilization facilitated phytoremediation of Cd-polluted soil by C. comosum.

Influence of soil pH on the sorption of ionizable chemicals: modeling advances.

PubMed

Franco, Antonio; Fu, Wenjing; Trapp, Stefan

2009-03-01

The soil-water distribution coefficient of ionizable chemicals (K(d)) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K(d) values normalized to organic carbon (K(OC)) from the literature, a method was developed to estimate the K(OC) of monovalent organic acids and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P(n)). Probably because of the lower pH near the organic colloid-water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals.

Shedding Light on the Grey Zone of Speciation along a Continuum of Genomic Divergence.

PubMed

Roux, Camille; Fraïsse, Christelle; Romiguier, Jonathan; Anciaux, Yoann; Galtier, Nicolas; Bierne, Nicolas

2016-12-01

Speciation results from the progressive accumulation of mutations that decrease the probability of mating between parental populations or reduce the fitness of hybrids-the so-called species barriers. The speciation genomic literature, however, is mainly a collection of case studies, each with its own approach and specificities, such that a global view of the gradual process of evolution from one to two species is currently lacking. Of primary importance is the prevalence of gene flow between diverging entities, which is central in most species concepts and has been widely discussed in recent years. Here, we explore the continuum of speciation thanks to a comparative analysis of genomic data from 61 pairs of populations/species of animals with variable levels of divergence. Gene flow between diverging gene pools is assessed under an approximate Bayesian computation (ABC) framework. We show that the intermediate "grey zone" of speciation, in which taxonomy is often controversial, spans from 0.5% to 2% of net synonymous divergence, irrespective of species life history traits or ecology. Thanks to appropriate modeling of among-locus variation in genetic drift and introgression rate, we clarify the status of the majority of ambiguous cases and uncover a number of cryptic species. Our analysis also reveals the high incidence in animals of semi-isolated species (when some but not all loci are affected by barriers to gene flow) and highlights the intrinsic difficulty, both statistical and conceptual, of delineating species in the grey zone of speciation.

Both temperature fluctuations and East Asian monsoons have driven plant diversification in the karst ecosystems from southern China.

PubMed

Kong, Hanghui; Condamine, Fabien L; Harris, A J; Chen, Junlin; Pan, Bo; Möller, Michael; Hoang, Van Sam; Kang, Ming

2017-11-01

Karst ecosystems in southern China are species-rich and have high levels of endemism, yet little is known regarding the evolutionary processes responsible for the origin and diversification of karst biodiversity. The genus Primulina (Gesneriaceae) comprises ca. 170 species endemic to southern China with high levels of ecological (edaphic) specialization, providing an exceptional model to study the plant diversification in karsts. We used molecular data from nine chloroplast and 11 nuclear regions and macroevolutionary analyses to assess the origin and cause of species diversification due to palaeoenvironmental changes and edaphic specialization in Primulina. We found that speciation was positively associated with changes in past temperatures and East Asian monsoons through the evolutionary history of Primulina. Climatic change around the mid-Miocene triggered an early burst followed by a slowdown of diversification rate towards the present with the climate cooling. We detected different speciation rates among edaphic types, and transitions among soil types were infrequently and did not impact the overall speciation rate. Our findings suggest that both global temperature changes and East Asian monsoons have played crucial roles in floristic diversification within the karst ecosystems in southern China, such that speciation was higher when climate was warmer and wetter. This is the first study to directly demonstrate that past monsoon activity is positively correlated with speciation rate in East Asia. This case study could motivate further investigations to assess the impacts of past environmental changes on the origin and diversification of biodiversity in global karst ecosystems, most of which are under threat. © 2017 John Wiley & Sons Ltd.

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

USGS Publications Warehouse

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

2016-01-01

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

Characterization of traffic-related ambient fine particulate matter (PM2.5) in an Asian city: Environmental and health implications

NASA Astrophysics Data System (ADS)

Zhang, Zhi-Hui; Khlystov, Andrey; Norford, Leslie K.; Tan, Zhen-Kang; Balasubramanian, Rajasekhar

2017-07-01

Vehicular traffic emission is an important source of particulate pollution in most urban areas. The detailed chemical speciation of traffic-related PM2.5 (fine particles) is relatively sparse in the literature, especially in Asian cities. To fill this knowledge gap, we carried out an intensive field study in Singapore from November 2015 to February 2016. PM2.5 samples were collected concurrently at a typical roadside microenvironment and at an urban background site. A detailed chemical speciation of PM2.5 samples was conducted to gain insights into the emission characteristics of traffic-related fine aerosols. Analyses of diagnostic ratios and molecular markers of selected chemical species were explored for source attribution of different classes of chemical constituents in traffic-related PM2.5. The human health risk due to inhalation of the particulate-bound PAHs (polycyclic aromatic hydrocarbons) and toxic trace elements was estimated for both adults and children. The overall results of the study indicate that gasoline-powered vehicles make a higher contribution to traffic-related fine aerosol components such as organic carbon (OC), particle-bound PAHs and particulate ammonium than that of diesel-powered vehicles. However, both types of vehicles contribute to traffic-related EC emissions significantly. The combustion of petroleum fuels and lubricating oil make significant contributions to the emission of n-alkanes and hopanes into the urban atmosphere, respectively. The study further reveals that some toxic trace elements are emitted from non-exhaust sources and that aromatic acids represent an important component of secondary organic aerosols. The emission of toxic trace elements from non-exhaust sources is of particular concern as they could pose a higher carcinogenic risk to both adults and children than other chemical species.

Crassulacean acid metabolism and epiphytism linked to adaptive radiations in the Orchidaceae.

PubMed

Silvera, Katia; Santiago, Louis S; Cushman, John C; Winter, Klaus

2009-04-01

Species of the large family Orchidaceae display a spectacular array of adaptations and rapid speciations that are linked to several innovative features, including specialized pollination syndromes, colonization of epiphytic habitats, and the presence of Crassulacean acid metabolism (CAM), a water-conserving photosynthetic pathway. To better understand the role of CAM and epiphytism in the evolutionary expansion of tropical orchids, we sampled leaf carbon isotopic composition of 1,103 species native to Panama and Costa Rica, performed character state reconstruction and phylogenetic trait analysis of CAM and epiphytism, and related strong CAM, present in 10% of species surveyed, to climatic variables and the evolution of epiphytism in tropical regions. Altitude was the most important predictor of photosynthetic pathway when all environmental variables were taken into account, with CAM being most prevalent at low altitudes. By creating integrated orchid trees to reconstruct ancestral character states, we found that C3 photosynthesis is the ancestral state and that CAM has evolved at least 10 independent times with several reversals. A large CAM radiation event within the Epidendroideae, the most species-rich epiphytic clade of any known plant group, is linked to a Tertiary species radiation that originated 65 million years ago. Our study shows that parallel evolution of CAM is present among subfamilies of orchids, and correlated divergence between photosynthetic pathways and epiphytism can be explained by the prevalence of CAM in low-elevation epiphytes and rapid speciation of high-elevation epiphytes in the Neotropics, contributing to the astounding diversity in the Orchidaceae.

Complexation of Cd, Ni, and Zn by DOC in polluted groundwater: A comparison of approaches using resin exchange, aquifer material sorption, and computer speciation models (WHAM and MINTEQA2)

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

Christensen, J.B.; Christensen, T.H.

1999-11-01

Complexation of cadmium (Cd), nickel (Ni), and zinc (Zn) by dissolved organic carbon (DOC) in leachate-polluted groundwater was measured using a resin equilibrium method and an aquifer material sorption technique. The first method is commonly used in complexation studies, while the second method better represents aquifer conditions. The two approaches gave similar results. Metal-DOC complexation was measured over a range of DOC concentrations using the resin equilibrium method, and the results were compared to simulations made by two speciation models containing default databases on metal-DOC complexes (WHAM and MINTEQA2). The WHAM model gave reasonable estimates of Cd and Ni complexationmore » by DOC for both leachate-polluted groundwater samples. The estimated effect of complexation differed less than 50% from the experimental values corresponding to a deviation on the activity of the free metal ion of a factor of 2.5. The effect of DOC complexation for Zn was largely overestimated by the WHAM model, and it was found that using a binding constant of 1.7 instead of the default value of 1.3 would improve the fit between the simulations and experimental data. The MINTEQA2 model gave reasonable predictions of the complexation of Cd and Zn by DOC, whereas deviations in the estimated activity of the free Ni{sup 2+} ion as compared to experimental results are up to a factor of 5.« less

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

ERIC Educational Resources Information Center

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

2005-01-01

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

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.

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

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

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

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

Geochemistry of some rare earth elements in groundwater, Vierlingsbeek, The Netherlands.

PubMed

Janssen, René P T; Verweij, Wilko

2003-03-01

Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach. For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation. The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands.

NetpathXL - An Excel Interface to the Program NETPATH

USGS Publications Warehouse

Parkhurst, David L.; Charlton, Scott R.

