Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

NASA Astrophysics Data System (ADS)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet

Determination of labile copper, cobalt, and chromium in textile mill wastewater

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

Crain, J.S.; Essling, A.M.; Kiely, J.T.

1997-01-01

Copper, chromium, and cobalt species present in filtered wastewater effluent were separated by cation exchange and reverse phase chromatography. Three sample fractions were obtained: one containing metal cations (i.e., trivalent Cr, divalent Cu, and divalent Co), one containing organic species (including metallized dyes), and one containing other unretained species. The metal content of each fraction was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The sum of the corrected data was compared to the metal content of a filtered effluent aliquot digested totally with fuming sulfuric acid. Other aliquots of the filtered effluent were spiked with the metals ofmore » interest and digested to confirm chemical yield and accuracy. Method detection limits were consistently below 20 {mu}g L{sup -1} for Cu, 30 {mu}g L{sup -1} for Co, and 10 {mu}g L{sup -1} for Cr. Spike recoveries for undifferentiated Cu and Cr were statistically indistinguishable from unity; although Co spike recoveries were slightly low ({approximately}95%), its chemical yield was 98%. Copper retention on the sodium sulfonate cation exchange resin was closely correlated with the [EDTA]/[Cu] ratio, suggesting that metals retained upon the cation exchange column were assignable to labile metal species; however, mass balances for all three elements, though reasonable ({approximately}90%), were significantly different from unity. Mechanical factors may have contributed to the material loss, but other data suggest that some metal species reacted irreversibly with the reverse phase column. 3 refs., 2 figs., 4 tabs.« less

Fate and lability of silver in soils: Effect of ageing

EPA Science Inventory

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the ^110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectrosco...

Diffusive Milli-Gels (DMG) for in situ assessment of metal bioavailability: A comparison with labile metal measurement using Chelex columns and acute toxicity to Ceriodaphnia dubia for copper in freshwaters.

PubMed

Perez, Magali; Simpson, Stuart L; Lespes, Gaëtane; King, Josh J; Adams, Merrin S; Jarolimek, Chad V; Grassl, Bruno; Schaumlöffel, Dirk

2016-12-01

Fluctuations in concentrations of bioavailable metals occur in most natural waters. In situ measurements are desirable to predict risks of adverse effects to aquatic organisms. We evaluated Diffusive Milli-Gels (DMG), a new in situ passive sampler, for assessing the bioavailability and toxicity of copper in waters exhibiting a wide range of characteristics. The performance was compared to an established Chelex-column method that measures labile copper concentrations by discrete sampling, and the ability to predict acute toxicity to the cladoceran, Ceriodaphnia dubia. The labile copper concentrations measured by the DMG and Chelex-column methods decreased with increasing dissolved organic carbon (DOC) (1.9-15 mg L -1 ) and hardness (21-270 mg CaCO 3  L -1 hardness), with 20-70% of total dissolved copper being present as labile copper. Toxicity decreased with increasing DOC and hardness. Strong linear relationships existed between the EC50 for C. dubia and DOC, and when the EC50 was related to either the labile copper concentrations measured by DMG (r 2  = 0.874) or the Chelex column (0.956) methods. The study demonstrates that the DMG passive sampler is a relevant tool for the in situ assessment of environmental risks posed by metals whose toxicity is strongly influenced by speciation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Labile, dissolved and particulate PAHs and trace metals in wastewater: passive sampling, occurrence, partitioning in treatment plants.

PubMed

Gourlay-Francé, C; Bressy, A; Uher, E; Lorgeoux, C

2011-01-01

The occurrence and the partitioning of polycyclic aromatic hydrocarbons (PAHs) and seven metals (Al, Cd, Cr, Cu, Ni, Pb and Zn) were investigated in activated sludge wastewater treatment plants by means of passive and active sampling. Concentrations total dissolved and particulate contaminants were determined in wastewater at several points across the treatment system by means of grab sampling. Truly dissolved PAHs were sampled by means of semipermeable membrane devices. Labile (inorganic and weakly complexed) dissolved metals were also sampled using the diffusive gradient in thin film technique. This study confirms the robustness and the validity of these two passive sampling techniques in wastewater. All contaminant concentrations decreased in wastewater along the treatment, although dissolved and labile concentrations sometimes increased for substances with less affinity with organic matter. Solid-liquid and dissolved organic matter/water partitioning constants were estimated. The high variability of both partitioning constants for a simple substance and the poor relation between K(D) and K(OW) shows that the binding capacities of particles and organic matter are not uniform within the treatment and that other process than equilibrium sorption affect contaminant repartition and fate in wastewater.

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the Vistula River plume (southern Baltic Sea).

PubMed

Sokolowski, A; Wolowicz, M; Hummel, H

2001-10-01

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe

Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine.

PubMed

Marmolejo-Rodríguez, Ana Judith; Prego, Ricardo; Meyer-Willerer, Alejandro; Shumilin, Evgueni; Cobelo-García, Antonio

2007-01-01

Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Peña Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%). According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Peña Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.

Transformation of metals speciation in a combined landfill leachate treatment.

PubMed

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

2011-04-01

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter >0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction <0.45 μm were considered as dissolved. Copyright © 2011 Elsevier B.V. All rights reserved.

Distribution of dissolved labile and particulate iron and copper in Terra Nova Bay polynya (Ross Sea, Antarctica) surface waters in relation to nutrients and phytoplankton growth

NASA Astrophysics Data System (ADS)

Rivaro, Paola; Ianni, Carmela; Massolo, Serena; Abelmoschi, M. Luisa; De Vittor, Cinzia; Frache, Roberto

2011-05-01

The distribution of the dissolved labile and of the particulate Fe and Cu together with dissolved oxygen, nutrients, chlorophyll a and total particulate matter was investigated in the surface waters of Terra Nova Bay polynya in mid-January 2003. The measurements were conducted within the framework of the Italian Climatic Long-term Interactions of the Mass balance in Antarctica (CLIMA) Project activities. The labile dissolved fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The dissolved labile Fe ranges from below the detection limit (0.15 nM) to 3.71 nM, while the dissolved labile Cu from below the detection limit (0.10 nM) to 0.90 nM. The lowest concentrations for both metals were observed at 20 m depth (the shallowest depth for which metals were measured). The concentration of the particulate Fe was about 5 times higher than the dissolved Fe concentration, ranging from 0.56 to 24.83 nM with an average of 6.45 nM. The concentration of the particulate Cu ranged from 0.01 to 0.71 nM with an average of 0.17 nM. The values are in agreement with the previous data collected in the same area. We evaluated the role of the Fe and Cu as biolimiting metals. The N:dissolved labile Fe ratios (18,900-130,666) would or would not allow a complete nitrate removal, on the basis of the N:Fe requirement ratios that we calculated considering the N:P and the C:P ratios estimated for diatoms. This finding partially agrees with the Si:N ratio that we found (2.29). Moreover we considered a possible influence of the dissolved labile Cu on the Fe uptake process.

Light availability affects sex lability in a gynodioecious plant.

PubMed

Varga, Sandra; Kytöviita, Minna-Maarit

2016-11-01

Sex lability (i.e., gender diphasy) in plants is classically linked to the larger resource needs associated with the female sexual function (i.e., seed production) compared to the male function (i.e., pollen production). Sex lability in response to the environment is extensively documented in dioecious species, but has been largely overlooked in gynodioecious plants. Here, we tested whether environmental conditions induce sex lability in the gynodioecious Geranium sylvaticum. We conducted a transplantation experiment in the field where plants with different sex expression were reciprocally transplanted between high light and low light habitats. We measured plants' reproductive output and sex expression over four years. Our results show that sex expression was labile over the study period. The light level at the destination habitat had a significant effect on sexual expression and reproductive output, because plants decreased their reproductive output when transplanted to the low light habitat. Transplantation origin did not affect any parameter measured. This study shows that sex expression in Geranium sylvaticum is labile and related to light availability. Sexually labile plants did not produce more seeds or pollen, and thus, there was no apparent fitness gain in sexually labile individuals. Sex lability in gynodioecious plants may be more common than previously believed because detection of sex lability necessitates data on the same individuals over time, which is rare in sexually dimorphic herbaceous plants. © 2016 Botanical Society of America.

Construction of hierarchically porous metal–organic frameworks through linker labilization

DOE PAGES

Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; ...

2017-05-25

One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragmentsmore » by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.« less

Construction of hierarchically porous metal–organic frameworks through linker labilization

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

Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng

One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragmentsmore » by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.« less

Size, speciation and lability of NOM-metal complexes in hyperalkaline cave dripwater

NASA Astrophysics Data System (ADS)

Hartland, Adam; Fairchild, Ian J.; Lead, Jamie R.; Zhang, Hao; Baalousha, Mohammed

2011-12-01

Transport of trace metals by natural organic matter (NOM) is potentially an important vector for trace metal incorporation in secondary cave precipitates [speleothems], yet little is known about the size distribution, speciation and metal binding properties of NOM in cave dripwaters. A hyperalkaline cave environment (ca. pH 11) was selected to provide information on colloid-metal interactions in cave waters, and to address the lack of high-pH data in natural systems in general. Colloidal (1 nm-1 μm) NOM in hyperalkaline cave dripwater from Poole's Cavern, UK, was characterised by flow field-flow fractionation (FlFFF) coupled to UV and fluorescence detectors and transmission electron microscopy (TEM) coupled to X-ray energy-dispersive spectroscopy (X-EDS); trace-metal lability was examined by diffusive gradients in thin films (DGT). Colloidal aggregates and small particulates (>1 μm) imaged by TEM were morphologically heterogeneous with qualitative elemental compositions (X-EDS spectra; n = 41) consistent with NOM aggregates containing aluminosilicates, and iron and titanium oxides. Globular organic colloids, with diameters between ca. 1 and 10 nm were the most numerous colloidal class and exhibited high UV-absorbance (254 nm) and fluorescence intensity (320:400 nm excitation: emission) in optical regions characteristic of humic-like compounds. Metal binding with humic substances was modelled using the WHAM 6.1 (model VI) and visual MINTEQ 3.0 (NICA-Donnan) speciation codes. At pH 11, both models predicted dominant humic binding of Cu (ca. 100%) and minimal binding of Ni and Co (ca. <1-7%). A DGT depletion experiment (7 days duration) with the hyperalkaline dripwater showed that the available proportion of each metal was much lower than its total concentration. Metal availability for DGT in the initial stages (24 h) was consistent with weaker binding of alkaline earth metals by humic substances (Ba > Sr > V > Cu > Ni > Co), compared to the transition metals

Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants.

PubMed

Shan, Xiao-Quan; Wang, Zhongwen; Wang, Weisheng; Zhang, Shuzhen; Wen, Bei

2003-02-01

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionlabile rhizosphere soil solution fraction, F(lrss). For the soil solutions extracted with a mixture of LMWOAs the concentrations of heavy metals and rare earth elements in F(2) and F(3) were quite similar. However, the mean concentrations of Cr, Ni, Zn, Cu, Pb, Cd, La, Ce, Pr, and Nd in F(lrss) accounted for 79.9%, 91.3%, 90.8%, 60.1%, 77.5%, 75.3%, 81.2%, 77.2%, 80.3%, and 79.5%, respectively, of their concentrations in F(2). In contrast, there were no differences in the extractable metal concentrations between the three fractions while the first step of the method recommended by the European Community of Reference (BCR), where 0.1 mol L(-1) acetic acid was used as an extractant. The single correlation analysis was made between metal concentrations in the different fractions of soil solutions and their concentrations in wheat. If the first step of BCR method was used there was no good correlation between heavy metals in soil pools and that in wheat shoots and roots. When LMWAOs were used a good correlation was obtained between the concentrations of heavy metals in soil pools and that in wheat roots, which followed a general order of r(1 kD, LMWOAs) >r(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients

Influence of an iron-rich amendment on chemical lability and plant (Raphanus sativus L.) availability of two metallic elements (As and Pb) on mine-impacted agricultural soils.

PubMed

Kim, Juhee; Kim, Yong-Seong; Hyun, Seunghun; Moon, Deok Hyun; Chang, Jun Young

2016-10-01

Variation of the chemical extractability and phytoavailability of two metallic elements (e.g., As and Pb) on amendment-treated soils was investigated. Four mine-impacted agricultural soils contaminated with both As (174-491 mg kg -1 ) and Pb (116-357 mg kg -1 ) were amended with an iron-rich sludge at the rate of 5 % (w/w). After a 4-, 8-, and 16-week incubation, the extractability of metallic elements was assessed by sequential extraction procedure (SEP; F1-F5). The control without amendment was also run. In amended soils, the labile element mass (i.e., F1 + F2) promptly decreased (15-48 % of As and 5-10 % of Pb) in 4 weeks, but the decrement was continued over 16 weeks up to 70 and 28 % for As and Pb, respectively. The labile mass decrement was quantitatively corresponded with the increment of F3 (bound to amorphous metal oxides). In plant test assessed by radish (Raphanus sativus) grown on the 16-week soils, up to 57 % of As and 28 % of Pb accumulation was suppressed and 10-43 % of growth (i.e., shoot/root elongation and fresh weight) was improved. For both the control and amended soils, element uptake by plant was well correlated with their labile soil concentrations (r 2  = 0.799 and 0.499 for As and Pb, respectively). The results confirmed that the iron-rich material can effectively suppress element uptake during R. sativus seedling growth, most likely due to the chemical stabilization of metallic elements in growth medium.

Size charge fractionation of metals in municipal solid waste landfill leachate.

PubMed

Oygard, Joar Karsten; Gjengedal, Elin; Røyset, Oddvar

2007-01-01

Municipal solid waste landfill leachates from 9 Norwegian sites were size charge fractionated in the field, to obtain three fractions: particulate and colloidal matter >0.45microm, free anions/non-labile complexes <0.45microm and free cations/labile complexes <0.45microm. The fractionation showed that Cd and Zn, and especially Cu and Pb, were present to a large degree (63-98%) as particulate and colloidal matter >0.45microm. Cr, Co and Ni were on the contrary present mostly as non-labile complexes (69-79%) <0.45microm. The major cations Ca, Mg, K, and Mn were present mainly as free cations/labile complexes <0.45microm, while As and Mo were present to a large degree (70-90%) as free anions/non-labile complexes <0.45microm. Aluminium was present mainly as particulate and colloidal matter >0.45microm. The particulate and colloidal matter >0.45microm was mainly inorganic; indicating that the metals present in this fraction were bound as inorganic compounds. The fractionation gives important information on the mobility and potential bioavailability of the metals investigated, in contrast to the total metal concentrations usually reported. To study possible changes in respective metal species in leachate in aerated sedimentation tanks, freshly sampled leachate was stored for 48h, and subsequently fractionated. This showed that the free heavy metals are partly immobilized during storage of leachate with oxygen available. The largest effects were found for Cd and Zn. The proportion of As and Cr present as particulate matter or colloids >0.45microm also increased.

'Inconstant males' and the maintenance of labile sex expression in subdioecious plants.