2008-01-01

NetpathXL is a revised version of NETPATH that runs under Windows? operating systems. NETPATH is a computer program that uses inverse geochemical modeling techniques to calculate net geochemical reactions that can account for changes in water composition between initial and final evolutionary waters in hydrologic systems. The inverse models also can account for the isotopic composition of waters and can be used to estimate radiocarbon ages of dissolved carbon in ground water. NETPATH relies on an auxiliary, database program, DB, to enter the chemical analyses and to perform speciation calculations that define total concentrations of elements, charge balance, and redox state of aqueous solutions that are then used in inverse modeling. Instead of DB, NetpathXL relies on Microsoft Excel? to enter the chemical analyses. The speciation calculation formerly included in DB is implemented within the program NetpathXL. A program DBXL can be used to translate files from the old DB format (.lon files) to NetpathXL spreadsheets, or to create new NetpathXL spreadsheets. Once users have a NetpathXL spreadsheet with the proper format, new spreadsheets can be generated by copying or saving NetpathXL spreadsheets. In addition, DBXL can convert NetpathXL spreadsheets to PHREEQC input files. New capabilities in PHREEQC (version 2.15) allow solution compositions to be written to a .lon file, and inverse models developed in PHREEQC to be written as NetpathXL .pat and model files. NetpathXL can open NetpathXL spreadsheets, NETPATH-format path files (.pat files), and NetpathXL-format path files (.pat files). Once the speciation calculations have been performed on a spreadsheet file or a .pat file has been opened, the NetpathXL calculation engine is identical to the original NETPATH. Development of models and viewing results in NetpathXL rely on keyboard entry as in NETPATH.

Characterising boiler ash from a circulating fluidised bed municipal solid waste incinerator and distribution of PCDD/F and PCB.

PubMed

Zhang, Mengmei; Buekens, Alfons; Li, Xiaodong

2018-05-31

In this study, ash samples were collected from five locations situated in the boiler of a circulating fluidised bed municipal solid waste incinerator (high- and low-temperature superheater, evaporator tubes and upper and lower economiser). These samples represent a huge range of flue gas temperatures and were characterised for their particle size distribution, surface characteristics, elemental composition, chemical forms of carbon and chlorine and distribution of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB). Enrichment of chlorine, one of the main elements of organochlorinated pollutants, and copper, zinc and lead, major catalytic metals for dioxin-like compounds, was observed in lower-temperature ash deposits. The speciation of carbon and chlorine on ash surfaces was established, showing a positive correlation between organic chlorine and oxygen-containing carbon functional groups. The load of PCDD/F and PCB (especially dioxin-like PCB) tends to rise rapidly with falling temperature of flue gas, reaching their highest value in economiser ashes. The formation of PCDD/F congeners through the chlorophenol precursor route apparently was enhanced downstream the boiler. Principal component analysis (PCA) was applied to study the links between the ash characteristics and distribution of chloro-aromatics. The primary purpose of this study is improving the understanding of any links between the characteristics of ash from waste heat systems and its potential to form PCDD/F and PCB. The question is raised whether further characterisation of fly ash may assist to establish a diagnosis of poor plant operation, inclusive the generation, destruction and eventual emission of persistent organic pollutants (POPs).

Latitude, elevational climatic zonation and speciation in New World vertebrates

PubMed Central

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

2012-01-01

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

Biogeochemical modeling of CO 2 and CH 4 production in anoxic Arctic soil microcosms

DOE PAGES

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; ...

2016-09-12

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Highly efficient electrocatalytic vapor generation of methylmercury based on the gold particles deposited glassy carbon electrode: A typical application for sensitive mercury speciation analysis in fish samples.

PubMed

Shi, Meng-Ting; Yang, Xin-An; Qin, Li-Ming; Zhang, Wang-Bing

2018-09-26

A gold particle deposited glassy carbon electrode (Au/GCE) was first used in electrochemical vapor generation (ECVG) technology and demonstrated to have excellent catalytic property for the electrochemical conversion process of aqueous mercury, especially for methylmercury (CH 3 Hg + ), to gaseous mercury. Systematical research has shown that the highly consistent or distinct difference between the atomic fluorescence spectroscopy signals of CH 3 Hg + and Hg 2+ can be achieved by controlling the electrolytic parameters of ECVG. Hereby, a new green and accurate method for mercury speciation analysis based on the distinguishing electrochemical reaction behavior of Hg 2+ and CH 3 Hg +  on the modified electrode was firstly established. Furthermore, electrochemical impedance spectra and the square wave voltammetry displayed that the ECVG reaction of CH 3 Hg +  may belong to the electrocatalytic mechanism. Under the selected conditions, the limits of detection of Hg 2+ and CH 3 Hg +  are 5.3 ng L -1 and 4.4 ng L -1 for liquid samples and 0.53 pg mg -1 and 0.44 pg mg -1 for solid samples, respectively. The precision of the 5 measurements is less than 6% within the concentration of Hg 2+ and CH 3 Hg +  ranging from 0.2 to 15.0 μg L -1 . The accuracy and practicability of the proposed method was verified by analyzing the mercury content in the certified reference material and several fish as well as water samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Temporal biomass dynamics of an Arctic plankton bloom in response to increasing levels of atmospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Schulz, K. G.; Bellerby, R. G. J.; Brussaard, C. P. D.; Büdenbender, J.; Czerny, J.; Engel, A.; Fischer, M.; Koch-Klavsen, S.; Krug, S. A.; Lischka, S.; Ludwig, A.; Meyerhöfer, M.; Nondal, G.; Silyakova, A.; Stuhr, A.; Riebesell, U.

2013-01-01

Ocean acidification and carbonation, driven by anthropogenic emissions of carbon dioxide (CO2), have been shown to affect a variety of marine organisms and are likely to change ecosystem functioning. High latitudes, especially the Arctic, will be the first to encounter profound changes in carbonate chemistry speciation at a large scale, namely the under-saturation of surface waters with respect to aragonite, a calcium carbonate polymorph produced by several organisms in this region. During a CO2 perturbation study in Kongsfjorden on the west coast of Spitsbergen (Norway), in the framework of the EU-funded project EPOCA, the temporal dynamics of a plankton bloom was followed in nine mesocosms, manipulated for CO2 levels ranging initially from about 185 to 1420 μatm. Dissolved inorganic nutrients were added halfway through the experiment. Autotrophic biomass, as identified by chlorophyll a standing stocks (Chl a), peaked three times in all mesocosms. However, while absolute Chl a concentrations were similar in all mesocosms during the first phase of the experiment, higher autotrophic biomass was measured as high in comparison to low CO2 during the second phase, right after dissolved inorganic nutrient addition. This trend then reversed in the third phase. There were several statistically significant CO2 effects on a variety of parameters measured in certain phases, such as nutrient utilization, standing stocks of particulate organic matter, and phytoplankton species composition. Interestingly, CO2 effects developed slowly but steadily, becoming more and more statistically significant with time. The observed CO2-related shifts in nutrient flow into different phytoplankton groups (mainly dinoflagellates, prasinophytes and haptophytes) could have consequences for future organic matter flow to higher trophic levels and export production, with consequences for ecosystem productivity and atmospheric CO2.

Temporal biomass dynamics of an Arctic plankton bloom in response to increasing levels of atmospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Schulz, K. G.; Bellerby, R. G. J.; Brussaard, C. P. D.; Büdenbender, J.; Czerny, J.; Engel, A.; Fischer, M.; Koch-Klavsen, S.; Krug, S. A.; Lischka, S.; Ludwig, A.; Meyerhöfer, M.; Nondal, G.; Silyakova, A.; Stuhr, A.; Riebesell, U.

2012-09-01

Ocean acidification and carbonation, driven by anthropogenic emissions of carbon dioxide (CO2), have been shown to affect a variety of marine organisms and are likely to change ecosystem functioning. High latitudes, especially the Arctic, will be the first to encounter profound changes in carbonate chemistry speciation at a large scale, namely the under-saturation of surface waters with respect to aragonite, a calcium carbonate polymorph produced by several organisms in this region. During a CO2 perturbation study in 2010, in the framework of the EU-funded project EPOCA, the temporal dynamics of a plankton bloom was followed in nine mesocosms, manipulated for CO2 levels ranging initially from about 185 to 1420 μatm. Dissolved inorganic nutrients were added halfway through the experiment. Autotrophic biomass, as identified by chlorophyll a standing stocks (Chl a), peaked three times in all mesocosms. However, while absolute Chl a concentrations were similar in all mesocosms during the first phase of the experiment, higher autotrophic biomass was measured at high in comparison to low CO2 during the second phase, right after dissolved inorganic nutrient addition. This trend then reversed in the third phase. There were several statistically significant CO2 effects on a variety of parameters measured in certain phases, such as nutrient utilization, standing stocks of particulate organic matter, and phytoplankton species composition. Interestingly, CO2 effects developed slowly but steadily, becoming more and more statistically significant with time. The observed CO2 related shifts in nutrient flow into different phytoplankton groups (mainly diatoms, dinoflagellates, prasinophytes and haptophytes) could have consequences for future organic matter flow to higher trophic levels and export production, with consequences for ecosystem productivity and atmospheric CO2.

Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

NASA Astrophysics Data System (ADS)

Ulevicius, V.; Byčenkienė, S.; Bozzetti, C.; Vlachou, A.; Plauškaitė, K.; Mordas, G.; Dudoitis, V.; Abbaszade, G.; Remeikis, V.; Garbaras, A.; Masalaite, A.; Blees, J.; Fröhlich, R.; Dällenbach, K. R.; Canonaco, F.; Slowik, J. G.; Dommen, J.; Zimmermann, R.; Schnelle-Kreis, J.; Salazar, G. A.; Agrios, K.; Szidat, S.; El Haddad, I.; Prévôt, A. S. H.

2015-09-01

In early spring the Baltic region is frequently affected by high pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m-3 and black carbon (BC) up to 17 μg m-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf) was the dominant fraction of PM1, with the primary (POCnf) and secondary (SOCnf) fractions contributing 26-44 % and 13-23 % to the TC, respectively. 5-8 % of the TC had a primary fossil origin (POCf), whereas the contribution of fossil secondary organic carbon (SOCf) was 4-13 %. Non-fossil EC (ECnf) and fossil EC (ECf) ranged from 13-24 % and 7-12 %, respectively. Isotope ratio of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

2015-12-01

Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in abiotic CaCO3 reflect changes in aqueous U(VI) speciation, which are in turn a function of carbonate ion chemistry and pH. Hence, the door is opened to the development of a possible 238U/235U proxy for the carbonate ion system. [1] DeCarlo et al., (2015), GCA, 162,151-165. [2] Reeder et a., (2001), GCA, 65, 3491-3503. [3] Weyer et al., (2008) GCA 72, 345-359.

Sorptive Uptake Studies of an Aryl-Arsenical with Iron Oxide Composites on an Activated Carbon Support

PubMed Central

Kwon, Jae H.; Wilson, Lee D.; Sammynaiken, Ramaswami

2014-01-01

Sorption uptake kinetics and equilibrium studies for 4-hydroxy-3-nitrobenzene arsonic acid (roxarsone) was evaluated with synthetic magnetite (Mag-P), commercial magnetite (Mag-C), magnetite 10%, 19%, and 32% composite material (CM-10, -19, -32) that contains granular activated carbon (GAC), and synthetic goethite at pH 7.00 in water at 21 °C for 24 h. GAC showed the highest sorptive removal of roxarsone and the relative uptake for each sorbent material with roxarsone are listed in descending order as follows: GAC (471 mg/g) > goethite (418 mg/g) > CM-10 (377 mg/g) CM-19 (254 mg/g) > CM-32 (227 mg/g) > Mag-P (132 mg/g) > Mag-C (29.5 mg/g). The As (V) moiety of roxarsone is adsorbed onto the surface of the iron oxide/oxyhydrate and is inferred as inner-sphere surface complexes; monodentate-mononuclear, bidentate-mononuclear, and bidentate-binuclear depending on the protolytic speciation of roxarsone. The phenyl ring of roxarsone provides the primary driving force for the sorptive interaction with the graphene surface of GAC and its composites. Thus, magnetite composites are proposed as multi-purpose adsorbents for the co-removal of inorganic and organic arsenicals due to the presence of graphenic and iron oxide active adsorption sites. PMID:28788545

Learning to speciate: The biased learning of mate preferences promotes adaptive radiation

PubMed Central

Gilman, R. Tucker; Kozak, Genevieve M.

2015-01-01

Bursts of rapid repeated speciation called adaptive radiations have generated much of Earth's biodiversity and fascinated biologists since Darwin, but we still do not know why some lineages radiate and others do not. Understanding what causes assortative mating to evolve rapidly and repeatedly in the same lineage is key to understanding adaptive radiation. Many species that have undergone adaptive radiations exhibit mate preference learning, where individuals acquire mate preferences by observing the phenotypes of other members of their populations. Mate preference learning can be biased if individuals also learn phenotypes to avoid in mates, and shift their preferences away from these avoided phenotypes. We used individual‐based computational simulations to study whether biased and unbiased mate preference learning promotes ecological speciation and adaptive radiation. We found that ecological speciation can be rapid and repeated when mate preferences are biased, but is inhibited when mate preferences are learned without bias. Our results suggest that biased mate preference learning may play an important role in generating animal biodiversity through adaptive radiation. PMID:26459795

A Multivariate Dynamic Spatial Factor Model for Speciated Pollutants and Adverse Birth Outcomes

DOE PAGES

Kaufeld, Kimberly Ann; Fuentes, Montse; Reich, Brian J.; ...

2017-09-11

Evidence suggests that exposure to elevated concentrations of air pollution during pregnancy is associated with increased risks of birth defects and other adverse birth outcomes. While current regulations put limits on total PM2.5 concentrations, there are many speciated pollutants within this size class that likely have distinct effects on perinatal health. However, due to correlations between these speciated pollutants, it can be difficult to decipher their effects in a model for birth outcomes. To combat this difficulty, we develop a multivariate spatio-temporal Bayesian model for speciated particulate matter using dynamic spatial factors. These spatial factors can then be interpolated tomore » the pregnant women’s homes to be used to model birth defects. The birth defect model allows the impact of pollutants to vary across different weeks of the pregnancy in order to identify susceptible periods. Here, the proposed methodology is illustrated using pollutant monitoring data from the Environmental Protection Agency and birth records from the National Birth Defect Prevention Study.« less

A Multivariate Dynamic Spatial Factor Model for Speciated Pollutants and Adverse Birth Outcomes

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

Kaufeld, Kimberly Ann; Fuentes, Montse; Reich, Brian J.

Evidence suggests that exposure to elevated concentrations of air pollution during pregnancy is associated with increased risks of birth defects and other adverse birth outcomes. While current regulations put limits on total PM2.5 concentrations, there are many speciated pollutants within this size class that likely have distinct effects on perinatal health. However, due to correlations between these speciated pollutants, it can be difficult to decipher their effects in a model for birth outcomes. To combat this difficulty, we develop a multivariate spatio-temporal Bayesian model for speciated particulate matter using dynamic spatial factors. These spatial factors can then be interpolated tomore » the pregnant women’s homes to be used to model birth defects. The birth defect model allows the impact of pollutants to vary across different weeks of the pregnancy in order to identify susceptible periods. Here, the proposed methodology is illustrated using pollutant monitoring data from the Environmental Protection Agency and birth records from the National Birth Defect Prevention Study.« less

The relationship between mantle pH and the deep nitrogen cycle

NASA Astrophysics Data System (ADS)

Mikhail, Sami; Barry, Peter H.; Sverjensky, Dimitri A.

2017-07-01

Nitrogen is distributed throughout all terrestrial geological reservoirs (i.e., the crust, mantle, and core), which are in a constant state of disequilibrium due to metabolic factors at Earth's surface, chemical weathering, diffusion, and deep N fluxes imposed by plate tectonics. However, the behavior of nitrogen during subduction is the subject of ongoing debate. There is a general consensus that during the crystallization of minerals from melts, monatomic nitrogen behaves like argon (highly incompatible) and ammonium behaves like potassium and rubidium (which are relatively less incompatible). Therefore, the behavior of nitrogen is fundamentally underpinned by its chemical speciation. In aqueous fluids, the controlling factor which determines if nitrogen is molecular (N2) or ammonic (inclusive of both NH4+ and NH30) is oxygen fugacity, whereas pH designates if ammonic nitrogen is NH4+ or NH30. Therefore, to address the speciation of nitrogen at high pressures and temperatures, one must also consider pH at the respective pressure-temperature conditions. To accomplish this goal we have used the Deep Earth Water Model (DEW) to calculate the activities of aqueous nitrogen from 1-5 GPa and 600-1000 °C in equilibrium with a model eclogite-facies mineral assemblage of jadeite + kyanite + quartz/coesite (metasediment), jadeite + pyrope + talc + quartz/coesite (metamorphosed mafic rocks), and carbonaceous eclogite (metamorphosed mafic rocks + elemental carbon). We then compare these data with previously published data for the speciation of aqueous nitrogen across these respective P-T conditions in equilibrium with a model peridotite mineral assemblage (Mikhail and Sverjensky, 2014). In addition, we have carried out full aqueous speciation and solubility calculations for the more complex fluids in equilibrium with jadeite + pyrope + kyanite + diamond, and for fluids in equilibrium with forsterite + enstatite + pyrope + diamond. Our results show that the pH of the fluid is controlled by mineralogy for a given pressure and temperature, and that pH can vary by several units in the pressure-temperature range of 1-5 GPa and 600-1000 °C. Our data show that increasing temperature stabilizes molecular nitrogen and increasing pressure stabilizes ammonic nitrogen. Our model also predicts a stark difference for the dominance of ammonic vs. molecular and ammonium vs. ammonia for aqueous nitrogen in equilibrium with eclogite-facies and peridotite mineralogies, and as a function of the total dissolved nitrogen in the aqueous fluid where lower N concentrations favor aqueous ammonic nitrogen stabilization and higher N concentrations favor aqueous N2. Overall, we present thermodynamic evidence for nitrogen to be reconsidered as an extremely dynamic (chameleon) element whose speciation and therefore behavior is determined by a combination of temperature, pressure, oxygen fugacity, chemical activity, and pH. We show that altering the mineralogy in equilibrium with the fluid can lead to a pH shift of up to 4 units at 5 GPa and 1000 °C. Therefore, we conclude that pH imparts a strong control on nitrogen speciation, and thus N flux, and should be considered a significant factor in high temperature geochemical modeling in the future. Finally, our modelling demonstrates that pH plays an important role in controlling speciation, and thus mass transport, of Eh-pH sensitive elements at temperatures up to at least 1000 °C.

A new comprehensive approach to characterizing carbonaceous aerosol with an application to wintertime Fresno, California PM2.5

USGS Publications Warehouse

Herckes, P.; Leenheer, J.A.; Collett, J.L.

2007-01-01

Fine particulate matter (PM2.5) samples were collected during a three week winter period in Fresno (CA). A composite sample was characterized by isolating several distinct fractions and characterizing them by infrared and nuclear magnetic resonance (NMR) spectroscopy. More than 80% of the organic matter in the aerosol samples was recovered and characterized. Only 35% of the organic matter was water soluble with another third soluble in dichloromethane and the remainder insoluble. Within the isolated water soluble material, hydrophobic acid and hydrophilic acids plus neutrals fractions contained the largest amounts of carbon. The hydrophobic acids fraction appears to contain significant amounts of lignin type structures, spectra of the hydrophilic acids plus neutrals fraction are indicative of carbohydrates and secondary organic material. The dichloromethane soluble fraction contains a variety of organic compound families typical of many previous studies of organic aerosol speciation, including alkanes, alkanols, alkanals and alkanoic acids. Finally the water and solvent insoluble fraction exhibits a strong aromaticity as one would expect from black or elemental carbon like material; however, these spectra also show a substantial amount of aliphaticity consistent with linear side chains on the aromatic structures.