PubMed

Ehlers, Bodil K; Bataillon, Thomas

2007-01-01

* Here, we evaluate the role of pollen limitation and selfing in the maintenance of labile sex expression in subdioecious plant species. * We used a literature survey to explore which factors correlated with a significant occurrence of hermaphrodites in dioecious species. We developed models to explore the selective maintenance of labile sex expression. The models had similar ecological assumptions but differed in the genetic basis of sex lability. * We found that a significant frequency of hermaphrodites was associated with animal pollination, and that hermaphrodites were 'inconstant' males with perfect flowers, suggesting evolution through the gynodioecious pathway. Models showed that a modifier converting pure males into inconstant males could be maintained under a wide range of reduction in both male and female fitness. Pollen limitation and self-fertilization facilitated invasion of the modifier. Depending on the genetics of sex determination, we found pure dioecy, stable subdioecy (trioecy), and situations where inconstant males coexisted with either pure females or pure males. Under selfing and pollen limitation, certain conditions selected for inconstant males which will drive populations to extinction. * We discuss our results in relation to the evolution towards, and the breakdown of, dioecy, and the ecological and evolutionary implications of labile sex expression.

Mood lability and psychopathology in youth.

PubMed

Stringaris, A; Goodman, R

2009-08-01

Mood lability is a concept widely used. However, data on its prevalence and morbid associations are scarce. We sought to establish the occurrence and importance of mood lability in a large community sample of children and adolescents by testing a priori hypotheses. Cross-sectional data were taken from a national mental health survey including 5326 subjects aged 8-19 years in the UK. The outcomes were prevalence and characteristics of mood lability and its associations with psychopathology and overall impairment. Mood lability occurred in more than 5% of the population of children and adolescents, both by parent and self-report. Mood lability was strongly associated with a wide range of psychopathology and was linked to significant impairment even in the absence of psychiatric disorders. Mood lability was particularly strongly associated with co-morbidity between internalizing and externalizing disorders, even when adjusting for the association with individual disorders. The pattern of results did not change after excluding youth with bipolar disorder or with episodes of elated mood. Clinically significant mood lability is relatively common in the community. Our findings indicate that mood lability is not a mere consequence of other psychopathology in that it is associated with significant impairment even in the absence of psychiatric diagnoses. Moreover, the pattern of association of mood lability with co-morbidity suggests that it could be a risk factor shared by both internalizing and externalizing disorders. Our data point to the need for greater awareness of mood lability and its implications for treatment.

Labile and Non-labile Soil Carbon Fractions Equally Contributed to Carbon Changes under Long-term Fertilization

NASA Astrophysics Data System (ADS)

Liang, F.; Li, J.; Xu, M.; Huang, S.

2017-12-01

Soil organic carbon (SOC) storages are altered under long-term fertilization in croplands, it however remains unclear how fast- to slow-cycling SOC fractions each respond to fertilization practices. Based on five two-decade Chinese long-term fertilization experiments (GZL: Gongzhuling; ZZ: Zhengzhou; CQ: Chongqing; JX: Jinxian; QY: Qiyang) under three fertilization treatments (CK: cropping with no fertilizer input; NPK: chemical nitrogen, phosphorus and potassium fertilizers; and NPKM: NPK with manure input), we quantified very labile, labile, non-labile and total SOC stocks at 0-20cm soil depth. Results showed that SOC stocks varied among sites (GZL, JX, CQ > ZZ, QY) and generally increased with fertilizations (CK-1 at ZZ, GZL, QY, CQ and JX, respectively. The corresponding changes of the sum of very labile and labile SOC fractions were 2.6, 2.0, 1.8, 0.8 and -0.5 Mg ha-1 at ZZ, QY, GZL, CQ and JX, respectively. Also, NPKM increased total SOC stock by 18.3, 16.2, 14.4, 10.5, and 6.5 Mg ha-1 at QY, GZL, ZZ, CQ and JX, respectively. The corresponding changes of the sum of very labile and labile SOC fractions were 8.6, 6.8, 6.6, 3.2 and -1.6 Mg ha-1 at QY, GZL, ZZ, CQ and JX, respectively. These results suggested that about half or more than half SOC stock accretions under fertilization were induced by increase in non-labile SOC fractions. It thus informs the importance of non-labile SOC fractions in contributing to soil C sequestration under long-term fertilizations in Chinese croplands. Future research should improve our mechanistic understanding of biogeochemical transformation of non-labile organic C in soils.

Freshwater processing of terrestrial dissolved organic matter: What governs lability?

NASA Astrophysics Data System (ADS)

D'Andrilli, J.; Smith, H. J.; Junker, J. R.; Scholl, E. A.; Foreman, C. M.

2016-12-01

Aquatic and terrestrial ecosystems are linked through the transfer of energy and materials. Allochthonous organic matter (OM) is central to freshwater ecosystem function, influencing local food webs, trophic state, and nutrient availability. In order to understand the nature and fate of OM from inland headwaters to the open ocean, it is imperative to understand the links between OM lability and ecosystem function. Thus, biological, chemical, and physical factors need to be evaluated together to inform our understanding of environmental lability. We performed a laboratory processing experiment on naturally occurring OM leachates from riparian leaves, grasses, and pine needles. Measures of water chemistry, OM optical and molecular characterization, bacterial abundances, microbial assemblage composition, respiration, and C:N:P were integrated to discern the nature and fate of labile and recalcitrant OM in a freshwater stream. Peak processing of all OM sources in the stream water occurred after two days, with spikes in bacterial cell abundances, respiration rates, microbial assemblage shifts, and maximum C utilization. Respiration rates and microbial assemblages were dependent on the degree of lability of the OM molecular composition. Within the first few days, no differences in respiration rates were observed between leachate sources, however, beyond day five, the rates diverged with C processing efficiency correlated with OM lability. Originally comprised of amino acid-like, labile fluorescent species, the inoculated stream water OM became more recalcitrant after 16 days, indicating humification processing over time. Our study highlights the importance of interdisciplinary approaches for understanding the processing and fate of OM in aquatic ecosystems.

Sensitivity-enhanced detection of non-labile proton and carbon NMR spectra on water resonances.

PubMed

Novakovic, Mihajlo; Martinho, Ricardo P; Olsen, Gregory L; Lustig, Michael S; Frydman, Lucio

2017-12-20

Chemical exchange saturation transfer (CEST) experiments enhance the NMR signals of labile protons by continuously transferring these protons' saturation to an abundant solvent pool like water. The present study expands these principles by fusing into these experiments homonuclear isotropic mixing sequences, enabling the water-enhanced detection of non-exchangeable species. Further opportunities are opened by the addition of coupling-mediated heteronuclear polarization transfers, which then impose on the water resonance a saturation stemming from non-labile heteronuclear species like 13 C. To multiplex the ensuing experiments, these relayed approaches are combined with time-domain schemes involving multiple Ramsey-labeling experiments imparting the frequencies of the non-labile sites on the water resonance, via chemical exchange. 13 C and 1 H NMR spectra were detected in this fashion with about two-fold SNR amplification vis-à-vis conventionally detected spectroscopies. When combined with non-uniform sampling principles, this methodology thus becomes a sensitive alternative to detect non-exchangeable species in biomolecules. Still, multiple parameters including the scalar couplings and solvent exchange rates, will affect the efficiency and consequently the practicality of the overall experiment.

The effect of acidification on the bioavailability and electrochemical lability of zinc in seawater

PubMed Central

Kim, Ja-Myung; Baars, Oliver

2016-01-01

A poorly studied but potentially important consequence of the CO2-induced acidification of the surface ocean is a possible change in the bioavailability of trace metals, which play a critical role in the productivity and population dynamics of marine ecosystems. We report laboratory and field experiments designed to compare quantitatively the effects of acidification on the bioavailability of Zn, a metal essential to the growth of phytoplankton and on the extent of its complexation by model and natural ligands. We observed a good correspondence between the effects of pH on the rate of Zn uptake by a model diatom and the chemical lability of Zn measured by anodic stripping voltammetry (ASV). In model laboratory systems, the chemical lability and the bioavailability of Zn could either increase or decrease at low pH depending on the mix of complexing ligands. In a sample of coastal surface water, we observed similar increases in the ASV-labile and bioavailable Zn concentrations upon acidification, a result contrary to previous observations. These results, which can likely be generalized to other bioactive trace metals, mutatis mutandis, demonstrate the intricacy of the effects of ocean acidification on the chemistry and the ecology of surface seawater. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035261

The effect of acidification on the bioavailability and electrochemical lability of zinc in seawater.

PubMed

Kim, Ja-Myung; Baars, Oliver; Morel, François M M

2016-11-28

A poorly studied but potentially important consequence of the CO 2 -induced acidification of the surface ocean is a possible change in the bioavailability of trace metals, which play a critical role in the productivity and population dynamics of marine ecosystems. We report laboratory and field experiments designed to compare quantitatively the effects of acidification on the bioavailability of Zn, a metal essential to the growth of phytoplankton and on the extent of its complexation by model and natural ligands. We observed a good correspondence between the effects of pH on the rate of Zn uptake by a model diatom and the chemical lability of Zn measured by anodic stripping voltammetry (ASV). In model laboratory systems, the chemical lability and the bioavailability of Zn could either increase or decrease at low pH depending on the mix of complexing ligands. In a sample of coastal surface water, we observed similar increases in the ASV-labile and bioavailable Zn concentrations upon acidification, a result contrary to previous observations. These results, which can likely be generalized to other bioactive trace metals, mutatis mutandis , demonstrate the intricacy of the effects of ocean acidification on the chemistry and the ecology of surface seawater.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).

Molecular imaging of labile iron(II) pools in living cells with a turn-on fluorescent probe.

PubMed

Au-Yeung, Ho Yu; Chan, Jefferson; Chantarojsiri, Teera; Chang, Christopher J

2013-10-09

Iron is an essential metal for living organisms, but misregulation of its homeostasis at the cellular level can trigger detrimental oxidative and/or nitrosative stress and damage events. Motivated to help study the physiological and pathological consequences of biological iron regulation, we now report a reaction-based strategy for monitoring labile Fe(2+) pools in aqueous solution and living cells. Iron Probe 1 (IP1) exploits a bioinspired, iron-mediated oxidative C-O bond cleavage reaction to achieve a selective turn-on response to Fe(2+) over a range of cellular metal ions in their bioavailable forms. We show that this first-generation chemical tool for fluorescence Fe(2+) detection can visualize changes in exchangeable iron stores in living cells upon iron supplementation or depletion, including labile iron pools at endogenous, basal levels. Moreover, IP1 can be used to identify reversible expansion of labile iron pools by stimulation with vitamin C or the iron regulatory hormone hepcidin, providing a starting point for further investigations of iron signaling and stress events in living systems as well as future probe development.

Biologically labile photoproducts from riverine non-labile dissolved organic carbon in the coastal waters

NASA Astrophysics Data System (ADS)

Kasurinen, V.; Aarnos, H.; Vähätalo, A.

2015-06-01

In order to assess the production of biologically labile photoproducts (BLPs) from non-labile riverine dissolved organic carbon (DOC), we collected water samples from ten major rivers, removed labile DOC and mixed the residual non-labile DOC with artificial seawater for microbial and photochemical experiments. Bacteria grew on non-labile DOC with a growth efficiency of 11.5% (mean; range from 3.6 to 15.3%). Simulated solar radiation transformed a part of non-labile DOC into BLPs, which stimulated bacterial respiration and production, but did not change bacterial growth efficiency (BGE) compared to the non-irradiated dark controls. In the irradiated water samples, the amount of BLPs stimulating bacterial production depended on the photochemical bleaching of chromophoric dissolved organic matter (CDOM). The apparent quantum yields for BLPs supporting bacterial production ranged from 9.5 to 76 (mean 39) (μmol C mol photons-1) at 330 nm. The corresponding values for BLPs supporting bacterial respiration ranged from 57 to 1204 (mean 320) (μmol C mol photons-1). According to the calculations based on spectral apparent quantum yields and local solar radiation, the annual production of BLPs ranged from 21 (St. Lawrence) to 584 (Yangtze) mmol C m-2 yr-1 in the plumes of the examined rivers. Complete photobleaching of riverine CDOM in the coastal ocean was estimated to produce 10.7 Mt C BLPs yr-1 from the rivers examined in this study and globally 38 Mt yr-1 (15% of riverine DOC flux from all rivers), which support 4.1 Mt yr-1 of bacterial production and 33.9 Mt yr-1 bacterial respiration.

In vivo bioluminescence imaging of labile iron accumulation in a murine model of Acinetobacter baumannii infection.

PubMed

Aron, Allegra T; Heffern, Marie C; Lonergan, Zachery R; Vander Wal, Mark N; Blank, Brian R; Spangler, Benjamin; Zhang, Yaofang; Park, Hyo Min; Stahl, Andreas; Renslo, Adam R; Skaar, Eric P; Chang, Christopher J

2017-11-28

Iron is an essential metal for all organisms, yet disruption of its homeostasis, particularly in labile forms that can contribute to oxidative stress, is connected to diseases ranging from infection to cancer to neurodegeneration. Iron deficiency is also among the most common nutritional deficiencies worldwide. To advance studies of iron in healthy and disease states, we now report the synthesis and characterization of iron-caged luciferin-1 (ICL-1), a bioluminescent probe that enables longitudinal monitoring of labile iron pools (LIPs) in living animals. ICL-1 utilizes a bioinspired endoperoxide trigger to release d-aminoluciferin for selective reactivity-based detection of Fe 2+ with metal and oxidation state specificity. The probe can detect physiological changes in labile Fe 2+ levels in live cells and mice experiencing iron deficiency or overload. Application of ICL-1 in a model of systemic bacterial infection reveals increased iron accumulation in infected tissues that accompany transcriptional changes consistent with elevations in both iron acquisition and retention. The ability to assess iron status in living animals provides a powerful technology for studying the contributions of iron metabolism to physiology and pathology.

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.

Metal Vinylidenes as Catalytic Species in Organic Reactions

PubMed Central

McClory, Andrew

2008-01-01

Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis. PMID:18172846

The Preparation of an Ultrastable Mesoporous Cr(III)-MOF via Reductive Labilization

DTIC Science & Technology

2015-09-02

of metal clusters from a template MOF with a known structure. Fe(III)-MOFs can serve as practical structural templates because iron resembles chromium ...clusters in PCN-333 are able to accommodate both di- and trivalent metal ions by varying the charges of the terminal ligands, the bridging oxygen atoms, and...molecules in trivalent aqua complexes27 Inert complexes Labile complexes M(OH2) Cr(OH2)6 3+ Ir(OH2)6 3+ V(OH2)6 3+ Fe(OH2)6 3+ Ti(OH2)6 3+ k (s1) 2.4 10

Monitoring trace metals in seawater using a diffusive gradient in thin film probe in Ulsan Bay, East Sea, Korea: Comparison with transplanted mussels

NASA Astrophysics Data System (ADS)

Kim, Mi Seon; Choi, Man Sik; Kim, Chan-Kook

2016-03-01

To evaluate the applicability of a diffusive gradient in thin film (DGT) probe for monitoring dissolved metals in coastal seawater, DGT-labile metal concentrations were compared with total dissolved metal concentrations using spiked and natural seawater samples in the laboratory and transplanted mussels ( Mytilus galloprovincialis). This was achieved through the simultaneous deployment of DGT probes and transplanted mussels in Ulsan Bay during winter and summer. DGT-labile metal concentrations were 45% (Cu) ~ 90% (Zn) of total dissolved concentrations, and the order of non-labile concentrations was Cu > Pb > Co ~ Ni > Cd ~ Zn in both metal-contaminated and non-contaminated seawater samples, which was similar to the order of stability of metal complexes in the Irving-Williams series. The overall variability of the DGT probe results within and between tanks was less than 10% (relative standard deviation: RSD) for all the metals tested during a 48-h deployment. The accumulation of metals, as determined by DGT probes, represented the spatial gradients better than the transplanted mussels did for all of the metals tested, and the extent of metal accumulation in mussels differed depending on the metal. The comparison of results for the DGT probe and the transplanted mussels in two seasons (winter and summer) suggested that metal accumulation in mussels was controlled by the physiological factors of mussels and partly by their diet (particulate metal loadings). The DGT probe could be used as a monitoring tool for dissolved metals in coastal seawater because its results explained only labile species. When using the DGT probe, slightly more than half of the total dissolved concentration in seawater samples for all the metals investigated displayed timeintegrated properties and distinct spatial gradients from pristine to metal-contaminated seawater.

Metal species involved in long distance metal transport in plants

PubMed Central

Álvarez-Fernández, Ana; Díaz-Benito, Pablo; Abadía, Anunciación; López-Millán, Ana-Flor; Abadía, Javier

2014-01-01

The mechanisms plants use to transport metals from roots to shoots are not completely understood. It has long been proposed that organic molecules participate in metal translocation within the plant. However, until recently the identity of the complexes involved in the long-distance transport of metals could only be inferred by using indirect methods, such as analyzing separately the concentrations of metals and putative ligands and then using in silico chemical speciation software to predict metal species. Molecular biology approaches also have provided a breadth of information about putative metal ligands and metal complexes occurring in plant fluids. The new advances in analytical techniques based on mass spectrometry and the increased use of synchrotron X-ray spectroscopy have allowed for the identification of some metal-ligand species in plant fluids such as the xylem and phloem saps. Also, some proteins present in plant fluids can bind metals and a few studies have explored this possibility. This study reviews the analytical challenges researchers have to face to understand long-distance metal transport in plants as well as the recent advances in the identification of the ligand and metal-ligand complexes in plant fluids. PMID:24723928

Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

NASA Astrophysics Data System (ADS)

Marzouk, E. R.; Chenery, S. R.; Young, S. D.

2013-12-01

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop

Non-labile silver species in biosolids remain stable throughout 50 years of weathering and ageing.

EPA Science Inventory

Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that...

Evolutionary lability of a complex life cycle in the aphid genus Brachycaudus.

PubMed

Emmanuelle, Jousselin; Gwenaelle, Genson; Armelle, Coeur d'acier

2010-09-28

Most aphid species complete their life cycle on the same set of host-plant species, but some (heteroecious species) alternate between different hosts, migrating from primary (woody) to secondary (herbaceous) host plants. The evolutionary processes behind the evolution of this complex life cycle have often been debated. One widely accepted scenario is that heteroecy evolved from monoecy on woody host plants. Several shifts towards monoecy on herbaceous plants have subsequently occurred and resulted in the radiation of aphids. Host alternation would have persisted in some cases due to developmental constraints preventing aphids from shifting their entire life cycle to herbaceous hosts (which are thought to be more favourable). According to this scenario, if aphids lose their primary host during evolution they should not regain it. The genus Brachycaudus includes species with all the types of life cycle (monoecy on woody plants, heteroecy, monoecy on herbs). We used this genus to test hypotheses concerning the evolution of life cycles in aphids. Phylogenetic investigation and character reconstruction suggest that life cycle is evolutionary labile in the genus. Though ancestral character states can be ambiguous depending on optimization methods, all analyses suggest that transitions from monoecy on herbs towards heteroecy have occurred several times. Transitions from heteroecy towards monoecy, are also likely. There have been many shifts in feeding behaviour but we found no significant correlation between life cycle changes and changes in diet. The transitions from monoecy on herbs towards heteroecy observed in this study go against a widely accepted evolutionary scenario: aphids in the genus Brachycaudus seem to be able to recapture their supposedly ancestral woody host. This suggests that the determinants of host alternation are probably not as complicated as previously thought. Definitive proofs of the lability of life cycle in Brachycaudus will necessitate

Changes in lead and zinc lability during weathering-induced acidification of desert mine tailings: Coupling chemical and micro-scale analyses.

PubMed

Hayes, Sarah M; White, Scott A; Thompson, Thomas L; Maier, Raina M; Chorover, Jon

2009-12-01

Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5 to 8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and "bioavailable" metal concentrations result from associated variation in particle-scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 - 13 g kg(-1)) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4 - 6 g kg(-1)) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools.

Changes in lead and zinc lability during weathering-induced acidification of desert mine tailings: Coupling chemical and micro-scale analyses

PubMed Central

Hayes, Sarah M.; White, Scott A.; Thompson, Thomas L.; Maier, Raina M.; Chorover, Jon

2009-01-01

Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5 to 8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and “bioavailable” metal concentrations result from associated variation in particle-scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 – 13 g kg−1) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4 – 6 g kg−1) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools. PMID:20161492

Volatile metal species in coal combustion flue gas.

PubMed

Pavageau, Marie-Pierre; Pécheyran, Christophe; Krupp, Eva M; Morin, Anne; Donard, Olivier F X

2002-04-01

Metals are released in effluents of most of combustion processes and are under intensive regulations. To improve our knowledge of combustion process and their resulting emission of metal to the atmosphere, we have developed an approach allowing usto distinguish between gaseous and particulate state of the elements emitted. This study was conducted on the emission of volatile metallic species emitted from a coal combustion plant where low/medium volatile coal (high-grade ash) was burnt. The occurrence of volatile metal species emission was investigated by cryofocusing sampling procedure and detection using low-temperature packed-column gas chromatography coupled with inductively coupled plasma-mass spectrometry as multielement detector (LT-GC/ICP-MS). Samples were collected in the stack through the routine heated sampling line of the plant downstream from the electrostatic precipitator. The gaseous samples were trapped with a cryogenic device and analyzed by LT-GC/ICP-MS. During the combustion process, seven volatile metal species were detected: three for Se, one for Sn, two for Hg, and one for Cu. Thermodynamic calculations and experimental metal species spiking experiments suggest that the following volatile metal species are present in the flue gas during the combustion process: COSe, CSSe, CSe2, SeCl2, Hg0, HgCl2, CuO-CuSO4 or CuSO4 x H2O, and SnO2 or SnCl2. The quantification of volatile species was compared to results traditionally obtained by standardized impinger-based sampling and analysis techniques recommended for flue gas combustion characterization. Results showed that concentrations obtained with the standard impinger approach are at least 10 times higher than obtained with cryogenic sampling, suggesting the trapping microaerosols in the traditional methods. Total metal concentrations in particles are also reported and discussed.

Effect of angiotensin II on iron-transporting protein expression and subsequent intracellular labile iron concentration in human glomerular endothelial cells.

PubMed

Tajima, Soichiro; Tsuchiya, Koichiro; Horinouchi, Yuya; Ishizawa, Keisuke; Ikeda, Yasumasa; Kihira, Yoshitaka; Shono, Masayuki; Kawazoe, Kazuyoshi; Tomita, Shuhei; Tamaki, Toshiaki

2010-07-01

Angiotensin II (Ang II)-induced endothelial injury, which is associated with atherosclerosis, is believed to be mediated by intracellular reactive oxygen species (ROS) through stimulation of nicotinamide adenine dinucleotide phosphate oxidase (NOX). Iron is essential for the amplification of oxidative stress. In this study, we investigated whether Ang II altered iron metabolism and whether the Ang II-induced endothelial injury is attributable to changes in iron metabolism of human glomerular endothelial cells (HGECs). When 90% iron-saturated human transferrin (90% Tf) was applied to HGECs without Ang II, the labile ferrous iron level was same as the effect of control in spite of a significant increase in the total cellular iron concentration. Treatment with Ang II and 30% Tf or 90% Tf significantly (P<0.01) increased the intracellular iron concentration, as well as labile ferrous iron and protein oxidation levels, compared with the effect of separate administration of each compound. Ang II treatment facilitated the protein expression of the Tf receptor, divalent metal transporter 1, and ferroportin 1 in a dose- and time-dependent manner. It was also found that simultaneous exposure of HGECs to Ang II and 90% Tf accelerated hydroxyl radical production, as shown by using an electron paramagnetic resonance spectrometer. These results suggest that Ang II not only induces production of ROS by NOX activation but also iron incorporation followed by an increase in labile iron in HGECs. Both of these events may participate in the progression of oxidative stress because of endothelial cell dysfunction through ferrous iron-mediated ROS generation.

Relationship between the lability of sediment-bound Cd and its bioaccumulation in edible oyster.

PubMed

Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita; Chennuri, Kartheek; Bardhan, Pratirupa

2015-11-15

A linkage between Cd speciation in sediments and its bioaccumulation in edible oyster (Crassostrea sp.) from a tropical estuarine system was established. Bioaccumulation of Cd in edible oyster increased with the increasing lability and dissociation rate constants of Cd-sediment complexes in the bottom sediments. Total Cd concentration in sediment was not a good indicator of Cd-bioavailability. Increasing trace metal competition in sediments increased lability and bioavailability of Cd in the tropical estuarine sediment. Low thermodynamic stability and high bioavailability of Cd in the estuarine sediment were responsible for high bioaccumulation of Cd in edible oysters (3.2-12.2mgkg(-1)) even though the total concentration of Cd in the bottom sediment was low (0.17-0.49mgkg(-1)). Copyright © 2015 Elsevier Ltd. All rights reserved.

Upregulation of transferrin receptor-1 induces cholangiocarcinoma progression via induction of labile iron pool.

PubMed

Jamnongkan, Wassana; Thanan, Raynoo; Techasen, Anchalee; Namwat, Nisana; Loilome, Watcharin; Intarawichian, Piyapharom; Titapun, Attapol; Yongvanit, Puangrat

2017-07-01

Labile iron pool is a cellular source of ions available for Fenton reactions resulting in oxidative stress. Living organisms avoid an excess of free irons by a tight control of iron homeostasis. We investigated the altered expression of iron regulatory proteins and iron discrimination in the development of liver fluke-associated cholangiocarcinoma. Additionally, the levels of labile iron pool and the functions of transferrin receptor-1 on cholangiocarcinoma development were also identified. Iron deposition was determined using the Prussian blue staining method in human cholangiocarcinoma tissues. We investigated the alteration of iron regulatory proteins including transferrin, transferrin receptor-1, ferritin, ferroportin, hepcidin, and divalent metal transporter-1 in cholangiocarcinoma tissues using immunohistochemistry. The clinicopathological data of cholangiocarcinoma patients and the expressions of proteins were analyzed. Moreover, the level of intracellular labile iron pool in cholangiocarcinoma cell lines was identified by the RhoNox-1 staining method. We further demonstrated transferrin receptor-1 functions on cell proliferation and migration upon small interfering RNA for human transferrin receptor 1 transfection. Results show that Iron was strongly stained in tumor tissues, whereas negative staining was observed in normal bile ducts of healthy donors. Interestingly, high iron accumulation was significantly correlated with poor prognosis of cholangiocarcinoma patients. The expressions of iron regulatory proteins in human cholangiocarcinoma tissues and normal liver from cadaveric donors revealed that transferrin receptor-1 expression was increased in the cancer cells of cholangiocarcinoma tissues when compared with the adjacent normal bile ducts and was significantly correlated with cholangiocarcinoma metastasis. Labile iron pool level and transferrin receptor-1 expression were significantly increased in KKU-214 and KKU-213 when compared with cholangiocyte

Estimating labile particulate iron concentrations in coastal waters from remote sensing data

NASA Astrophysics Data System (ADS)

McGaraghan, Anna R.; Kudela, Raphael M.

2012-02-01

Owing to the difficulties inherent in measuring trace metals and the importance of iron as a limiting nutrient for biological systems, the ability to monitor particulate iron concentration remotely is desirable. This study examines the relationship between labile particulate iron, described here as weak acid leachable particulate iron or total dissolvable iron, and easily obtained bio-optical measurements. We develop a bio-optical proxy that can be used to estimate large-scale patterns of labile iron concentrations in surface waters, and we extend this by including other environmental variables in a multiple linear regression statistical model. By utilizing a ratio of optical backscatter and fluorescence obtained by satellite, we identify patterns in iron concentrations confirmed by traditional shipboard sampling. This basic relationship is improved with the addition of other environmental parameters in the statistical linear regression model. The optical proxy detects known temporal and spatial trends in average surface iron concentrations in Monterey Bay. The proxy is robust in that similar performance was obtained using two independent particulate iron data sets, but it exhibits weaker correlations than the full statistical model. This proxy will be a valuable tool for oceanographers seeking to monitor iron concentrations in coastal regions and allows for better understanding of the variability of labile particulate iron in surface waters to complement direct measurement of leachable particulate or total dissolvable iron.

Assessment of the labile fractions of copper and zinc in marinas and port areas in Southern Brazil.

PubMed

Costa, Luiza Dy Fonseca; Wallner-Kersanach, Mônica

2013-08-01

The dissolved labile and labile particulate fractions (LPF) of Cu and Zn were analyzed during different seasons and salinity conditions in estuarine waters of marina, port, and shipyard areas in the southern region of the Patos Lagoon (RS, Brazil). The dissolved labile concentration was determined using the diffusive gradients in thin films technique (DGT). DGT devices were deployed in seven locations of the estuary for 72 h and the physicochemical parameters were also measured. The LPF of Cu and Zn was determined by daily filtering of water samples. Seasonal variation of DGT-Cu concentrations was only significant (p < 0.05) at one shipyard area, while DGT-Zn was significant (p < 0.05) in every locations. The LPF of Cu and Zn concentrations demonstrated seasonal and spatial variability in all locations, mainly at shipyard areas during high salinity conditions. In general, except the control location, the sampling locations showed mean variations of 0.11-0.45 μg L(-1) for DGT-Cu, 0.89-9.96 μg L(-1) for DGT-Zn, 0.65-3.69 μg g(-1) for LPF-Cu, and 1.35-10.87 μg g(-1) for LPF-Zn. Shipyard areas demonstrated the most expressive values of labile Cu and Zn in both fractions. Strong relationship between DGT-Zn and LPF-Zn was found suggesting that the DGT-Zn fraction originates from the suspended particulate matter. Water salinity and suspended particulate matter content indicated their importance for the control of the labile concentrations of Cu and Zn in the water column. These parameters must be taken into consideration for comparison among labile metals in estuaries.

Rhizosphere Environment and Labile Phosphorus Release from Organic Waste-Amended Soils.