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

PubMed

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

2012-01-01

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

Radiating on Oceanic Islands: Patterns and Processes of Speciation in the Land Snail Genus Theba (Risso 1826)

PubMed Central

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

2012-01-01

Island radiations have played a major role in shaping our current understanding of allopatric, sympatric and parapatric speciation. However, the fact that species divergence correlates with island size emphasizes the importance of geographic isolation (allopatry) in speciation. Based on molecular and morphological data, we investigated the diversification of the land snail genus Theba on the two Canary Islands of Lanzarote and Fuerteventura. Due to the geological history of both islands, this study system provides ideal conditions to investigate the interplay of biogeography, dispersal ability and differentiation in generating species diversity. Our analyses demonstrated extensive cryptic diversification of Theba on these islands, probably driven mainly by non-adaptive allopatric differentiation and secondary gene flow. In a few cases, we observed a complete absence of gene flow among sympatrically distributed forms suggesting an advanced stage of speciation. On the Jandía peninsula genome scans suggested genotype-environment associations and potentially adaptive diversification of two closely related Theba species to different ecological environments. We found support for the idea that genetic differentiation was enhanced by divergent selection in different environments. The diversification of Theba on both islands is therefore best explained by a mixture of non-adaptive and adaptive speciation, promoted by ecological and geomorphological factors. PMID:22493687

Migration and speciation of heavy metal in salinized mine tailings affected by iron mining.

PubMed

Zhang, Xu; Yang, Huanhuan; Cui, Zhaojie

2017-10-01

The negative effects of heavy metals have aroused much attention due to their high toxicity to human beings. Migration and transformation trend of heavy metals have a close relationship with soil safety. Researching on migration and transformation of heavy metals in tailings can provide a reliable basis for pollution management and ecosystem restoration. Heavy metal speciation plays an important role in risk assessment. We chose Anshan tailings for our study, including field investigations and laboratory research. Four typical heavy metal elements of mine tailings {Fe (373.89 g/kg), Mn (2,303.80 mg/kg), Pb (40.99 mg/kg) and Cr (199.92 mg/kg)} were studied via Tessier test in vertical and horizontal direction. The main speciation of heavy metals in Anshan tailings was the residual. However, heavy metals have a strong ability for migration and transformation in vertical and horizontal directions. Its tendency to change from stable to unstable speciation results in increasing bioavailability and potential bioavailability. Fe, Mn, Pb and Cr showed different ability in the migration and transformation process (Mn > Pb > Fe > Cr) depending on the characteristics of heavy metals and physicochemical properties of the environment.

The biological pump and lower trophic level controls on carbon cycling in Lake Superior: Insights from a multi-pronged study

NASA Astrophysics Data System (ADS)

Schreiner, K. M.; Bramburger, A.; Ozersky, T.; Sheik, C.; Steinman, B. A.

2016-02-01

Lake Superior is the largest freshwater lake in the world, supporting economically important fisheries and providing drinking water to hundreds of thousands of people. In recent decades, summer surface water temperature and the intensity and duration of water column stratification in the lake has increased steadily. These physical changes have resulted in significant perturbations to lower trophic level ecosystem characteristics. Recent observations of Great Lakes plankton assemblages have revealed multi-decadal patterns of community reorganization, with increased relative abundance of taxa characteristic of warmer waters. These changes, coupled with changing nutrient concentrations and colonization by non-native taxa, threaten to shift trophic structure and carbon dynamics at the bottom of the food web. To this end, this study seeks to quantify the impacts of this ecosystem shift on carbon fixation, the biological pump, and organic carbon cycling in Lake Superior. Utilizing a combined sampling approach, in the summer of 2015 we collected water, sediment, and biological samples across a nearshore-to-offshore gradient in the western arm of Lake Superior. Analyses included the community composition of bacteria, archaea, phytoplankton, and zooplankton; water column carbon and nutrient speciation; algal pigments and pigment degradation products; and net primary productivity. The collection of surface sediments allowed for additional assessment of benthic-pelagic coupling. The novel combination of this wide-ranging set of analyses to a locally and globally important water body like Lake Superior allowed us to fully assess the interactions between lower trophic level biology and carbon and nutrient cycling throughout the water column. Preliminary data indicates that microbial community composition was variable across the western arm of Lake Superior and showed signs of stratification at individual stations (>100 m deep). Sample collection occurred soon after lake stratification in July 2015, and the presence of a deep chlorophyll maximum was noted. The results shed light on the functioning of the biological pump and nutrient and carbon dynamics in a changing ecosystem and provides insight on how further change in Lake Superior and other aquatic systems will affect ecosystem function and services.

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.

The role of Quaternary environmental change in plant macroevolution: the exception or the rule?

PubMed Central

Willis, Katherine J; Niklas, Karl J

2004-01-01

The Quaternary has been described as an important time for genetic diversification and speciation. This is based on the premise that Quaternary climatic conditions fostered the isolation of populations and, in some instances, allopatric speciation. However, the 'Quaternary Ice-Age speciation model' rests on two key assumptions: (i) that biotic responses to climate change during the Quaternary were significantly different from those of other periods in Earth's history; and (ii) that the mechanisms of isolation during the Quaternary were sufficient in time and space for genetic diversification to foster speciation. These assumptions are addressed by examining the plant fossil record for the Quaternary (in detail) and for the past 410 Myr, which encompasses previous intervals of icehouse Earth. Our examination of the Quaternary record indicates that floristic responses to climate changes during the past 1.8 Myr were complex and that a distinction has to be made between those plants that were able to withstand the extremes of glacial conditions and those that could not. Generation times are also important as are different growth forms (e.g. herbaceous annuals and arborescent perennials), resulting in different responses in terms of genetic divergence rates during isolation. Because of these variations in the duration of isolation of populations and genomic diversification rates, no canonical statement about the predominant floristic response to climatic changes during the Quaternary (i.e. elevated rates of speciation or extinction, or stasis) is currently possible. This is especially true because of a sampling bias in terms of the fossil record of tree species over that of species with non-arborescent growth forms. Nevertheless, based on the available information, it appears that the dominant response of arborescent species during the Quaternary was extinction rather than speciation or stasis. By contrast, our examination of the fossil record of vascular plants for the past 410 Myr indicates that speciation rates often increased during long intervals of icehouse Earth (spanning up to 50 Myr). Therefore, longer periods of icehouse Earth than those occurring during the Quaternary may have isolated plant populations for sufficiently long periods of time to foster genomic diversification and allopatric speciation. Our results highlight the need for more detailed study of the fossil record in terms of finer temporal and spatial resolution than is currently available to examine the significance of intervals of icehouse Earth. It is equally clear that additional and detailed molecular studies of extant populations of Quaternary species are required in order to determine the extent to which these 'relic' species have genomically diversified across their current populations. PMID:15101573

Geochemistry of rare earth elements within waste rocks from the Montviel carbonatite deposit, Québec, Canada.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Pelletier, Mia

2018-04-01

Several rare earth element (REE) mine projects around the world are currently at the feasibility stage. Unfortunately, few studies have evaluated the contamination potential of REE and their effects on the environment. In this project, the waste rocks from the carbonatites within the Montviel proterozoic alkaline intrusion (near Lebel-sur-Quévillon, Quebec, Canada) are assessed in this research. The mineralization is mainly constituted by light REE (LREE) fluorocarbonates (qaqarssukite-Ce, kukharenkoite-Ce), LREE carbonates (burbankite, Sr-Ba-Ca-REE, barytocalcite, strontianite, Ba-REE-carbonates), and phosphates (apatite, monazite). The gangue minerals are biotites, chlorite, albite, ankerite, siderite, and calcite. The SEM-EDS analyses show that (i) the majority of REE are associated with the fine fraction (< 106 μm), (ii) REE are mainly associated with carbonates, (iii) all analyzed minerals preferably contain LREE (La, Ce, Pr, Nd, Sm, Eu), (iv) the sum of LREE in each analyzed mineral varies between ~ 3 and 10 wt%, (v) the heavy REE (HREE) identified are Gd and Yb at < 0.4 wt%, and (vi) three groups of carbonate minerals were observed containing variable concentrations of Ca, Na, and F. Furthermore, the mineralogical composition of REE-bearing minerals, REE mobility, and REE speciation was investigated. The leachability and geochemical behavior of these REE-bearing mine wastes were tested using normalized kinetic testing (humidity cells). Leachate results displayed higher LREE concentrations, with decreasing shale-normalized patterns. Thermodynamical equilibrium calculations suggest that the precipitation of secondary REE minerals may control the REE mobility.

Distribution and potential sources and sinks of copper chelators in the Sargasso Sea

NASA Astrophysics Data System (ADS)

Moffett, J. W.; Zika, R. G.; Brand, L. E.