NASA Astrophysics Data System (ADS)

Dao, Thanh H.

2015-04-01

Crop residues and biofertilizers are primary sources of nutrients for organic crop production. However, soils treated with large amounts of nutrient-enriched manure have elevated phosphorus (P) levels in regions of intensive animal agriculture. Surpluses occurred in these amended soils, resulting in large pools of exchangeable inorganic P (Pi) and enzyme-labile organic P (Po) that averaging 30.9 and 68.2 mg kg-1, respectively. Organic acids produced during crop residue decomposition can promote the complexation of counter-ions and decouple and release unbound Pi from metal and alkali metal phosphates. Animal manure and cover crop residues also contain large amounts of soluble organic matter, and likely generate similar ligands. However, a high degree of heterogeneity in P spatial distribution in such amended fields, arising from variances in substrate physical forms ranging from slurries to dried solids, composition, and diverse application methods and equipment. Distinct clusters of Pi and Po were observed, where accumulation of the latter forms was associated with high soil microbial biomass C and reduced phosphomonoesterases' activity. Accurate estimates of plant requirements and lability of soil P pools, and real-time plant and soil P sensing systems are critical considerations to optimally manage manure-derived nutrients in crop production systems. An in situ X-ray fluorescence-based approach to sensing canopy and soil XRFS-P was developed to improve the yield-soil P relationship for optimal nutrient recommendations in addition to allowing in-the-field verification of foliar P status.

Effects of drying-wetting and freezing-thawing cycle on leachability of metallic elements in mine soils

NASA Astrophysics Data System (ADS)

Bang, H.; Kim, J.; Hyun, S.

2016-12-01

Mine leachate derived from contaminated mine sites with metallic elements can pose serious risks on human society and environment. Only labile fraction of metallic elements in mine soils is subject to leaching and movement by rainfall. Lability of metallic element in soil is a function of bond strengths between metal and soil surfaces, which is influenced by environmental condition (e.g., rainfall intensity, duration, temperature, etc.) The purpose of this study was to elucidate the effects of various climate conditions on the leaching patterns and lability of metallic elements in mine soils. To do this, two mine soils were sampled from two abandoned mine sites located in Korea. Leaching test were conducted using batch decant-refill method. Various climatic conditions were employed in leaching test such as (1) oven drying (40oC) - wetting cycles, (2) air drying (20oC) - wetting cycle, and (3) freezing (-40oC) - thawing cycles. Duration of drying and freezing were varied from 4 days to 2 weeks. Concentration of metallic elements, pH, Eh and concentration of dissolved iron and sulfate in leachate from each leaching process was measured. To identify the changes of labile fraction in mine soils after each of drying or freezing period, sequential extraction procedure (five fraction) was used to compare labile fraction (i.e., F1 + F2) of metallic elements. The concentration of metallic elements in mine leachate was increased after drying and freezing procedure. The amounts of released metallic element from mine soils was changed depending on their drying or freezing period. In addition, labile fraction of metallic elements in soil was also changed after drying and freezing. The changes in labile fraction after drying and freezing might be due to the increased soil surface area by pore water volume expansion. Further study is therefore needed to evaluate the impact of altered physical properties of soils such as hydration of soil surface area and shrinking by drying and

Emotional Lability and Affective Synchrony in Borderline Personality Disorder

PubMed Central

Schoenleber, Michelle; Berghoff, Christopher R.; Tull, Matthew T.; DiLillo, David; Messman-Moore, Terri; Gratz, Kim L.

2015-01-01

Extant research on emotional lability in borderline personality disorder (BPD) has focused almost exclusively on lability of individual emotions or emotion types, with limited research considering how different types of emotions shift together over time. Thus, this study examined the temporal dynamics of emotion in BPD at the level of both individual emotions (i.e., self-conscious emotions [SCE], anger, and anxiety) and mixed emotions (i.e., synchrony between emotions). One hundred forty-four women from the community completed a diagnostic interview and laboratory study involving five emotion induction tasks (each of which was preceded and followed by a 5-min resting period or neutral task). State ratings of SCE, anger, and anxiety were provided at 14 time points (before and after each laboratory task and resting period). Hierarchical linear modeling results indicate that women with BPD reported greater mean levels of SCE and Anxiety (but not Anger), and greater lability of Anxiety. Women with BPD also exhibited greater variability in lability of all three emotions (suggestive of within-group differences in the relevance of lability to BPD). Results also revealed synchrony (i.e., positive relations) between each possible pair of emotions, regardless of BPD status. Follow-up regression analyses suggest the importance of accounting for lability when examining the role of synchrony in BPD, as the relation of SCE-Anger synchrony to BPD symptom severity was moderated by Anger and SCE lability. Specifically, synchronous changes in SCE and Anger were associated with greater BPD symptom severity when large shifts in SCE were paired with minor shifts in Anger. PMID:27362623

CE of phytosiderophores and related metal species in plants.

PubMed

Xuan, Yue; Scheuermann, Enrico B; Meda, Anderson R; Jacob, Peter; von Wirén, Nicolaus; Weber, Günther

2007-10-01

Phytosiderophores (PS) and the closely related substance nicotianamine (NA) are key substances in metal uptake into graminaceous plants. Here, the CE separation of these substances and related metal species is demonstrated. In particular, the three PS 2'-deoxymugineic acid (DMA), mugineic acid (MA), and 3-epi-hydroxymugineic acid (epi-HMA), and NA, are separated using MES/Tris buffer at pH 7.3. Moreover, three Fe(III) species of the different PS are separated without any stability problems, which are often present in chromatographic analyses. Also divalent metal species of Cu, Ni, and Zn with the ligands DMA and NA are separated with the same method. By using a special, zwitterionic CE capillary, even the separation of two isomeric Fe(III) chelates with the ligand ethylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid (EDDHA) is possible (i.e., meso-Fe(III)-EDDHA and rac-Fe(III)-EDDHA), and for fast separations of NA and respective divalent and trivalent metal species, a polymer CE microchip with suppressed EOF is described. The proposed CE method is applicable to real plant samples, and enables to detect changes of metal species (Cu-DMA, Ni-NA), which are directly correlated to biological processes.

Characterization of plasma labile heme in hemolytic conditions

PubMed Central

Gouveia, Zélia; Carlos, Ana R.; Yuan, Xiaojing; Aires-da-Silva, Frederico; Stocker, Roland; Maghzal, Ghassan J.; Leal, Sónia S.; Gomes, Cláudio M.; Todorovic, Smilja; Iranzo, Olga; Ramos, Susana; Santos, Ana C.; Hamza, Iqbal; Gonçalves, João; Soares, Miguel P.

2018-01-01

Extracellular hemoglobin, a byproduct of hemolysis, can release its prosthetic heme groups upon oxidation. This produces metabolically active heme that is exchangeable between acceptor proteins, macromolecules and low molecular weight ligands, termed here labile heme. As it accumulates in plasma labile heme acts in a pro-oxidant manner and regulates cellular metabolism while exerting pro-inflammatory and cytotoxic effects that foster the pathogenesis of hemolytic diseases. Here, we developed and characterized a panel of heme-specific single domain antibodies (sdAbs) that together with a cellular-based heme reporter assay, allow for quantification and characterization of labile heme in plasma during hemolytic conditions. Using these approaches, we demonstrate that when generated during hemolytic conditions labile heme is bound to plasma molecules with an affinity higher than 10−7 m and that 2–8% (∼ 2–5 μm) of the total amount of heme detected in plasma can be internalized by bystander cells, termed here bioavailable heme. Acute, but not chronic, hemolysis is associated with transient reduction of plasma heme-binding capacity, that is, the ability of plasma molecules to bind labile heme with an affinity higher than 10−7 m. The heme-specific sdAbs neutralize the pro-oxidant activity of soluble heme in vitro, suggesting that these maybe used to counter the pathologic effects of labile heme during hemolytic conditions. Finally, we show that heme-specific sdAbs can be used to visualize cellular heme. In conclusion, we describe a panel of heme-specific sdAbs that when used with other approaches provide novel insights to the pathophysiology of heme. PMID:28783254

Heavy metal tolerance and removal potential in mixed-species biofilm.

PubMed

Grujić, Sandra; Vasić, Sava; Čomić, Ljiljana; Ostojić, Aleksandar; Radojević, Ivana

2017-08-01

The aim of the study was to examine heavy metal tolerance (Cd 2+ , Zn 2+ , Ni 2+ and Cu 2+ ) of single- and mixed-species biofilms (Rhodotorula mucilaginosa and Escherichia coli) and to determine metal removal efficiency (Cd 2+ , Zn 2+ , Ni 2+ , Cu 2+ , Pb 2+ and Hg 2+ ). Metal tolerance was quantified by crystal violet assay and results were confirmed by fluorescence microscopy. Metal removal efficiency was determined by batch biosorption assay. The tolerance of the mixed-species biofilm was higher than the single-species biofilms. Single- and mixed-species biofilms showed the highest sensitivity in the presence of Cu 2+ (E. coli-MIC 4 mg/ml, R. mucilaginosa-MIC 8 mg/ml, R. mucilaginosa/E. coli-MIC 64 mg/ml), while the highest tolerance was observed in the presence of Zn 2+ (E. coli-MIC 80 mg/ml, R. mucilaginosa-MIC 161 mg/ml, R. mucilaginosa-E. coli-MIC 322 mg/ml). The mixed-species biofilm exhibited better efficiency in removal of all tested metals than single-species biofilms. The highest efficiency in Cd 2+ removal was shown by the E. coli biofilm (94.85%) and R. mucilaginosa biofilm (97.85%), individually. The highest efficiency in Cu 2+ (99.88%), Zn 2+ (99.26%) and Pb 2+ (99.52%) removal was shown by the mixed-species biofilm. Metal removal efficiency was in the range of 81.56%-97.85% for the single- and 94.99%-99.88% for the mixed-species biofilm.

The evolution of labile traits in sex- and age-structured populations.

PubMed

Childs, Dylan Z; Sheldon, Ben C; Rees, Mark

2016-03-01

Many quantitative traits are labile (e.g. somatic growth rate, reproductive timing and investment), varying over the life cycle as a result of behavioural adaptation, developmental processes and plastic responses to the environment. At the population level, selection can alter the distribution of such traits across age classes and among generations. Despite a growing body of theoretical research exploring the evolutionary dynamics of labile traits, a data-driven framework for incorporating such traits into demographic models has not yet been developed. Integral projection models (IPMs) are increasingly being used to understand the interplay between changes in labile characters, life histories and population dynamics. One limitation of the IPM approach is that it relies on phenotypic associations between parents and offspring traits to capture inheritance. However, it is well-established that many different processes may drive these associations, and currently, no clear consensus has emerged on how to model micro-evolutionary dynamics in an IPM framework. We show how to embed quantitative genetic models of inheritance of labile traits into age-structured, two-sex models that resemble standard IPMs. Commonly used statistical tools such as GLMs and their mixed model counterparts can then be used for model parameterization. We illustrate the methodology through development of a simple model of egg-laying date evolution, parameterized using data from a population of Great tits (Parus major). We demonstrate how our framework can be used to project the joint dynamics of species' traits and population density. We then develop a simple extension of the age-structured Price equation (ASPE) for two-sex populations, and apply this to examine the age-specific contributions of different processes to change in the mean phenotype and breeding value. The data-driven framework we outline here has the potential to facilitate greater insight into the nature of selection and its

Localization of alkali-labile sites in donkey (Equus asinus) and stallion (Equus caballus) spermatozoa.

PubMed

Cortés-Gutiérrez, Elva I; Dávila-Rodríguez, Martha I; López-Fernández, Carmen; Fernández, José Luis; Crespo, Francisco; Gosálvez, Jaime

2014-01-15

The presence of constitutive alkali-labile sites (ALS) has been investigated using a protocol of DNA breakage detection-fluorescence in situ hybridization and comet assay in spermatozoa of donkey (Equus asinus) and stallion (Equus caballus). These results were compared with those obtained using a similar experimental approach using somatic cells. The relative abundance of ALS was of the order of four times more in spermatozoa than in somatic cells. Alkali-labile sites showed a tendency to cluster localized at the equatorial-distal regions of the sperm. The amount of hybridized signal in the ALS in the sperm of donkey (Equus asinus) was 1.3 times greater than in stallion (Equus caballus), and the length of the comet tail obtained in donkey sperm was 1.6 times longer than that observed in stallion (P < 0.05); however, these differences were not appreciated in somatic cells. In conclusion, ALS localization in sperm is not a randomized event and a different pattern of ALS distribution occurs for each species. These results suggest that ALS represents a species-specific issue related to chromatin organization in sperm and somatic cells in mammalian species, and they might diverge even with very short phylogenetic distances. Copyright © 2014 Elsevier Inc. All rights reserved.

Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA

USGS Publications Warehouse

Balistrieri, L.S.; Seal, R.R.; Piatak, N.M.; Paul, B.

2007-01-01

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 ??g/L in the dynamic mixing and reaction zone that is downstream of the river's confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO4 concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates. The uptake of dissolved metals by aquatic organisms is dependent on the aqueous speciation of the metals and kinetics of complexation reactions between metals, ligands and solid surfaces. Dissolved speciation of Cd, Cu, Ni and Zn in the mixing and reaction zone is assessed using the diffusive gradients in thin films (DGT) technique and results of speciation calculations using the Biotic Ligand Model (BLM). Data from open and restricted pore DGT units indicate that almost all dissolved metal species are inorganic and that aqueous labile or DGT available metal concentrations are generally equal to total dissolved concentrations in the mixing zone. Exceptions occur when labile metal concentrations are underestimated due to competition between H+ and metal ions for Chelex-100 binding sites in the DGT units at low pH values. Calculations using the BLM indicate that dissolved Cd and Zn species in the mixing and reaction zone are predominantly inorganic

Pharmacological ascorbate and ionizing radiation (IR) increase labile iron in pancreatic cancer☆

PubMed Central

Moser, Justin C.; Rawal, Malvika; Wagner, Brett A.; Du, Juan; Cullen, Joseph J.; Buettner, Garry R.

2013-01-01

Labile iron, i.e. iron that is weakly bound and is relatively unrestricted in its redox activity, has been implicated in both the pathogenesis as well as treatment of cancer. Two cancer treatments where labile iron may contribute to their mechanism of action are pharmacological ascorbate and ionizing radiation (IR). Pharmacological ascorbate has been shown to have tumor-specific toxic effects due to the formation of hydrogen peroxide. By catalyzing the oxidation of ascorbate, labile iron can enhance the rate of formation of hydrogen peroxide; labile iron can also react with hydrogen peroxide. Here we have investigated the magnitude of the labile iron pool in tumor and normal tissue. We also examined the ability of pharmacological ascorbate and IR to change the size of the labile iron pool. Although a significant amount of labile iron was seen in tumors (MIA PaCa-2 cells in athymic nude mice), higher levels were seen in murine tissues that were not susceptible to pharmacological ascorbate. Pharmacological ascorbate and irradiation were shown to increase the labile iron in tumor homogenates from this murine model of pancreatic cancer. As both IR and pharmacological ascorbate may rely on labile iron for their effects on tumor tissues, our data suggest that pharmacological ascorbate could be used as a radio-sensitizing agent for some radio-resistant tumors. PMID:24396727

[Novel Hyphenated Techniques of Atomic Spectrometry for Metal Species Interaction with Biomolecules].

PubMed

Li, Yan; Yan, Xiu-ping

2015-09-01

Trace metals may be adopted by biological systems to assist in the syntheses and metabolic functions of genes (DNA and RNA) and proteins in the environment. These metals may be beneficial or may pose a risk to humans and other life forms. Novel hybrid techniques are required for studies on the interaction between different metal species and biomolecules, which is significant for biology, biochemistry, nutrition, agriculture, medicine, pharmacy, and environmental science. In recent years, our group dwells on new hyphenated techniques based on capillary electrophoresis (CE), electrothermal atomic absorption spectrometry (ETAAS), and inductively coupled plasma mass spectroscopy (ICP-MS), and their application for different metal species interaction with biomolecules such as DNA, HSA, and GSH. The CE-ETAAS assay and CE-ICP-MS assay allow sensitively probing the level of biomolecules such as DNA damage by different metal species and extracting the kinetic and thermodynamic information on the interactions of different metal species with biomolecules, provides direct evidences for the formation of different metal species--biomolecule adducts. In addition, the consequent structural information were extracted from circular dichroism (CD) and X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The present works represent the most complete and extensive study to date on the interactions between different metal species with biomolecules, and also provide new evidences for and insights into the interactions of different metal species with biomolecules for further understanding of the toxicological effects of metal species.

An ultrahigh-resolution mass spectrometry index to estimate natural organic matter lability

PubMed Central

D'Andrilli, Juliana; Cooper, William T; Foreman, Christine M; Marshall, Alan G

2015-01-01

Rationale Determining the chemical constituents of natural organic matter (NOM) by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICRMS) remains the ultimate measure for probing its source material, evolution, and transport; however, lability and the fate of organic matter (OM) in the environment remain controversial. FTICRMS-derived elemental compositions are presented in this study to validate a new interpretative method to determine the extent of NOM lability from various environments. Methods FTICRMS data collected over the last decade from the same 9.4 tesla instrument using negative electrospray ionization at the National High Magnetic Field Laboratory in Tallahassee, Florida, was used to validate the application of a NOM lability index. Solid-phase extraction cartridges were used to isolate the NOM prior to FTICRMS; mass spectral peaks were calibrated internally by commonly identified NOM homologous series, and molecular formulae were determined for NOM composition and lability analysis. Results A molecular lability boundary (MLB) was developed from the FTICRMS molecular data, visualized from van Krevelen diagrams, dividing the data into more and less labile constituents. NOM constituents above the MLB at H/C ≥1.5 correspond to more labile material, whereas NOM constituents below the MLB, H/C <1.5, exhibit less labile, more recalcitrant character. Of all marine, freshwater, and glacial environments considered for this study, glacial ecosystems were calculated to contain the most labile OM. Conclusions The MLB extends our interpretation of FTICRMS NOM molecular data to include a metric of lability, and generally ranked the OM environments from most to least labile as glacial > marine > freshwater. Applying the MLB is useful not only for individual NOM FTICRMS studies, but also provides a lability threshold to compare and contrast molecular data with other FTICRMS instruments that survey NOM from around the world. Copyright © 2015

Microbially driven export of labile organic carbon from the Greenland ice sheet

NASA Astrophysics Data System (ADS)

Musilova, Michaela; Tranter, Martyn; Wadham, Jemma; Telling, Jon; Tedstone, Andrew; Anesio, Alexandre M.

2017-04-01

Glaciers and ice sheets are significant sources of dissolved organic carbon and nutrients to downstream subglacial and marine ecosystems. Climatically driven increases in glacial runoff are expected to intensify the impact of exported nutrients on local and regional downstream environments. However, the origin and bioreactivity of dissolved organic carbon from glacier surfaces are not fully understood. Here, we present simultaneous measurements of gross primary production, community respiration, dissolved organic carbon composition and export from different surface habitats of the Greenland ice sheet, throughout the ablation season. We found that microbial production was significantly correlated with the concentration of labile dissolved organic species in glacier surface meltwater. Further, we determined that freely available organic compounds made up 62% of the dissolved organic carbon exported from the glacier surface through streams. We therefore conclude that microbial communities are the primary driver for labile dissolved organic carbon production and recycling on glacier surfaces, and that glacier dissolved organic carbon export is dependent on active microbial processes during the melt season.

Transient acidosis while retrieving a fear-related memory enhances its lability

PubMed Central

Du, Jianyang; Price, Margaret P; Taugher, Rebecca J; Grigsby, Daniel; Ash, Jamison J; Stark, Austin C; Hossain Saad, Md Zubayer; Singh, Kritika; Mandal, Juthika; Wemmie, John A; Welsh, Michael J

2017-01-01

Attenuating the strength of fearful memories could benefit people disabled by memories of past trauma. Pavlovian conditioning experiments indicate that a retrieval cue can return a conditioned aversive memory to a labile state. However, means to enhance retrieval and render a memory more labile are unknown. We hypothesized that augmenting synaptic signaling during retrieval would increase memory lability. To enhance synaptic transmission, mice inhaled CO2 to induce an acidosis and activate acid sensing ion channels. Transient acidification increased the retrieval-induced lability of an aversive memory. The labile memory could then be weakened by an extinction protocol or strengthened by reconditioning. Coupling CO2 inhalation to retrieval increased activation of amygdala neurons bearing the memory trace and increased the synaptic exchange from Ca2+-impermeable to Ca2+-permeable AMPA receptors. The results suggest that transient acidosis during retrieval renders the memory of an aversive event more labile and suggest a strategy to modify debilitating memories. DOI: http://dx.doi.org/10.7554/eLife.22564.001 PMID:28650315

Feasibility of labile Zn phytoextraction using enhanced tobacco and sunflower: results of five- and one-year field-scale experiments in Switzerland.

PubMed

Herzig, Rolf; Nehnevajova, Erika; Pfistner, Charlotte; Schwitzguebel, Jean-Paul; Ricci, Arturo; Keller, Charles

2014-01-01

Phytoextraction with somaclonal variants of tobacco and sunflower mutant lines (non-GMs) with enhanced metal uptake and tolerance can be a sustainable alternative to conventional destructive decontamination methods, especially for stripping bioavailable zinc excess in topsoil. The overall results of a 5-year time series experiment at field scale in north-eastern Switzerland confirm that the labile Zn pool in soil can be lowered by 45-70%, whereas subplots without phytoextraction treatment maintained labile Zn concentrations. In 2011, the phytoextraction experiment site was enlarged by a factor of 3, and the labile 0.1 M NaNO3 extractable Zn concentration in the soil was reduced up to 58% one period after harvest. A Mass Balance Analysis confirmed soil Zn decontamination in line with plant Zn uptake. The plants partially take Zn from the non-labile pool of the totaL The sustainability of Zn phytoextraction in subplots that no longer exceed the Swiss trigger value is now assessed over time. In contrary to the phytoextraction of total soil Zn which needs a long cleaning up time, the bioavailable Zn stripping is feasible within a few years period.

A simple approach to estimate daily loads of total, refractory, and labile organic carbon from their seasonal loads in a watershed

Treesearch

Ying Ouyang; Johnny M. Grace; Wayne C. Zipperer; Jeff Hatten; Janet Dewey

2018-01-01

Loads of naturally occurring total organic carbons (TOC), refractory organic carbon (ROC), and labile organic carbon (LOC) instreams control the availability of nutrients and the solubility and toxicity of contaminants and affect biological activities throughabsorption of light and complex metals with production of carcinogenic compounds....

Accumulation and effects of metal mixtures in two seaweed species.

PubMed

Jarvis, Tayler A; Bielmyer-Fraser, Gretchen K

2015-05-01

Metal pollution, due to various anthropogenic sources, may pose a threat to marine ecosystems. Metals can be introduced into food chains via bioaccumulation in primary producers, and may potentially lead to toxic effects. Macroalgae are used as food by a wide variety of organisms, and are therefore extremely important in aquatic systems. This study investigated the accumulation and effects of metals in two macroalgae species. The green seaweed, Ulva lactuca and the red seaweed, Agardhiella subulata were each concurrently exposed to five metals (Cu, Ni, Pb, Cd, and Zn) and U. lactuca was also exposed to each metal individually for 48 h. Metal accumulation in the seaweed was measured, and various photosynthetic parameters were assessed, using imaging pulse amplitude modulated (PAM) fluorometry. Increased metal accumulation occurred in both seaweed species after 48 h exposure to metal mixtures and each metal individually. The distribution of metals in both seaweed species changed with increasing metal exposure concentrations, resulting in higher proportions of Cu and Zn in the metal-exposed groups, as compared to respective controls. Further, U. lactuca accumulated higher concentrations of metals when exposed to each metal individually rather than in metal mixtures, suggesting interactions among metals for uptake and/or bioaccumulation. Significant impairment of photosynthetic parameters in U. lactuca was observed after exposure to 100 and 1000 μg/L metal mixtures, as well as 100 μg/L of either Cd or Cu. These results demonstrate metal bioaccumulation and toxic effects in important primary producers, and may have implications for higher trophic levels. Published by Elsevier Inc.

Fusion of Escherichia coli heat-stable enterotoxin and heat-labile enterotoxin B subunit.

PubMed

Guzman-Verduzco, L M; Kupersztoch, Y M

1987-11-01

The 3' terminus of the DNA coding for the extracellular Escherichia coli heat-stable enterotoxin (ST) devoid of transcription and translation stop signals was fused to the 5' terminus of the DNA coding for the periplasmic B subunit of the heat-labile enterotoxin (LTB) deleted of ribosomal binding sites and leader peptide. By RNA-DNA hybridization analysis, it was shown that the fused DNA was transcribed in vivo into an RNA species in close agreement with the expected molecular weight inferred from the nucleotide sequence. The translation products of the fused DNA resulted in a hybrid molecule recognized in Western blots (immunoblots) with antibodies directed against the heat-labile moiety. Anti-LTB antibodies coupled to a solid support bound ST and LTB simultaneously when incubated with ST-LTB cellular extracts. By [35S]cysteine pulse-chase experiments, it was shown that the fused ST-LTB polypeptide was converted from a precursor with an equivalent electrophoretic mobility of 20,800 daltons to an approximately 18,500-dalton species, which accumulated within the cell. The data suggest that wild-type ST undergoes at least two processing steps during its export to the culture supernatant. Blocking the natural carboxy terminus of ST inhibited the second proteolytic step and extracellular delivery of the hybrid molecule.

Estimating rates and patterns of morphological evolution from phylogenies: lessons in limb lability from Australian Lerista lizards

PubMed Central

Wiens, John J

2009-01-01

Squamates (lizards and snakes) offer an exciting model system for research on the evolution of body form. A new phylogenetic study in BMC Evolutionary Biology of Australian lizards shows remarkable evolutionary lability in digit numbers among closely related species, but also highlights important challenges in this area. PMID:19291259

Identification of metal species by ESI-MS/MS through release of free metals from the corresponding metal-ligand complexes

PubMed Central

Tsednee, Munkhtsetseg; Huang, Yu-Chen; Chen, Yet-Ran; Yeh, Kuo-Chen

2016-01-01

Electrospray ionization-mass spectrometry (ESI-MS) is used to analyze metal species in a variety of samples. Here, we describe an application for identifying metal species by tandem mass spectrometry (ESI-MS/MS) with the release of free metals from the corresponding metal–ligand complexes. The MS/MS data were used to elucidate the possible fragmentation pathways of different metal–deoxymugineic acid (–DMA) and metal–nicotianamine (–NA) complexes and select the product ions with highest abundance that may be useful for quantitative multiple reaction monitoring. This method can be used for identifying different metal–ligand complexes, especially for metal species whose mass spectra peaks are clustered close together. Different metal–DMA/NA complexes were simultaneously identified under different physiological pH conditions with this method. We further demonstrated the application of the technique for different plant samples and with different MS instruments. PMID:27240899

Using solid 13C NMR coupled with solution 31P NMR spectroscopy to investigate molecular species and lability of organic carbon and phosphorus from aquatic plants in Tai Lake, China.

PubMed

Liu, Shasha; Zhu, Yuanrong; Wu, Fengchang; Meng, Wei; Wang, Hao; He, Zhongqi; Guo, Wenjing; Song, Fanhao; Giesy, John P

2017-01-01

Forms and labilities of plant-derived organic matters (OMs) including carbon (C) and phosphorus (P) were fundamental for understanding their release, degradation and environmental behaviour in lake ecosystems. Thus, solid 13 C and solution 31 P nuclear magnetic resonance (NMR) spectroscopy were used to characterize biomass of six aquatic plants in Tai Lake, China. The results showed that carbohydrates (61.2% of the total C) were predominant C functional group in the solid 13 C NMR spectra of plant biomass, which may indicate high lability and bioavailability of aquatic plants-derived organic matter in lakes. There was 72.6-103.7% of the total P in aquatic plant biomass extracted by NaOH-EDTA extracts. Solution 31 P NMR analysis of these NaOH-EDTA extracts further identified several molecular species of P including orthophosphate (50.1%), orthophosphate monoesters (46.8%), DNA (1.6%) and pyrophosphate (1.4%). Orthophosphate monoesters included β-glycerophosphate (17.7%), hydrolysis products of RNA (11.7%), α-glycerophosphate (9.2%) and other unknown monoesters (2.1%). Additionally, phytate, the major form of organic P in many lake sediments, was detected in floating plant water poppy. These inorganic P (e.g. orthophosphate and pyrophosphate) and organic P (e.g. diester and its degradation products) identified in plant biomass were all labile and bioavailable P, which would play an important role in recycling of P in lakes. These results increased knowledge of chemical composition and bioavailability of OMs derived from aquatic plants in lakes.

Repeated Labilization-Reconsolidation Processes Strengthen Declarative Memory in Humans

PubMed Central

Forcato, Cecilia; Rodríguez, María L. C.; Pedreira, María E.

2011-01-01

The idea that memories are immutable after consolidation has been challenged. Several reports have shown that after the presentation of a specific reminder, reactivated old memories become labile and again susceptible to amnesic agents. Such vulnerability diminishes with the progress of time and implies a re-stabilization phase, usually referred to as reconsolidation. To date, the main findings describe the mechanisms associated with the labilization-reconsolidation process, but little is known about its functionality from a biological standpoint. Indeed, two functions have been proposed. One suggests that destabilization of the original memory after the reminder allows the integration of new information into the background of the original memory (memory updating), and the other suggests that the labilization-reconsolidation process strengthens the original memory (memory strengthening). We have previously reported the reconsolidation of human declarative memories, demonstrating memory updating in the framework of reconsolidation. Here we deal with the strengthening function attributed to the reconsolidation process. We triggered labilization-reconsolidation processes successively by repeated presentations of the proper reminder. Participants learned an association between five cue-syllables and their respective response-syllables. Twenty-four hours later, the paired-associate verbal memory was labilized by exposing the subjects to one, two or four reminders. The List-memory was evaluated on Day 3 showing that the memory was improved when at least a second reminder was presented in the time window of the first labilization-reconsolidation process prompted by the earlier reminder. However, the improvement effect was revealed on Day 3, only when at least two reminders were presented on Day2 and not as a consequence of only retrieval. Therefore, we propose central concepts for the reconsolidation process, emphasizing its biological role and the parametrical constrains

An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

PubMed

Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

2015-04-08

An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.