1990-01-01

Copper speciation has been studied at an oligotrophic station in the southwestern Sargasso Sea to determine the distribution of Cu binding ligands and evaluate their potential sources and sinks. Speciation was studied using a ligand exchange/liquid-liquid partition procedure used in a previous study in Florida coastal waters [ MOFFET and ZIKA (1987a) Marine Chemistry, 21, 301-313]. Copper speciation was dominated by organic complexation at all depths studied (16-950 m). Complexation was greatest in the region of the chlorophyll maximum. In this region, speciation was dominated by two ligands or ligand classes; L 1, with K cond. = 10 13.2, concentration = 2 nM, and a weaker but more abundant ligand class, L 2 with Kincond. = 10 9.7, concentration = 80 nM. From 140 to 16 m, [Cu(II)] free/[Cu(II)] total increases by a factor of 20, due to a decrease in [L 1] to a value below the ambient Cu concentration. Exposure of water from 140 m to sunlight indicated that photochemical decomposition of L 1 may account for the decrease. Below the chlorophyll maximum there is a gradual increase in [Cu(II)] free/[Cu(II)] total suggesting that the ligands are of recent biological origin rather than derived from refractory materials. Cultures of a ubiquitous marine cyanobacterium, Synechococcus sp. produced a ligand with K cond. comparable to L 1, indicating that a biological source is plausible.

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.

A High-Resolution Multitechniques Approach to Characterize Bio-Organo-Mineral Associations Within Rock Samples: Tracking Biological vs Abiotic Processes? Towards a Better Understanding of the Deep Carbon Cycle.

NASA Astrophysics Data System (ADS)

Pisapia, C.

2015-12-01

Among all elements, carbon plays one of the major roles for the sustainability of life on Earth. Past considerations of the carbon cycle have mainly focused on surface processes occurring at the atmosphere, oceans and shallow crustal environments. By contrast, little is known about the Deep Carbon cycle whereas both geochemical and biological processes may induce organic carbon production and/or consumption at depth. Indeed, the nowadays-recognized capability of geochemical processes such as serpentinization to generate abiotic organic compounds as well as the existence of a potentially important intraterrestrial life raises questions about the limit of biotic/abiotic carbon on Earth's deep interior and how it impacts global biogeochemical cycles. It is then mandatory to increase our knowledge on the nature and extent of carbon reservoirs along with their sources, sinks and fluxes in the subsurface. This implies to be able to finely characterize organomineral associations within crustal rocks although it might be hampered by the scarceness and heterogeneous micrometric spatial distribution of organic molecules in natural rocks. We then developed an in situ analytical strategy based on the combination of high-resolution techniques to track organic molecules at the pore level in natural rocks and to determine their biological or abiotic origin. We associated classical high-resolution techniques and synchrotron-based imaging techniques in order to characterize their nature and localization (SEM/TEM, coupled CLSM/Raman spectroscopy, Tof-SIMS) along with their 3D-distribution relatively to mineral phases (S-FTIR, S-DeepUV, XANES, Biphoton microscopy). The effectiveness of this approach to shed light on the speciation and nature of carbon in subsurface environments will be illustrated through the study of (i) subsurface ecosystems and abiotic organic carbon within ultramafic rocks of the oceanic lithosphere as putative analogs for the nature and functioning of primitive ecosystems on Earth and of (ii) ecosystems inhabiting Archean craton and potentially playing a role in punk-rock karstification processes and rocks weathering.

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.

Temporal Variability of Stemflow Dissolved Organic Carbon (DOC) Concentrations and Quality from Morphologically Contrasting Deciduous Canopies

NASA Astrophysics Data System (ADS)

van Stan, J. T.; Levia, D. F.; Inamdar, S. P.; Mitchell, M. J.; Mage, S. M.

2010-12-01

Dissolved organic carbon (DOC) inputs from canopy-derived hydrologic fluxes play a significant role in the terrestrial carbon budgets of forested ecosystems. However, no studies known to the authors have examined the variability of both DOC concentrations and quality for stemflow across time scales, nor has any study to date evaluated the effects of canopy structure on stemflow DOC characteristics. This investigation seeks to rectify this knowledge gap by examining the variability of stemflow DOC concentrations and quality across contrasting canopy morphologies and time scales (seasonal, storm and intrastorm). Bulk and intrastorm stemflow samples from a less dense, rough-barked, more plagiophile (Liriodendron tulipifera L. (tulip poplar)) and a denser, thin-barked, more erectophile (Fagus grandifolia Ehrh. (American beech)) canopy were collected and analyzed for DOC quality using metrics derived from UV-vis spectroscopy (E2:E3 ratio, SUVA254, select spectral slope (S), and spectral slope ratios (SR)). Our results suggest that stemflow DOC concentrations and quality change as crown architectural traits enhance or diminish hydrologic retention time within the canopy. The architecture of L. tulipifera canopies likely retards the flow of intercepted water, increasing chemical exchange with bark and foliar surfaces. UV-vis metrics indicated that this increased chemical exchange, particularly with bark surfaces, generally enhanced aromatic hydrocarbon content and increased molecular weight. Because leaf presence influenced DOC quality, stemflow DOC characteristics also varied seasonally in response to canopy condition. At the inter- and intrastorm scale, stemflow DOC concentration and quality varied with meteorological and antecedent canopy conditions. Since recent studies have linked stemflow production to preferential subsurface transport of dissolved chemistries, trends in DOC speciation and fluxes described in this study may impact soil environments within wooded ecosystems.

Speciation and Lability of Ag-, AgCl- and Ag2S-Nanoparticles in Soil Determined by X-ray Absorption Spectroscopy and Diffusive Gradients in Thin Films

EPA Science Inventory

Long-term speciation and lability of silver (Ag-), silver chloride (AgCl-) and silver sulfide nanoparticles (Ag₂S-NPs) in soil were studied by X-ray absorption spectroscopy (XAS), and newly developed "nano" Diffusive Gradients in Thin Films (DGT) devices. These nano-D...

Spatial Associations and Chemical Composition of Organic Carbon Sequestered in Fe, Ca, and Organic Carbon Ternary Systems.

PubMed

Sowers, Tyler D; Adhikari, Dinesh; Wang, Jian; Yang, Yu; Sparks, Donald L

2018-05-25

Organo-mineral associations of organic carbon (OC) with iron (Fe) oxides play a major role in environmental OC sequestration, a process crucial to mitigating climate change. Calcium has been found to have high coassociation with OC in soils containing high Fe content, increase OC sorption extent to poorly crystalline Fe oxides, and has long been suspected to form bridging complexes with Fe and OC. Due to the growing realization that Ca may be an important component of C cycling, we launched a scanning transmission X-ray microscopy (STXM) investigation, paired with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, in order to spatially resolve Fe, Ca, and OC relationships and probe the effect of Ca on sorbed OC speciation. We performed STXM-NEXAFS analysis on 2-line ferrihydrite reacted with leaf litter-extractable dissolved OC and citric acid in the absence and presence of Ca. Organic carbon was found to highly associate with Ca ( R 2 = 0.91). Carboxylic acid moieties were dominantly sequestered; however, Ca facilitated the additional sequestration of aromatic and phenolic moieties. Also, C NEXAFS revealed polyvalent metal ion complexation. Our results provide evidence for the presence of Fe-Ca-OC ternary complexation, which has the potential to significantly impact how organo-mineral associations are modeled.

Colloidal stability of carbonate-coated silver nanoparticles in synthetic and natural freshwater.

PubMed

Piccapietra, Flavio; Sigg, Laura; Behra, Renata

2012-01-17

To gain important information on fate, mobility, and bioavailability of silver nanoparticles (AgNP) in aquatic systems, the influence of pH, ionic strength, and humic substances on the stability of carbonate-coated AgNP (average diameter 29 nm) was systematically investigated in 10 mM carbonate and 10 mM MOPS buffer, and in filtered natural freshwater. Changes in the physicochemical properties of AgNP were measured using nanoparticle tracking analysis, dynamic light scattering, and ultraviolet-visible spectroscopy. According to the pH-dependent carbonate speciation, below pH 4 the negatively charged surface of AgNP became positive and increased agglomeration was observed. Electrolyte concentrations above 2 mM Ca(2+) and 100 mM Na(+) enhanced AgNP agglomeration in the synthetic media. In the considered concentration range of humic substances, no relevant changes in the AgNP agglomeration state were measured. Agglomeration of AgNP exposed in filtered natural freshwater was observed to be primarily controlled by the electrolyte type and concentration. Moreover, agglomerated AgNP were still detected after 7 days of exposure. Consequently, slow sedimentation and high mobility of agglomerated AgNP could be expected under the considered natural conditions. A critical evaluation of the different methods used is presented as well.

Influence of UVB radiation on aquatic ecosystems

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

Lean, D.R.S.

The impact of increased UVB (290--320 nm) radiation due to stratospheric ozone depletion is placed in context with how historical levels of both UVB and UVa (320--400 nm) have influenced the structure of aquatic communities and geochemistry of lakes and their drainage basins. Suggestions for the development of generalized models for predicting the impact of UV radiation are provided and illustrate that both the response of a particular process as a function of wavelength and reliable predictions for underwater spectral irradiance are needed. Direct effects on organisms are discussed in light of problems due to adaptation, avoidance, repair and consequencesmore » of changes from sensitive to tolerant species composition. Indirect effects mediated through photochemically produced highly reactive reduced oxygen species are introduced and related to redox reactions and metal speciation using the mercury cycle as an example. Although neglected in existing global carbon budgets, UV radiation is responsible for significant release of carbon dioxide and carbon monoxide as well as many other organic metabolites from refractory dissolved organic carbon (DOC). Finally, it was argued that some lakes are losing the sun screen provided by DOC, the principal attenuator of UV radiation, due to increased acidification and lower DOC export due to the warmer drier climate conditions.« less

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

PubMed

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

2017-11-01

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

Impact of phenazine-1-carboxylic acid upon iron speciation and microbial biomass in the rhizosphere of wheat

NASA Astrophysics Data System (ADS)

LeTourneau, M.; Marshall, M.; Grant, M.; Freeze, P.; Cliff, J. B.; Lai, B.; Strawn, D. G.; Thomashow, L. S.; Weller, D. M.; Harsh, J. B.

2015-12-01

Phenazine-1-carboxylic acid (PCA) is a redox-active antibiotic produced by diverse bacterial taxa, and has been shown to facilitate interactions between biofilms and iron (hydr)oxides in culture systems (Wang et al. 2011, J Bacteriol 192: 365). Because rhizobacterial biofilms are a major sink for plant-derived carbon and source for soil organic matter (SOM), and Fe (hydr)oxides have reactive surfaces that influence the stability of microbial biomass and SOM, PCA-producing rhizobacteria could influence soil carbon fluxes. Large populations of Pseudomonas fluorescens strains producing PCA in concentrations up to 1 μg/g root have been observed in the rhizosphere of non-irrigated wheat fields covering 1.56 million hectares of central Washington state. This is one of the highest concentrations ever reported for a natural antibiotic in a terrestrial ecosystem (Mavrodi et al. 2012, Appl Environ Microb 78: 804). Microscopic comparisons of PCA-producing (PCA+) and non-PCA-producing (PCA-) rhizobacterial colony morphologies, and comparisons of Fe extractions from rhizosphere soil inoculated with PCA+ and PCA- strains suggest that PCA promotes biofilm development as well as dramatic Fe transformations throughout the rhizosphere (unpublished data). In order to illustrate PCA-mediated interactions between biofilms and Fe (hydr)oxides in the rhizosphere, identify the specific Fe phases favored by PCA, and establish the ramifications for stability and distribution of microbial biomass and SOM, we have collected electron micrographs, X-ray fluorescence images, X-ray absorption near-edge spectra, and secondary-ion mass spectrometry images of wheat root sections inoculated with 15N-labelled PCA+ or PCA- rhizobacteria. These images and spectra allow us to assess the accumulation, turnover, and distribution of microbial biomass, the associations between Fe and other nutrients such as phosphorus, and the redox status and speciation of iron in the presence and absence of PCA. This information provides a starting point to model the impact of PCA upon carbon fluxes in Columbia Basin agro-ecosystems and other environments where PCA-producing bacteria are prevalent.

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.

Evaluating factors that dictate struvite stone composition: A multi-institutional clinical experience from the EDGE Research Consortium.

PubMed

Flannigan, Ryan K; Battison, Andrew; De, Shubha; Humphreys, Mitchell R; Bader, Markus; Lellig, Ekaterina; Monga, Manoj; Chew, Ben H; Lange, Dirk

2018-04-01

Struvite stones account for 15% of urinary calculi and are typically associated with urease-producing urinary tract infections and carry significant morbidity. This study aims to characterize struvite stones based on purity of stone composition, bacterial speciation, risk factors, and clinical features. Retrospective data was collected from patients diagnosed with infection stones between 2008 and 2012. Stone analysis, perioperative urine cultures, bacterial speciation, and clinical data were collected and analyzed. The purity of struvite stones was determined. Statistical comparisons were made among homogeneous and heterogeneous struvite stones. From the four participating centres, 121 struvite stones were identified. Only 13.2% (16/121) were homogenous struvite. Other components included calcium phosphate (42.1%), calcium oxalate (33.9%), calcium carbonate (27.3%), and uric acid (5.8%). Partial or full staghorn calculi occurred in 23.7% of cases. Urease-producing bacteria were only present in 30% of cases. Proteus, E. coli, and Enterococcus were the most common bacterial isolates from perioperative urine, and percutaneous nephrolithotomy was the most common modality of treatment. Only 40% of patients had a urinalysis that was nitrite-positive, indicating that urinalysis alone is not reliable for diagnosing infection stones. The study's limitation is its retrospective nature; as such, the optimal timing of cultures with respect to stone analysis or treatment was not always possible, urine cultures were often not congruent with stone cultures in the same patient, and our findings of E. coli commonly cultured does not suggest causation. Struvite stones are most often heterogeneous in composition. Proteus remains a common bacterial isolate; however, E. coli and Enterococcus were also frequently identified. This new data provides evidence that patients with struvite stones can have urinary tract pathogens other than urease-producing bacteria, thus challenging previous conventional dogma.

Assessment of primary and secondary ambient particle trends using satellite aerosol optical depth and ground speciation data in the New England region, United States

PubMed Central

Lee, Hyung Joo; Kang, Choong-Min; Coull, Brent A.; Bell, Michelle L.; Koutrakis, Petros

2014-01-01

The effectiveness of air pollution emission control policies can be evaluated by examining ambient pollutant concentration trends that are observed at a large number of ground monitoring sites over time. In this paper, we used ground monitoring measurements in conjunction with satellite aerosol optical depth (AOD) data to investigate fine particulate matter (PM2.5; particulate matter with aerodynamic diameter ≤2.5 μm) trends and their spatial patterns over a large U.S. region, New England, during 2000–2008. We examined the trends in rural and urban areas to get a better insight about the trends of regional and local source emissions. Decreases in PM2.5 concentrations (μg/m3) were more pronounced in urban areas than in rural ones. In addition, the highest and lowest PM2.5 decreases (μg/m3) were observed for winter and summer, respectively. Together, these findings suggest that primary particle concentrations decreased more relative to secondary ones. This is also supported by the analysis of the speciation data which showed that downward trends of primary pollutants including black carbon were stronger than those of secondary pollutants including sulfate. Furthermore, this study found that ambient primary pollutants decreased at the same rate as their respective source emissions. This was not the case for secondary pollutants which decreased at a slower rate than that of their precursor emissions. This indicates that concentrations of secondary pollutants depend not only on the primary emissions but also on the availability of atmospheric oxidants which might not change during the study period. This novel approach of investigating spatially varying concentration trends, in combination with ground PM2.5 species trends, can be of substantial regulatory importance. PMID:24906074

Long-term leaching from recycled concrete aggregates applied as sub-base material in road construction.

PubMed

Engelsen, Christian J; van der Sloot, Hans A; Petkovic, Gordana

2017-06-01

In the present study, the metal leaching from recycled concrete aggregates (RCA) used in road sub-base is presented after >10years of exposure. The released levels of inorganic constituents, the effect of small variation of pH and the use of de-icing salt during winter season were studied. In addition, speciation modelling for the major elements has been provided. The pH varied from 7.5 to 8.5 for the sub-base constructed with RCA whereas the pH of around 8 was obtained for the test section not affected by the traffic and de-icing salts. Despite a small variation in pH, the leachability of Al, Ca and Mg was found to be strongly dependent on pH and fair agreement between the measured and predicted concentrations was obtained. The speciation modelling indicated that gibbsite, calcite and magnesite controlled the solubility of Al, Ca and Mg, respectively, which was in agreement with the expected carbonation products. Due to the larger pH fluctuations in the test sections exposed to the road traffic, increased concentrations were observed for the oxyanions. The same effect was not seen for the trace metal cations Cd, Cu, Ni, Pb and Zn. The distinct pH dependent leaching profile (solubility maximum in the mildly basic pH region) for vanadium could be seen after 10years of exposure. The simplified risk assessment showed that the released quantities did not exceed the chosen acceptance criteria for groundwater and fresh water. The results obtained for the test section not influenced by road dust and de-icing salts, complied with these criteria even without considering any dilution effects caused by the mixing of pore water with groundwater. Copyright © 2017 Elsevier B.V. All rights reserved.

Spatial Distribution of Ozone Precursors in the Uinta Basin

NASA Astrophysics Data System (ADS)

Mangum, C. D.; Lyman, S. N.

2012-12-01

Wintertime ozone mixing ratios in the Uinta Basin of Utah exceeding the EPA National Ambient Air Quality Standards measured during 2010 and 2011 led to a large campaign carried out in 2012 that included a study of the spatial distribution of ozone precursors in the Basin. In this study, speciated hydrocarbon mixing ratios (compounds with 6-11 carbon atoms) were measure at 10 sites around the Uinta Basin with Radiello passive samplers, and NO2, NO, and NOx (NO2 + NO) mixing ratios were measured at 16 sites with Ogawa passive sampler and active sampling instruments. Analysis of the Radiello passive samplers was carried out by CS2 desorption and analyzed on a Shimadzu QP-2010 GCMS. Analysis of the Ogawa passive samplers was done via 18.2 megohm water extraction and analyzed with a Dionex ICS-3000 ion chromatography system. February average hydrocarbon mixing ratios were highest in the area of maximum gas production (64.5 ppb as C3), lower in areas of oil production (24.3-30.0 ppb as C3), and lowest in urban areas and on the Basin rim (1.7-17.0 ppb as C3). February average for NOx was highest in the most densely populated urban area, Vernal (11.2 ppb), lower in in the area of maximum gas production (6.1 ppb), and lower still in areas of oil production and on the Basin Rim (0.6-2.7 ppb). Hydrocarbon speciation showed significant differences in spatial distribution around the Basin. Higher mixing ratios of toluene and other aromatics were much more prevalent in gas producing areas than oil producing areas. Similar mixing ratios of straight-chain alkane were observed in both areas. Higher mixing ratios of cycloalkanes were slightly more prevalent in gas producing than oil producing areas.

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

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).