Labile trace metal contribution of the runoff collector to a semi-urban river.

PubMed

Villanueva, J D; Granger, D; Binet, G; Litrico, X; Huneau, F; Peyraube, N; Le Coustumer, P

2016-06-01

In this study, the distribution of labile trace metals (LTMs; Cd, Co, Cr, Cu, Ni, Pb, and Zn) in a semi-urban runoff collector was examined to assess its influence to a natural aqueous system (Jalle River, Bordeaux, France). This river is of high importance as it is part of a natural reserve dedicated to conserving aquatic flora and fauna. Two sampling campaigns with a differing precipitation condition (period 1, spring season; and period 2, summer season associated with storms) were considered. Precipitation and water flow were monitored. The collector is active as it is receptive to precipitation changes. It influences the river through discharging water, contributing LTMs, and channeling the mass fluxes. During period 2 where precipitation rate is higher, 25 % of the total water volume of the river was supplied by the collector. LTMs were detected at the collector. Measurements were done by using diffusive gradient in thin films (DGT) probes deployed during 1, 7, and 14 days in each period. The results showed that in an instantaneous period (day 1 or D1), most of these trace metals are above the environmental quality standards (Cd, Co, Cr, and Zn). The coefficient of determination (r (2) > 0.50) employed confirmed that the LTM concentrations in the downstream can be explained by the collector. While Co and Cr are from the upstream and the collector, Cd, Cu, and Zn are mostly provided by the collector. Ni, however, is mostly delivered by the upstream. Using the concentrations observed, the river can be affected by the collector in varying ways: (1) adding effect, resulting from the mix of the upstream and the collector (if upstream ˂ downstream); (2) diluted (if upstream ˃ downstream); and (3) conservative or unaffected (upstream ~ downstream). The range of LTM mass fluxes that the collector holds are as follows: (1) limited range or ˂10 g/day, Cd (0.04-1.75 g/day), Co (0.08-05.42 g/day), Ni (0.06-1.45 g/day), and Pb (0.08-9.89 g/day); (2) moderate

Changes in metal mobility assessed by EDTA kinetic extraction in three polluted soils after repeated phytoremediation using a cadmium/zinc hyperaccumulator.

PubMed

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

2018-03-01

Phytoextraction is one of the most promising technologies for the decontamination of metal-polluted agricultural soils. Effects of repeated phytoextraction by the cadmium (Cd)/zinc (Zn) hyperaccumulator Sedum plumbizincicola on metal (Cd, Zn, copper (Cu) and lead (Pb)) mobility were investigated in three contaminated soils with contrasting properties. EDTA kinetic extraction and the two first-order reactions model showed advantages in the assessment of soil metal mobility and clearly discriminated changes in metal fractions induced by phytoextraction. Repeated phytoextraction led to large decreases in readily labile (Q 1 0 ) and less labile (Q 2 0 ) fractions of Cd and Zn in all three soils with the sole exception of an increase in the Q 2 0 of Zn in the highly polluted soil. However, Q 1 0 fractions of soil Cu and Pb showed apparent increases with the sole exception of Pb in the acid polluted soil but showed a higher desorption rate constant (k 1 ). Furthermore, S. plumbizincicola decreased the non-labile fraction (Q 3 0 ) of all metals tested, indicating that the hyperaccumulator can redistribute soil metals from non-labile to labile fractions. This suggests that phytoextraction decreased the mobility of the metals hyperaccumulated by the plant (Cd and Zn) but increased the mobility of the metals not hyperaccumulated (Cu and Pb). Thus, phytoextraction of soils contaminated with mixtures of metals must be performed carefully because of potential increases in the mobility of non-hyperaccumulated metals in the soil and the consequent environmental risks. Copyright © 2017 Elsevier Ltd. All rights reserved.

Application of poly (ethyleneimine) solution as a binding agent in DGT technique for measurement of heavy metals in water.

PubMed

Sui, Dian-Peng; Fan, Hong-Tao; Li, Jing; Li, You; Li, Qiong; Sun, Ting

2013-09-30

A 0.050 mol L(-1) solution of poly (ethyleneimine) (PEI), had been used as a novel binding agent of diffusive gradients in thin-films (DGT) technique (PEI-DGT) for measuring the concentrations of labile Cu(2+), Cd(2+) and Pb(2+) in waters. The binding capacities of the PEI-DGT for Cu(2+), Cd(2+) and Pb(2+) were 11.8, 10.2 and 10.6 μmol L(-1), respectively. The performance of PEI-DGT was independence of pH in the range of 4-8 and ionic strength in the range from 1×10(-4) to 0.1 mol L(-1) (as NaNO3). PEI-DGT could measure 104.7±5.2% of the total concentration of Cd(2+) (0.500 mg L(-1)), 95.2±4.3% of the total Cu(2+) (0.500 mg L(-1)) and 99.2±3.4% of the total Pb(2+) (0.500 mg L(-1)) in synthetic solution. Effects of the ligands on the measurement of labile metals were also investigated in synthetic solutions containing the various concentrations of EDTA and humic acid. In EDTA solution, the concentrations of labile metals measured by PEI-DGT showed good agreement with the theoretical concentrations of free metal ions. In humic acid solution, the concentrations of labile metals measured by PEI-DGT decreased with the increase of the concentrations of humic acid. Several DGT devices with various binding agents, including PEI, sodium polyacrylate and poly(4-styrenesulfonate) solution, were used for the measurement of labile fractions of Cu(2+), Cd(2+) and Pb(2+) in the spiked waters and in mine wastewaters. The results showed that the concentrations of labile metal measured by DGT devices with different binding agents could be significantly different, indicating that the labile fractions of metals were dependent on the binding strength of the binding agents with metals. By choosing binding agents, the useful information on the speciation and bioavailability of the analytes can be provided. Copyright © 2013 Elsevier B.V. All rights reserved.

Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

PubMed

Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

2015-08-18

Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

Protection of Pyruvate,Pi Dikinase from Maize against Cold Lability by Compatible Solutes 1

PubMed Central

Krall, John P.; Edwards, Gerald E.; Andreo, Carlos S.

1989-01-01

Most C4 species are chilling sensitive and certain enzymes like pyruvate,Pi dikinase of the C4 pathway are also cold labile. The ability of cations and compatible solutes to protect maize (Zea mays) dikinase against cold lability was examined. The enzyme in desalted extracts at pH 8 from preilluminated leaves could be protected against cold lability (at 0°C) by the divalent cations Mn2+, Mg2+, and Ca2+. There was substantial protection by sulfate based salts but little protection by chloride based salts of potassium or ammonium (concentration 250 millimolar). The degree of protection against cold lability under limiting MgCl2 (5 millimolar) was pH sensitive (maximum protection at pH 8), but independent of ionic strength (up to 250 millimolar by addition of KCl). In catalysis Mg2+ is required and Mn2+ could not substitute as a cofactor. Several compatible solutes reduced or prevented the cold inactivation of dikinase (in desalted extracts and the partially purified enzyme), including glycerol, proline, glycinebetaine and trimethylamine-N-oxide (TMAO). TMAO and Mg2+ had an additive effect in protecting dikinase against cold inactivation. TMAO could largely substitute for the divalent cation and addition of TMAO during cold treatment prevented further inactivation. Cold inactivation was partially reversed by incubation at room temperature; with addition of TMAO reversal was complete. The temperature dependence of inactivation at pH 8 and 3 millimolar MgCl2 was evaluated by incubation at 2 to 17°C for 45 minutes, followed by assay at room temperature. At preincubation temperatures below 11°C there was a progressive inactivation which could be prevented by TMAO (450 millimolar). The results are discussed relative to possible effects of the solutes on the quaternary structure of this enzyme, which is known to dissociate at low temperatures. PMID:16666527

The adsorption properties of CHx species on metal modified graphene

NASA Astrophysics Data System (ADS)

Tang, Yanan; Shen, Zigang; Chen, Weiguang; Zhu, Dalei; Chai, Huadou; Zhao, Mingyu

2018-05-01

The adsorption geometries of CHx species (x = 0, 1, 2, 3 and 4) on the metal embedded graphene (M-graphene) substrates and the change in electronic structure and magnetic property of systems are analyzed using the first-principles calculations. The calculated results show that the doped metal atoms can provide transferred electrons to neighboring carbon atoms at defective site and thus exhibit positive charges, as well as turning the adsorption sensing of M-graphene for detecting CHx species. Compared with the adsorbed CH3, the adsorption of C, CH and CH2 species exhibit more stability ( >3.0 eV) on M-graphene. Besides, more stable C atom on M-graphene can effectively turn the magnetic property of systems as compared with other species. This result provides a useful reference for fabricating the functional metal-graphene complex as gas sensors and catalytic materials.

Tuning reactivity of diphenylpropynone derivatives with metal-associated amyloid-β species via structural modifications.

PubMed

Liu, Yuzhong; Kochi, Akiko; Pithadia, Amit S; Lee, Sanghyun; Nam, Younwoo; Beck, Michael W; He, Xiaoming; Lee, Dongkuk; Lim, Mi Hee

2013-07-15

A diphenylpropynone derivative, DPP2, has been recently demonstrated to target metal-associated amyloid-β (metal-Aβ) species implicated in Alzheimer's disease (AD). DPP2 was shown to interact with metal-Aβ species and subsequently control Aβ aggregation (reactivity) in vitro; however, its cytotoxicity has limited further biological applications. In order to improve reactivity toward Aβ species and lower cytotoxicity, along with gaining an understanding of a structure-reactivity-cytotoxicity relationship, we designed, prepared, and characterized a series of small molecules (C1/C2, P1/P2, and PA1/PA2) as structurally modified DPP2 analogues. A similar metal binding site to that of DPP2 was contained in these compounds while their structures were varied to afford different interactions and reactivities with metal ions, Aβ species, and metal-Aβ species. Distinct reactivities of our chemical family toward in vitro Aβ aggregation in the absence and presence of metal ions were observed. Among our chemical series, the compound (C2) with a relatively rigid backbone and a dimethylamino group was observed to noticeably regulate both metal-free and metal-mediated Aβ aggregation to different extents. Using our compounds, cell viability was significantly improved, compared to that with DPP2. Lastly, modifications on the DPP framework maintained the structural properties for potential blood-brain barrier (BBB) permeability. Overall, our studies demonstrated that structural variations adjacent to the metal binding site of DPP2 could govern different metal binding properties, interactions with Aβ and metal-Aβ species, reactivity toward metal-free and metal-induced Aβ aggregation, and cytotoxicity of the compounds, establishing a structure-reactivity-cytotoxicity relationship. This information could help gain insight into structural optimization for developing nontoxic chemical reagents toward targeting metal-Aβ species and modulating their reactivity in biological

Memory expression is independent of memory labilization/reconsolidation.

PubMed

Barreiro, Karina A; Suárez, Luis D; Lynch, Victoria M; Molina, Víctor A; Delorenzi, Alejandro

2013-11-01

There is growing evidence that certain reactivation conditions restrict the onset of both the destabilization phase and the restabilization process or reconsolidation. However, it is not yet clear how changes in memory expression during the retrieval experience can influence the emergence of the labilization/reconsolidation process. To address this issue, we used the context-signal memory model of Chasmagnathus. In this paradigm a short reminder that does not include reinforcement allows us to evaluate memory labilization and reconsolidation, whereas a short but reinforced reminder restricts the onset of such a process. The current study investigated the effects of the glutamate antagonists, APV (0.6 or 1.5 μg/g) and CNQX (1 μg/g), prior to the reminder session on both behavioral expression and the reconsolidation process. Under conditions where the reminder does not initiate the labilization/reconsolidation process, APV prevented memory expression without affecting long-term memory retention. In contrast, APV induced amnesic effects in the long-term when administered before a reminder session that triggers reconsolidation. Under the present parametric conditions, the administration of CNQX prior to the reminder that allows memory to enter reconsolidation impairs this process without disrupting memory expression. Overall, the present findings suggest that memory reactivation--but not memory expression--is necessary for labilization and reconsolidation. Retrieval and memory expression therefore appear not to be interchangeable concepts. Copyright © 2013 Elsevier Inc. All rights reserved.

Impact of Labile Zinc on Heart Function: From Physiology to Pathophysiology

PubMed Central

Turan, Belma; Tuncay, Erkan

2017-01-01

Zinc plays an important role in biological systems as bound and histochemically reactive labile Zn2+. Although Zn2+ concentration is in the nM range in cardiomyocytes at rest and increases dramatically under stimulation, very little is known about precise mechanisms controlling the intracellular distribution of Zn2+ and its variations during cardiac function. Recent studies are focused on molecular and cellular aspects of labile Zn2+ and its homeostasis in mammalian cells and growing evidence clarified the molecular mechanisms underlying Zn2+-diverse functions in the heart, leading to the discovery of novel physiological functions of labile Zn2+ in parallel to the discovery of subcellular localization of Zn2+-transporters in cardiomyocytes. Additionally, important experimental data suggest a central role of intracellular labile Zn2+ in excitation-contraction coupling in cardiomyocytes by shaping Ca2+ dynamics. Cellular labile Zn2+ is tightly regulated against its adverse effects through either Zn2+-transporters, Zn2+-binding molecules or Zn2+-sensors, and, therefore plays a critical role in cellular signaling pathways. The present review summarizes the current understanding of the physiological role of cellular labile Zn2+ distribution in cardiomyocytes and how a remodeling of cellular Zn2+-homeostasis can be important in proper cell function with Zn2+-transporters under hyperglycemia. We also emphasize the recent investigations on Zn2+-transporter functions from the standpoint of human heart health to diseases together with their clinical interest as target proteins in the heart under pathological condition, such as diabetes. PMID:29137144

Impact of Labile Zinc on Heart Function: From Physiology to Pathophysiology.

PubMed

Turan, Belma; Tuncay, Erkan

2017-11-12

Zinc plays an important role in biological systems as bound and histochemically reactive labile Zn 2+ . Although Zn 2+ concentration is in the nM range in cardiomyocytes at rest and increases dramatically under stimulation, very little is known about precise mechanisms controlling the intracellular distribution of Zn 2+ and its variations during cardiac function. Recent studies are focused on molecular and cellular aspects of labile Zn 2+ and its homeostasis in mammalian cells and growing evidence clarified the molecular mechanisms underlying Zn 2+ -diverse functions in the heart, leading to the discovery of novel physiological functions of labile Zn 2+ in parallel to the discovery of subcellular localization of Zn 2+ -transporters in cardiomyocytes. Additionally, important experimental data suggest a central role of intracellular labile Zn 2+ in excitation-contraction coupling in cardiomyocytes by shaping Ca 2+ dynamics. Cellular labile Zn 2+ is tightly regulated against its adverse effects through either Zn 2+ -transporters, Zn 2+ -binding molecules or Zn 2+ -sensors, and, therefore plays a critical role in cellular signaling pathways. The present review summarizes the current understanding of the physiological role of cellular labile Zn 2+ distribution in cardiomyocytes and how a remodeling of cellular Zn 2+ -homeostasis can be important in proper cell function with Zn 2+ -transporters under hyperglycemia. We also emphasize the recent investigations on Zn 2+ -transporter functions from the standpoint of human heart health to diseases together with their clinical interest as target proteins in the heart under pathological condition, such as diabetes.

Dinuclear PhotoCORMs: Dioxygen-Assisted Carbon Monoxide Uncaging from Long-Wavelength-Absorbing Metal-Metal-Bonded Carbonyl Complexes.

PubMed

Li, Zhi; Pierri, Agustin E; Huang, Po-Ju; Wu, Guang; Iretskii, Alexei V; Ford, Peter C

2017-06-05

We describe a new strategy for triggering the photochemical release of caged carbon monoxide (CO) in aerobic media using long-wavelength visible and near-infrared (NIR) light. The dinuclear rhenium-manganese carbonyl complexes (CO) 5 ReMn(CO) 3 (L), where L = phenanthroline (1), bipyridine (2), biquinoline (3), or phenanthrolinecarboxaldehyde (4), each show a strong metal-metal-bond-to-ligand (σ MM → π L *) charge-transfer absorption band at longer wavelengths. Photolysis with deep-red (1 and 2) or NIR (3 and 4) light leads to homolytic cleavage of the Re-Mn bonds to give mononuclear metal radicals. In the absence of trapping agents, these radicals primarily recombine to reform dinuclear complexes. In oxygenated media, however, the radicals react with dioxygen to form species much more labile toward CO release via secondary thermal and/or photochemical reactions. Conjugation of 4, with an amine-terminated poly(ethylene glycol) oligomer, gives a water-soluble derivative with similar photochemistry. In this context, we discuss the potential applications of these dinuclear complexes as visible/NIR-light-photoactivated CO-releasing moieties (photoCORMs).

Characteristics of labile organic carbon fractions in reclaimed mine soils: Evidence from three reclaimed forests in the Pingshuo opencast coal mine, China.

PubMed

Yuan, Ye; Zhao, Zhongqiu; Li, Xuezhen; Wang, Yangyang; Bai, Zhongke

2018-02-01

The reclamation of discarded spoils has the potential to stimulate carbon (C) sequestration in reclaimed mine soils (RMSs). Nevertheless, to date the temporal dynamics of labile organic C fractions have not been sufficiently elucidated in RMSs. In this study, soil organic carbon (SOC) and labile organic C fractions, including microbial biomass organic C (MBC), easily oxidizable organic C (EOC) and dissolved organic C (DOC), were determined in Robinia pseudoacacia monoculture forests (reclamation periods of 0, 8, 10, 13, 15, 18 and 30years), Pinus tabuliformis forests (reclamation periods of 0, 10, 19, 23 and 25years) and Ulmus pumila forests (reclamation periods of 0, 18, 20 and 22years) situated on RMSs in the Pingshuo opencast coal mine, China. Changes in labile organic C fractions within the soil profiles (0-100cm) were also identified at the 18- or 19-year plots under the three monoculture forests. Our results showed that, SOC and labile organic C fractions, together with soil microbial quotient (SMQ) and C management index (CMI), increased with time since reclamation, indicating that the quality of RMSs improved over time after initial reclamation under the three forest types. R. pseudoacacia significantly increased the accretion of SOC and EOC in the early stage of reclamation while P. tabuliformis accelerated the accumulation of the MBC fraction. Results for U. pumila indicated that this species had a better ability to store C in RMSs 10years or more after reclamation. SOC and labile organic C fractions both had S-shaped distributions within the soil profiles (0-100cm), with the 0-20cm layer recording the highest values (P<0.05). Labile organic C fractions were closely associated and correlated with soil physicochemical properties; our results also showed that nitrogen played an important role in the development of labile organic C fractions. Overall, reclamation accelerated the accretion of both SOC and labile organic C fractions, results of which varied

Exotic species with explicit noble metal-noble gas-noble metal linkages.

PubMed

Moreno, Norberto; Restrepo, Albeiro; Hadad, C Z

2018-02-14

We present a study of the isoelectronic Pt 2 Ng 2 F 4 and [Au 2 Ng 2 F 4 ] 2+ species with noble gas atoms (Ng = Kr, Xe, Rn) acting as links bridging the two noble metal atoms. The stability of the species is investigated using several thermodynamic, kinetic and reactivity indicators. The results are compared against [AuXe 4 ] 2+ , which is thermodynamically unstable in the gas phase but is stabilized in the solid state to the point that it has been experimentally detected as [AuXe 4 ](Sb 2 F 11 ) 2 (S. Seidel and K. Seppelt, Science, 2000, 290, 117-118). Our results indicate that improving upon [AuXe 4 ] 2+ , these exotic combinations between the a priori non-reactive noble metals and noble gases lead to metastable species, and, therefore, they have the possibility of existing in the solid state under adequate conditions. Our calculations include accurate energies and geometries at both the CCSD/SDDALL and MP2/SDDALL levels. We offer a detailed description of the nature of the bonding interactions using orbital and density-based analyses. The computational evidence suggests partially covalent and ionic interactions as the stabilization factors.

DNA lability induced by nimustine and ramustine in rat glioma cells.

PubMed Central

Mineura, K; Fushimi, S; Itoh, Y; Kowada, M

1988-01-01

The DNA labile sites induced by two nitrosoureas, nimustine (ACNU) and ramustine (MCNU) synthesised in Japan, have been examined in highly reiterated DNA sequences of rat glioma cells. Reiterated fragments of 167 and 203 base pairs (bp), obtained after Hind III and Hae III restriction endonuclease digestion of rat glioma cells DNA, were used as target DNA sequences to determine the labile sites. In vitro reaction with ACNU and MCNU resulted in scission products corresponding to the locations of guanine. Subsequent piperidine hydrolysis produced more frequent breaks of the phosphodiester bonds at guanine positions, thus forming alkali-labile sites. Images PMID:3236017

Trace metals in upland headwater lakes in Ireland.

PubMed

Burton, Andrew; Aherne, Julian; Hassan, Nouri

2013-10-01

Trace elements (n = 23) in Irish headwater lakes (n = 126) were investigated to determine their ambient concentrations, fractionation (total, dissolved, and non-labile), and geochemical controls. Lakes were generally located in remote upland, acid-sensitive regions along the coastal margins of the country. Total trace metal concentrations were low, within the range of natural pristine surface waters; however, some lakes (~20 %) had inorganic labile aluminum and manganese at levels potentially harmful to aquatic organisms. Redundancy analysis indicated that geochemical weathering was the dominant controlling factor for total metals, compared with acidity for dissolved metals. In addition, many metals were positively correlated with dissolved organic carbon indicating their affinity (or complexation) with humic substances (e.g., aluminum, iron, mercury, lead). However, a number of trace metals (e.g., aluminum, mercury, zinc) were correlated with anthropogenic acidic deposition (i.e., non-marine sulfate), suggesting atmospheric sources or elevated leaching owing to acidic deposition. As transboundary air pollution continues to decline, significant changes in the cycling of trace metals is anticipated.

A universal fluorogenic switch for Fe(ii) ion based on N-oxide chemistry permits the visualization of intracellular redox equilibrium shift towards labile iron in hypoxic tumor cells.

PubMed

Hirayama, Tasuku; Tsuboi, Hitomi; Niwa, Masato; Miki, Ayaji; Kadota, Satoki; Ikeshita, Yukie; Okuda, Kensuke; Nagasawa, Hideko

2017-07-01

Iron (Fe) species play a number of biologically and pathologically important roles. In particular, iron is a key element in oxygen sensing in living tissue where its metabolism is intimately linked with oxygen metabolism. Regulation of redox balance of labile iron species to prevent the generation of iron-catalyzed reactive oxygen species (ROS) is critical to survival. However, studies on the redox homeostasis of iron species are challenging because of a lack of a redox-state-specific detection method for iron, in particular, labile Fe 2+ . In this study, a universal fluorogenic switching system is established, which is responsive to Fe 2+ ion based on a unique N-oxide chemistry in which dialkylarylamine N-oxide is selectively deoxygenized by Fe 2+ to generate various fluorescent probes of Fe 2+ -CoNox-1 (blue), FluNox-1 (green), and SiRhoNox-1 (red). All the probes exhibited fluorescence enhancement against Fe 2+ with high selectivity both in cuvette and in living cells. Among the probes, SiRhoNox-1 showed an excellent fluorescence response with respect to both reaction rate and off/on signal contrast. Imaging studies were performed showing the intracellular redox equilibrium shift towards labile iron in response to reduced oxygen tension in living cells and 3D tumor spheroids using SiRhoNox-1, and it was found that the hypoxia induction of labile Fe 2+ is independent of iron uptake, hypoxia-induced signaling, and hypoxia-activated enzymes. The present studies demonstrate the feasibility of developing sensitive and specific fluorescent probes for Fe 2+ with refined photophysical characteristics that enable their broad application in the study of iron in various physiological and pathological conditions.

Metal speciation and potential bioavailability changes during discharge and neutralisation of acidic drainage water.

PubMed

Simpson, Stuart L; Vardanega, Christopher R; Jarolimek, Chad; Jolley, Dianne F; Angel, Brad M; Mosley, Luke M

2014-05-01

The discharge of acid drainage from the farm irrigation areas to the Murray River in South Australia represents a potential risk to water quality. The drainage waters have low pH (2.9-5.7), high acidity (up to 1190 mg L(-1) CaCO3), high dissolved organic carbon (10-40 mg L(-1)), and high dissolved Al, Co, Ni and Zn (up to 55, 1.25, 1.30 and 1.10 mg L(-1), respectively) that represent the greatest concern relative to water quality guidelines (WQGs). To provide information on bioavailability, changes in metal speciation were assessed during mixing experiments using filtration (colloidal metals) and Chelex-lability (free metal ions and weak inorganic metal complexes) methods. Following mixing of drainage and river water, much of the dissolved aluminium and iron precipitated. The concentrations of other metals generally decreased conservatively in proportion to the dilution initially, but longer mixing periods caused increased precipitation or adsorption to particulate phases. Dissolved Co, Mn and Zn were typically 95-100% present in Chelex-labile forms, whereas 40-70% of the dissolved nickel was Chelex-labile and the remaining non-labile fraction of dissolved nickel was associated with fine colloids or complexed by organic ligands that increased with time. Despite the different kinetics of precipitation, adsorption and complexation reactions, the dissolved metal concentrations were generally highly correlated for the pooled data sets, indicating that the major factors controlling the concentrations were similar for each metal (pH, dilution, and time following mixing). For dilutions of the drainage waters of less than 1% with Murray River water, none of the metals should exceed the WQGs. However, the high concentrations of metals associated with fine precipitates within the receiving waters may represent a risk to some aquatic organisms. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Recognition- and Reactivity-Based Fluorescent Probes for Studying Transition Metal Signaling in Living Systems

PubMed Central

2015-01-01

Conspectus Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed “recognition” and “reactivity”. Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give

Radial metal concentration profiles in trees growing on highly contaminated soils.

PubMed

Superville, Pierre-Jean; de Winter, Niels; Phung, Anh Tuan; Proix, Nicolas; Baeyens, Willy; Gao, Yue

2017-04-01

The soil around Metaleurop, a big smelter, is heavily contaminated by Zn, Pb, Cd and Cu. In order to compare the impact of different soil amendments on the metal availability to trees, the polluted soil section was divided in a reference parcel and two others with either sulfo-calcic or silico-aluminous ash amendments. Five different tree species were planted on the parcels and the uptake of heavy metals in these trees was studied. Total and labile metal fractions were assessed in each of the 3 parcels. The mobility and assimilation of the metals was highest in the non-amended, reference soil parcel which had the lowest pH, organic matter and carbonate content. In all soils, pH decreased while organic matter content and mobility of the metals increased over time. Highest bulk concentrations of trace metals were found in white willow trees (Salix alba L.). Laser ablation-ICPMS was used to study changes in metal accumulation over a period of 10 years after planting the trees. The radial metal profiles in the trunk core samples varied between elements and tree species, however, in all willow trees the radial Cd and Zn profiles were significantly correlated. Radial pollutant concentration patterns are discussed in terms of seasonal effects, health status, tree species and metal mobility in the soil. For Cd and Zn, the profiles were influenced by their mobility in the soils. In general, periodical patterns were observed for Pb. Cu concentration profiles were decreasing over time, with the strongest decrease in the initial growth period. Copyright © 2016 Elsevier Ltd. All rights reserved.

Elemental composition and functional groups in soil labile organic matter fractions

USDA-ARS?s Scientific Manuscript database

Labile organic matter fractions are major components involved in nutrient cycle in soil. In this chapter, we examine three labile organic matter fraction: light fraction (LF), humic acid (HA) and fulvic acid (HA) in Alabama cotton soils (ultisol) amended with chemical fertilizer (NH4NO3) and poult...

Indirect effects of heavy metals on parasites may cause shifts in snail species compositions.

PubMed

Lefcort, H; Aguon, M Q; Bond, K A; Chapman, K R; Chaquette, R; Clark, J; Kornachuk, P; Lang, B Z; Martin, J C

2002-07-01

We studied the direct and indirect effects of pollution on the distributions and abundances of two closely related species of pulmonate freshwater snails. Physella columbiana is more numerous at heavy metal-polluted lakes, and Lymnaea palustris is more numerous at reference lakes. Both species are present at all sites, as are predatory bluegill sunfish (Lepomis macrochirus). The direct effects examined included the snails' growth and reproduction in both the presence and absence of heavy metals and their short-term survival when exposed to large concentrations of heavy metals. The indirect effects were the species' ability to elude capture by sunfish and the diversity and abundance of parasites within the snails. We found that heavy metals had little direct effect on growth and reproduction and that both species acquired similar levels of metals in their tissues. Interestingly, P. columbiana (the more abundant species in polluted lakes) actually exhibited higher recruitment in the absence of metals than did L. palustris (reference lakes). L. palustris has life history characteristics that favor increased growth and reduced reproduction. These characteristics resulted in decreased predation of adults by gape-limited predators and a greater ability to cope with heavy parasite burdens. P. columbiana exhibited slower growth, which resulted in increased predation although higher reproduction rates may compensate.The major effect of heavy metals on species distributions was indirect on the snails' parasites. Parasites appeared to be very susceptible to metals, and this resulted in lower parasite diversity and intensities at polluted sites for both species of snails. P. columbiana may only be able to outcompete L. palustris at polluted sites due to the indirect effects of heavy metals; the negative effect of heavy metals on parasites, and a proposed negative effect of metals on the foraging ability of sunfish that favors the faster-reproducing P. columbiana.