Coast of California Storm and Tidal Waves Study. Shoreline Movement Data Report. Portuguese Point to Mexican Border (1852-1982),

DTIC Science & Technology

1985-12-01

34.uld not be used for site-specific shoreline ch~n i analisi For USe in engieering or planning studies, the companion analysis report haid be consulted...compiled from aerial photoraphy talum 1982. This is a speciat poros map designed for use by the U.S. Army Corps of Engineers. Natonal Oceanic and...is a speciat purpose map deisigned for use by the U.S. Army Corps of Engineers, National Ocemc and Atmospheric Administration. andother agencies

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Molecular evolution and the latitudinal biodiversity gradient.

PubMed

Dowle, E J; Morgan-Richards, M; Trewick, S A

2013-06-01

Species density is higher in the tropics (low latitude) than in temperate regions (high latitude) resulting in a latitudinal biodiversity gradient (LBG). The LBG must be generated by differential rates of speciation and/or extinction and/or immigration among regions, but the role of each of these processes is still unclear. Recent studies examining differences in rates of molecular evolution have inferred a direct link between rate of molecular evolution and rate of speciation, and postulated these as important drivers of the LBG. Here we review the molecular genetic evidence and examine the factors that might be responsible for differences in rates of molecular evolution. Critical to this is the directionality of the relationship between speciation rates and rates of molecular evolution.

The origins of tropical marine biodiversity.

PubMed

Bowen, Brian W; Rocha, Luiz A; Toonen, Robert J; Karl, Stephen A

2013-06-01

Recent phylogeographic studies have overturned three paradigms for the origins of marine biodiversity. (i) Physical (allopatric) isolation is not the sole avenue for marine speciation: many species diverge along ecological boundaries. (ii) Peripheral habitats such as oceanic archipelagos are not evolutionary graveyards: these regions can export biodiversity. (iii) Speciation in marine and terrestrial ecosystems follow similar processes but are not the same: opportunities for allopatric isolation are fewer in the oceans, leaving greater opportunity for speciation along ecological boundaries. Biodiversity hotspots such as the Caribbean Sea and the Indo-Pacific Coral Triangle produce and export species, but can also accumulate biodiversity produced in peripheral habitats. Both hotspots and peripheral ecosystems benefit from this exchange in a process dubbed biodiversity feedback. Copyright © 2013 Elsevier Ltd. All rights reserved.

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...

Fate of copper complexes in hydrothermally altered deep-sea sediments from the Central Indian Ocean Basin.

PubMed

Chakraborty, Parthasarathi; Sander, Sylvia G; Jayachandran, Saranya; Nath, B Nagender; Nagaraju, G; Chennuri, Kartheek; Vudamala, Krushna; Lathika, N; Mascarenhas-Pereira, Maria Brenda L

2014-11-01

The current study aims to understand the speciation and fate of Cu complexes in hydrothermally altered sediments from the Central Indian Ocean Basin and assess the probable impacts of deep-sea mining on speciation of Cu complexes and assess the Cu flux from this sediment to the water column in this area. This study suggests that most of the Cu was strongly associated with different binding sites in Fe-oxide phases of the hydrothermally altered sediments with stabilities higher than that of Cu-EDTA complexes. The speciation of Cu indicates that hydrothermally influenced deep-sea sediments from Central Indian Ocean Basin may not significantly contribute to the global Cu flux. However, increasing lability of Cu-sediment complexes with increasing depth of sediment may increase bioavailability and Cu flux to the global ocean during deep-sea mining. Copyright © 2014 Elsevier Ltd. All rights reserved.

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

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

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE PAGES

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; ...

2017-10-06

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Multi-instrument comparison and compilation of non-methane organic gas emissions from biomass burning and implications for smoke-derived secondary organic aerosol precursors

NASA Astrophysics Data System (ADS)

Hatch, Lindsay E.; Yokelson, Robert J.; Stockwell, Chelsea E.; Veres, Patrick R.; Simpson, Isobel J.; Blake, Donald R.; Orlando, John J.; Barsanti, Kelley C.

2017-01-01

Multiple trace-gas instruments were deployed during the fourth Fire Lab at Missoula Experiment (FLAME-4), including the first application of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC × GC-TOFMS) for laboratory biomass burning (BB) measurements. Open-path Fourier transform infrared spectroscopy (OP-FTIR) was also deployed, as well as whole-air sampling (WAS) with one-dimensional gas chromatography-mass spectrometry (GC-MS) analysis. This combination of instruments provided an unprecedented level of detection and chemical speciation. The chemical composition and emission factors (EFs) determined by these four analytical techniques were compared for four representative fuels. The results demonstrate that the instruments are highly complementary, with each covering some unique and important ranges of compositional space, thus demonstrating the need for multi-instrument approaches to adequately characterize BB smoke emissions. Emission factors for overlapping compounds generally compared within experimental uncertainty, despite some outliers, including monoterpenes. Data from all measurements were synthesized into a single EF database that includes over 500 non-methane organic gases (NMOGs) to provide a comprehensive picture of speciated, gaseous BB emissions. The identified compounds were assessed as a function of volatility; 6-11 % of the total NMOG EF was associated with intermediate-volatility organic compounds (IVOCs). These atmospherically relevant compounds historically have been unresolved in BB smoke measurements and thus are largely missing from emission inventories. Additionally, the identified compounds were screened for published secondary organic aerosol (SOA) yields. Of the total reactive carbon (defined as EF scaled by the OH rate constant and carbon number of each compound) in the BB emissions, 55-77 % was associated with compounds for which SOA yields are unknown or understudied. The best candidates for future smog chamber experiments were identified based on the relative abundance and ubiquity of the understudied compounds, and they included furfural, 2-methyl furan, 2-furan methanol, and 1,3-cyclopentadiene. Laboratory study of these compounds will facilitate future modeling efforts.

Influence of Matrix Composition on the Bioaccessibility of Copper, Zinc and Nickel in Urban Residential Dust and Soil

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

Rasmussen,P.; Beauchemin, S.; Nugent, M.

2008-01-01

This study examines factors affecting oral bioaccessibility of metals in household dust, in particular metal speciation, organic carbon content, and particle size, with the goal of addressing risk assessment information requirements. Investigation of copper (Cu) and zinc (Zn) speciation in two size fractions of dust (< 36 {mu} m and 80-150 {mu} m) using synchrotron X-ray absorption spectroscopy (XAS) indicates that the two metals are bound to different components of the dust: Cu is predominately associated with the organic phase of the dust, while Zn is predominately associated with the mineral fraction. Total and bioaccessible Cu, nickel (Ni), and Znmore » were determined (on dry weight basis) in the < 150 {mu} m size fraction of a set of archived indoor dust samples (n = 63) and corresponding garden soil samples (n = 66) from the City of Ottawa, Canada. The median bioaccessible Cu content is 66 {mu} g g-1 in dust compared to 5 {mu} g g-1 in soil; the median bioaccessible Ni content is 16 {mu} g g-1 in dust compared to 2 {mu} g g-1 in soil; and the median bioaccessible Zn content is 410 {mu} g g-1 in dust compared to 18 {mu} g g-1 in soil. For the same data set, the median total Cu content is 152 {mu} g g-1 in dust compared to 17 {mu} g g-1 in soil; the median total Ni content is 41 {mu} g g-1 in dust compared to 13 {mu} g g-1 in soil; and the median total Zn content is 626 {mu} g g-1 in dust compared to 84 {mu} g g-1 in soil. Organic carbon is elevated in indoor dust (median 28%) compared to soil (median 5%), and is a key factor controlling metal partitioning and therefore bioaccessibility. The results show that house dust and soil have distinct geochemical signatures and should not be treated as identical media in exposure and risk assessments. Separate measurements of the indoor and outdoor environment are essential to improve the accuracy of residential risk assessments.« less

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...

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

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

Geochemical speciation and dynamic of copper in tropical semi-arid soils exposed to metal-bearing mine wastes.

PubMed

Perlatti, Fabio; Otero, Xosé Luis; Macias, Felipe; Ferreira, Tiago Osório

2014-12-01

The potentially hazardous effects of rock wastes disposed at open pit in three different areas (Pr: Ore processing; Wr: Waste rock and Bd: Border) of an abandoned copper mine were evaluated in this study, with emphasis on acid drainage generation, metal contamination and copper geochemical dynamics in soils. Samples of waste rock were analyzed by Energy dispersive X-ray fluorescence (XRF), scanning electron microscopy with microanalysis (SEM-EDS) and X-ray diffraction (XRD). Soil samples were analyzed to determine the total metal contents (XRF), mineralogy (XRD), pH (H2O and H2O2), organic and inorganic carbon, % of total N, S and P, particle size, and a sequential extraction procedure was used to identify the different copper fractions. As a result of the prevalence of carbonates over sulphides in the wastes, the soil pH remained close to neutral, with absence of acid mine drainage. The geochemical interaction between these mineral phases seems to be the main mechanism to release Cu(2)(+) ions. Total Cu in soils from the Pr area reached 11,180mg.kg(-1), while in Wr and Bd areas the values reached, on average, 4683 and 1086mg.kg(-1), respectively, indicating a very high level of soil contamination. In the Pr and Wr, the Cu was mainly associated with carbonates and amorphous iron oxides. In the Bd areas, the presence of vegetation has influenced the geochemical behavior of copper by increasing the dissolution of carbonates, affecting the buffer capacity of soils against sulphide oxidation, reducing the pH levels and enhancing the proportion of exchangeable and organic bound Cu. The present findings show that the use of plants or organic amendments in mine sites with high concentration of Cu carbonate-containing wastes should be viewed with caution, as the practice may enhance the mobilization of copper to the environment due to an increase in the rate of carbonates dissolution. Copyright © 2014 Elsevier B.V. All rights reserved.

Application of Sequential Extractions and X-ray Absorption Spectroscopy to Determine the Speciation of Chromium in Northern New Jersey Marsh Soils Developed in Chromite ore Processing Residue (COPR)

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

Elzinga, E.; Cirmo, A

2010-01-01

The Cr speciation in marsh soils developed in weathering chromite ore processing residue (COPR) was characterized using sequential extractions and synchrotron microbeam and bulk X-ray absorption spectroscopic (XAS) analyses. The sequential extractions suggested substantial Cr associated with reducible and oxidizable soil components, and significant non-extractable residual Cr. Notable differences in Cr speciation estimates from three extraction schemes underscore the operationally defined nature of Cr speciation provided by these methods. Micro X-ray fluorescence maps and {mu}-XAS data indicated the presence of {micro}m-sized chromite particles scattered throughout the weathered COPR matrix. These particles derive from the original COPR material, and have relativelymore » high resistance towards weathering, and therefore persist even after prolonged leaching. Bulk XAS data further indicated Cr(III) incorporated in Fe(OH){sub 3}, and Cr(III) associated with organic matter. The low Cr contents of the weathered material (200-850 ppm) compared to unweathered COPR (20,000-60,000 ppm) point to substantial Cr leaching during COPR weathering, with partial repartitioning of released Cr into secondary Fe(OH){sub 3} phases and organics. The effects of anoxia on Cr speciation, and the potential of active COPR weathering releasing Cr(VI) deeper in the profile require further study.« less

Genetic change and rates of cladogenesis

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

Avise, J.C.; Ayala, F.J.

1975-12-01

Models are introduced which predict ratios of mean levels of genetic divergence in species-rich versus species-poor phylads under two competing assumptions: (1) genetic differentiation is a function of time, unrelated to the number of cladogenetic events and (2) genetic differentiation is proportional to the number of speciation events in the group. The models are simple, general, and biologically real, but not precise. They lead to qualitatively distinct predictions about levels of genetic divergence depending upon the relationship between rates of speciation and amount of genetic change. When genetic distance between species is a function of time, mean genetic distances inmore » speciose and depauperate phylads of equal evolutionary age are very similar. On the contrary, when genetic distance is a function of the number of speciations in the history of a phylad, the ratio of mean genetic distances separating species in speciose versus depauperate phylads is greater than one, and increases rapidly as the frequency of speciations in one group relative to the other increases. The models may be tested with data from natural populations to assess (1) possible correlations between rates of anagenesis and cladogenesis and (2) the amount of genetic differentiation accompanying the speciation process. The data collected in electrophoretic surveys and other kinds of studies can be used to test the predictions of the models. For this purpose genetic distances need to be measured in speciose and depauperate phylads of equal evolutionary age. The limited information presently available agrees better with the model predicting that genetic change is primarily a function of time, and is not correlated with rates of speciation. Further testing of the models is, however, required before firm conclusions can be drawn. (auth)« less

The evolution of conditional dispersal and reproductive isolation along environmental gradients

PubMed Central

Payne, Joshua L.; Mazzucco, Rupert; Dieckmann, Ulf

2011-01-01

Dispersal modulates gene flow throughout a population’s spatial range. Gene flow affects adaptation at local spatial scales, and consequently impacts the evolution of reproductive isolation. A recent theoretical investigation has demonstrated that local adaptation along an environmental gradient, facilitated by the evolution of limited dispersal, can lead to parapatric speciation even in the absence of assortative mating. This and other studies assumed unconditional dispersal, so individuals start dispersing without regard to local environmental conditions. However, many species disperse conditionally; their propensity to disperse is contingent upon environmental cues, such as the degree of local crowding or the availability of suitable mates. Here, we use an individual-based model in continuous space to investigate by numerical simulation the relationship between the evolution of threshold-based conditional dispersal and parapatric speciation driven by frequency-dependent competition along environmental gradients. We find that, as with unconditional dispersal, parapatric speciation occurs under a broad range of conditions when reproduction is asexual, and under a more restricted range of conditions when reproduction is sexual. In both the asexual and sexual cases, the evolution of conditional dispersal is strongly influenced by the slope of the environmental gradient: shallow environmental gradients result in low dispersal thresholds and high dispersal distances, while steep environmental gradients result in high dispersal thresholds and low dispersal distances. The latter, however, remain higher than under unconditional dispersal, thus undermining isolation by distance, and hindering speciation in sexual populations. Consequently, the speciation of sexual populations under conditional dispersal is triggered by a steeper gradient than under unconditional dispersal. Enhancing the disruptiveness of frequency-dependent selection, more box-shaped competition kernels dramatically lower the speciation-enabling slope of the environmental gradient. PMID:21194533

Synergistic selection between ecological niche and mate preference primes diversification.

PubMed

Boughman, Janette W; Svanbäck, Richard

2017-01-01

The ecological niche and mate preferences have independently been shown to be important for the process of speciation. Here, we articulate a novel mechanism by which ecological niche use and mate preference can be linked to promote speciation. The degree to which individual niches are narrow and clustered affects the strength of divergent natural selection and population splitting. Similarly, the degree to which individual mate preferences are narrow and clustered affects the strength of divergent sexual selection and assortative mating between diverging forms. This novel perspective is inspired by the literature on ecological niches; it also explores mate preferences and how they may contribute to speciation. Unlike much comparative work, we do not search for evolutionary patterns using proxies for adaptation and sexual selection, but rather we elucidate how ideas from niche theory relate to mate preference, and how this relationship can foster speciation. Recognizing that individual and population niches are conceptually and ecologically linked to individual and population mate preference functions will significantly increase our understanding of rapid evolutionary diversification in nature. It has potential to help solve the difficult challenge of testing the role of sexual selection in the speciation process. We also identify ecological factors that are likely to affect individual niche and individual mate preference in synergistic ways and as a consequence to promote speciation. The ecological niche an individual occupies can directly affect its mate preference. Clusters of individuals with narrow, differentiated niches are likely to have narrow, differentiated mate preference functions. Our approach integrates ecological and sexual selection research to further our understanding of diversification processes. Such integration may be necessary for progress because these processes seem inextricably linked in the natural world. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

The evolution of conditional dispersal and reproductive isolation along environmental gradients.

PubMed

Payne, Joshua L; Mazzucco, Rupert; Dieckmann, Ulf

2011-03-21

Dispersal modulates gene flow throughout a population's spatial range. Gene flow affects adaptation at local spatial scales, and consequently impacts the evolution of reproductive isolation. A recent theoretical investigation has demonstrated that local adaptation along an environmental gradient, facilitated by the evolution of limited dispersal, can lead to parapatric speciation even in the absence of assortative mating. This and other studies assumed unconditional dispersal, so individuals start dispersing without regard to local environmental conditions. However, many species disperse conditionally; their propensity to disperse is contingent upon environmental cues, such as the degree of local crowding or the availability of suitable mates. Here, we use an individual-based model in continuous space to investigate by numerical simulation the relationship between the evolution of threshold-based conditional dispersal and parapatric speciation driven by frequency-dependent competition along environmental gradients. We find that, as with unconditional dispersal, parapatric speciation occurs under a broad range of conditions when reproduction is asexual, and under a more restricted range of conditions when reproduction is sexual. In both the asexual and sexual cases, the evolution of conditional dispersal is strongly influenced by the slope of the environmental gradient: shallow environmental gradients result in low dispersal thresholds and high dispersal distances, while steep environmental gradients result in high dispersal thresholds and low dispersal distances. The latter, however, remain higher than under unconditional dispersal, thus undermining isolation by distance, and hindering speciation in sexual populations. Consequently, the speciation of sexual populations under conditional dispersal is triggered by a steeper gradient than under unconditional dispersal. Enhancing the disruptiveness of frequency-dependent selection, more box-shaped competition kernels dramatically lower the speciation-enabling slope of the environmental gradient. Copyright © 2010 Elsevier Ltd. All rights reserved.

Carbonic Anhydrase, Calcification Dynamics and Stable Isotope Vital Effects: Deep Sea Corals and Beyond

NASA Astrophysics Data System (ADS)

Chen, S.; Gagnon, A. C.; Adkins, J. F.

2017-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Speciation dynamics in the SE Asian tropics: Putting a time perspective on the phylogeny and biogeography of Sundaland tree squirrels, Sundasciurus.

PubMed

den Tex, Robert-Jan; Thorington, Richard; Maldonado, Jesus E; Leonard, Jennifer A

2010-05-01

Tropical rainforests are well known for their extraordinarily high levels of biodiversity. The origin of this species richness is still debated. For instance, the museum hypothesis states that over evolutionary time more and more species will accumulate with relatively few extinctions. In contrast, the Pleistocene diversification model argues that during the last 2 million years, climatic factors (glaciations) caused environmental changes that drove isolation and vicariant speciation events. In this study, we construct a molecular phylogeny of the Sundaland (Malay Peninsula, Sumata, Borneo, Palawan) and Greater Mindanao (Mindanao, Samar, Leyte) tree squirrels (genus Sundasciurus). Our results show that most speciation events in this forest dependent taxon occurred before the Pleistocene and that even the timing of intra-specific splits among populations from different landmasses are relatively old. Additionally, we found unexpectedly high divergence within and between highland populations of S. tenuis on Sumatra and the Malay Peninsula, highlighting the importance of Pliocene events in both speciation and within species divergences in this region. Copyright 2010 Elsevier Inc. All rights reserved.

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

PubMed

Christie, Kyle; Strauss, Sharon Y

2018-05-01

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