Maternal emotion socialization differentially predicts third-grade children's emotion regulation and lability.

PubMed

Rogers, Megan L; Halberstadt, Amy G; Castro, Vanessa L; MacCormack, Jennifer K; Garrett-Peters, Patricia

2016-03-01

Numerous parental emotion socialization factors have been implicated as direct and indirect contributors to the development of children's emotional competence. To date, however, no study has combined parents' emotion-related beliefs, behaviors, and regulation strategies in one model to assess their cumulative-as well as unique-contributions to children's emotion regulation. We considered the 2 components that have recently been distinguished: emotion regulation and emotional lability. We predicted that mothers' beliefs about the value of and contempt for children's emotions, mothers' supportive and nonsupportive reactions to their children's emotions, as well as mothers' use of cognitive reappraisal and suppression of their own emotions would each contribute unique variance to their children's emotion regulation and lability, as assessed by children's teachers. The study sample consisted of an ethnically and socioeconomically diverse group of 165 mothers and their third-grade children. Different patterns emerged for regulation and lability: Controlling for family income, child gender, and ethnicity, only mothers' lack of suppression as a regulatory strategy predicted greater emotion regulation in children, whereas mothers' valuing of children's emotions, mothers' lack of contempt for children's emotions, mothers' use of cognitive reappraisal to reinterpret events, and mothers' lack of emotional suppression predicted less lability in children. These findings support the divergence of emotion regulation and lability as constructs and indicate that, during middle childhood, children's lability may be substantially and uniquely affected by multiple forms of parental socialization. (c) 2016 APA, all rights reserved).

Homeostasis of metals in the progression of Alzheimer's disease.

PubMed

González-Domínguez, Raúl; García-Barrera, Tamara; Gómez-Ariza, José Luis

2014-06-01

In order to study the involvement of metals in the progression of Alzheimer's disease, serum samples from patients with Alzheimer and mild cognitive impairment were investigated. For this purpose, metal content was analyzed after size-fractionation of species and then, inter-element and inter-fraction ratios were computed. In this way, the analysis allowed discovering changes that could be used as markers of disease, but also provided a new insight into the interactions in the homeostasis of elements in neurodegeneration and its progression. Aluminum and labile forms of iron and copper were increased in demented patients, while manganese, zinc and selenium were reduced. Interestingly, levels of different elements, principally iron, aluminum and manganese, were closely inter-related, which could evidence a complex interdependency between the homeostasis of the different metals in this disorder. On the other hand, imbalances in metabolism of copper, zinc and selenium could be associated to abnormal redox status. Therefore, this study may contribute to our understanding of the pathological mechanisms related to metals in Alzheimer's disease.

Biogeochemical implications of labile phosphorus in forest soils determined by the Hedley fractionation procedure.

PubMed

Johnson, Arthur H; Frizano, Jaqueline; Vann, David R

2003-05-01

Forest ecologists and biogeochemists have used a variety of extraction techniques to assess labile vs. non-labile soil P pools in chronosequences, the balance between biological vs. geochemical control of P transformations across a wide range of soil orders, the role of plants with either N-fixing or mycorrhizal symbionts in controlling soil P fractions, and to make inferences about plant-available P. Currently, variants of the sequential extraction procedure developed by M. J. Hedley and co-workers afford the greatest discrimination among labile and non-labile organic and inorganic P pools. Results of recent studies that used this technique to evaluate P fractions in forest soils indicate the following: (1) in intact, highly weathered forest soils of the humid tropics, Hedley-labile P values are several times larger than extractable P values resulting from mildly acidic extracting solutions which were commonly used in the past 2 decades; (2) pools of Hedley-labile P are several times larger than the annual forest P requirement and P required from the soil annually in both temperate and tropical forests; (3) long-term trends in non-labile P pools during pedogenesis are adequately represented by the Walker and Syers' model of changes in P fractionation during soil development. However, to better represent trends in pools that can supply plant-available P across forest soils of different age and weathering status, the paradigm should be modified; and (4) across a wide range of tropical and temperate forest soils, organic matter content is an important determinant of Hedley-labile P.

Observations of Metallic Species in Mercury's Exosphere

NASA Technical Reports Server (NTRS)

Killen, Rosemary M.; Potter, Andrew E.; Vervack, Ronald J., Jr.; Bradley, E. Todd; McClintock, William E.; Anderson, Carrie M.; Burger, Matthew H.

2010-01-01

From observations of the metallic species sodium (Na), potassium (K), and magnesium (Mg) in Mercury's exosphere, we derive implications for source and loss processes. All metallic species observed exhibit a distribution and/or line width characteristic of high to extreme temperature - tens of thousands of degrees K. The temperatures of refractory species, including magnesium and calcium, indicate that the source process for the atoms observed in the tail and near-planet exosphere are consistent with ion sputtering and/or impact vaporization of a molecule with subsequent dissociation into the atomic form. The extended Mg tail is consistent with a surface abundance of 5-8% Mg by number, if 30% of impact-vaporized Mg remains as MgO and half of the impact vapor condenses. Globally, ion sputtering is not a major source of Mg, but locally the sputtered source can be larger than the impact vapor source. We conclude that the Na and K in Mercury's exosphere can be derived from a regolith composition similar to that of Luna 16 soil (or Apollo 17 orange glass), in which the abundance by number is 0.0027 (0.0028) for Na and 0.0006 (0.0045) for K.

Effects of labile carbon addition on a headwater stream food web

Treesearch

Heidi S. Wilcox; J. Bruce Wallace; Judy L. Meyer; Jonathan P. Benstead

2005-01-01

We added dextrose for two 8-week periods (summer and autumn) to a highly heterotrophic headwater stream in North Carolina, U.S.A., to examine the responses of its benthic food web to increased labile carbon. We hypothesized that addition of labile carbon would elevate microbial abundance and activity, resulting in greater resource availability and higher...

Oxygen consumption and labile dissolved organic carbon uptake by benthic biofilms

NASA Astrophysics Data System (ADS)

de Falco, Natalie; Boano, Fulvio; Arnon, Shai

2015-04-01

Biogeochemical activity in streams is often magnified at interfaces, such as in the case of biofilm growth near the surface of the stream sediments. The objective of this study was to evaluate the relative importance of surficial biofilms versus the biofilm in the hyporheic zone to the processes of biodegradation of a labile dissolved organic carbon (DOC) and to oxygen consumption. Experiments were conducted in a recirculating flume, equipped with a drainage system that enables the control on losing and gaining fluxes. A surficial biofilm was developed over a sandy streambed with dune-shaped bed forms, by providing labile DOC (sodium benzoate) and nitrate. Homogeneously distributed biofilm was obtained by the same feeding strategy but with mixing the sediments manually on a daily basis. After the biofilm growth period, transformation of the labile DOC under different overlying velocities and losing or gaining fluxes was studied after spiking with sodium benzoate and by monitoring the decrease in DOC concentration in the bulk water over time using an online UV/Vis spectrophotometer. In addition, oxygen profiles across the water-streambed interface were measured at different locations along the bed form using oxygen microelectrodes. Preliminary results showed that the rate of labile DOC degradation increased exponentially with increasing overlying water velocity, regardless of the type of biofilm. Gaining and losing conditions did not play a critical role in the DOC degradation regardless of the type of biofilm, because the labile DOC was quickly utilized close to the surface. Under losing conditions, complete depletion of oxygen was observed within the top 5 millimeters, regardless of the biofilm type. In contrast, oxygen profiles under gaining condition showed an incomplete consumption of oxygen followed by an increase in the concentration of oxygen deeper in the sediments due to the upward flow of oxygenated groundwater. The results suggest that the transformation

The five-factor model of impulsivity-like traits and emotional lability in aggressive behavior.

PubMed

Dvorak, Robert D; Pearson, Matthew R; Kuvaas, Nicholas J

2013-01-01

Factors that increase automatic psychological processes may result in impulsive action and, consequently, aggressive behavior. The current cross-sectional study examined the association between the five-factor model of impulsivity-like traits (negative urgency, positive urgency, premeditation, perseverance, and sensation seeking), emotional lability, and physically aggressive behaviors among college students (n = 481) in a negative binomial hurdle model. In the logistic portion of the model, emotional lability was related to a higher likelihood of engaging in aggressive acts in the past 6 months. The association between emotional lability and the likelihood of aggressive behavior was moderated by two impulsivity-like traits: negative urgency and positive urgency. Specifically, emotional lability was related to engaging in aggressive acts among those with high negative urgency, and among those with low positive urgency. In the count portion of the model, emotional lability was uniquely related to the number of aggressive acts in the past 6 months. Our results indicate that emotional lability and facets of impulsivity interactively relate to engagement in aggressive behavior, suggesting that these variables be integrated into models of aggression. © 2013 Wiley Periodicals, Inc.

Ultrafast photochemistry of polyatomic molecules containing labile halogen atoms in solution

NASA Astrophysics Data System (ADS)

Mereshchenko, Andrey S.

Because breaking and making of chemical bonds lies at the heart of chemistry, this thesis focuses on dynamic studies of labile molecules in solutions using ultrafast transient absorption spectroscopy. Specifically, my interest is two-fold: (i) novel reaction intermediates of polyhalogenated carbon, boron and phosphorus compounds; (ii) photophysics and photochemistry of labile copper(II) halide complexes. Excitation of CH2Br2, CHBr3, BBr 3, and PBr3 into n(Br)sigma*(X-Br) states, where X=C, B, or P, leads to direct photoisomerization with formation of isomers having Br-Br bonds as well as rupture of one of X-Br bonds with the formation of a Br atom and a polyatomic radical fragment, which subsequently recombine to form similar isomer products. Nonpolar solvation stabilizes the isomers, consistent with intrinsic reaction coordinate calculations of the isomer ground state potential energy surfaces at the density functional level of theory, and consequently, the involvement of these highly energetic species on chemically-relevant time scales needs to be taken into account. Monochlorocomplexes in methanol solutions promoted to the ligand-to-metal charge transfer (LMCT) excited state predominantly undergo internal conversion via back electron transfer, giving rise to vibrationally hot ground-state parent complexes. Copper-chloride homolitical bond dissociation yielding the solvated copper(I) and Cl- atom/solvent CT complexes constitutes a minor pathway. Insights into ligand substitution mechanisms were acquired by monitoring the recovery of monochloro complexes at the expense of two unexcited dichloro- and unsubstituted forms of Cu(II) complexes also present in the solution. Detailed description of ultrafast excited-state dynamics of CuCl 42- complexes in acetonitrile upon excitation into all possible Ligand Field (LF) excited states and two most intense LMCT transitions is reported. The LF states were found to be nonreactive with lifetimes remarkably longer than those

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.

Affect lability predicts occurrence of suicidal ideation in bipolar patients: a two-year prospective study.

PubMed

Ducasse, D; Jaussent, I; Guillaume, S; Azorin, J M; Bellivier, F; Belzeaux, R; Bougerol, T; Etain, B; Gard, S; Henry, C; Kahn, J P; Leboyer, M; Loftus, J; Passerieux, C; Olié, E; Courtet, P

2017-05-01

The aim of our study was to investigate, in bipolar patients, whether affect lability was associated with suicidal ideation incidence during 2-year follow-up, and which subtype of affect lability was associated with suicidal ideation. A total of 319 euthymic or mildly depressed bipolar outpatients recruited in the French FondaMental Advanced Centres of Expertise for Bipolar Disorder were divided into two subgroups according to the occurrence of suicidal ideation during a 2-year follow-up. Affect lability was assessed by the French version of the Affect Lability Scale. Bipolar patients with high affect lability were more likely to report suicidal ideation during follow-up, even after adjustment for age, study level, rapid cycling, current depression level, anxiety disorder, and lifetime history SA (OR = 2.47; 95% CI [1.15-5.30], P = 0.01). The risk of suicidal ideation increased with the level of affect lability. More specifically, the propensity to switch from neutral to elation affect, from anxious to depressive affect (or inversely), and from neutral to anger affect predicted suicidal ideation. Reducing affective lability could become a new therapeutic target of suicidal prevention in bipolar disorder. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Assessment of heavy metal tolerance in native plant species from soils contaminated with electroplating effluent.

PubMed

Sainger, Poonam Ahlawat; Dhankhar, Rajesh; Sainger, Manish; Kaushik, Anubha; Singh, Rana Pratap

2011-11-01

Heavy metals concentrations of (Cr, Zn, Fe, Cu and Ni) were determined in plants and soils contaminated with electroplating industrial effluent. The ranges of total soil Cr, Zn, Fe, Cu and Ni concentrations were found to be 1443-3240, 1376-3112, 683-2228, 263-374 and 234-335 mg kg⁻¹, respectively. Metal accumulation, along with hyperaccumulative characteristics of the screened plants was investigated. Present study highlighted that metal accumulation in different plants varied with species, tissues and metals. Only one plant (Amaranthus viridis) accumulated Fe concentrations over 1000 mg kg⁻¹. On the basis of TF, eight plant species for Zn and Fe, three plant species for Cu and two plant species for Ni, could be used in phytoextraction technology. Although BAF of all plant species was lesser than one, these species exhibited high metal adaptability and could be considered as potential hyperaccumulators. Phytoremediation potential of these plants can be used to remediate metal contaminated soils, though further investigation is still needed. Copyright © 2011 Elsevier Inc. All rights reserved.

Radiation-induced heat-labile sites that convert into DNA double-strand breaks

NASA Technical Reports Server (NTRS)

Rydberg, B.; Chatterjee, A. (Principal Investigator)

2000-01-01

The yield of DNA double-strand breaks (DSBs) in SV40 DNA irradiated in aqueous solution was found to increase by more than a factor of two as a result of postirradiation incubation of the DNA at 50 degrees C and pH 8.0 for 24 h. This is in agreement with data from studies performed at 37 degrees C that were published previously. Importantly, similar results were also obtained from irradiation of mammalian DNA in agarose plugs. These results suggest that heat-labile sites within locally multiply damaged sites are produced by radiation and are subsequently transformed into DSBs. Since incubation at 50 degrees C is typically employed for lysis of cells in commonly used pulsed-field gel assays for detection of DSBs in mammalian cells, the possibility that heat-labile sites are present in irradiated cells was also studied. An increase in the apparent number of DSBs as a function of lysis time at 50 degrees C was found with kinetics that was similar to that for irradiated DNA, although the magnitude of the increase was smaller. This suggests that heat-labile sites are also formed in the cell. If this is the case, a proportion of DSBs measured by the pulsed-field gel assays may occur during the lysis step and may not be present in the cell as breaks but as heat-labile sites. It is suggested that such sites consist mainly of heat-labile sugar lesions within locally multiply damaged sites. Comparing rejoining of DSBs measured with short and long lysis procedure indicates that the heat-labile sites are repaired with fast kinetics in comparison with repair of the bulk of DSBs.

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

Effects of experimental CO2 leakage on solubility and transport of seven trace metals in seawater and sediment.

PubMed

Ardelan, Murat V; Steinnes, Eiliv; Lierhagen, Syverin; Linde, Sven Ove

2009-12-01

The impact of CO(2) leakage on solubility and distribution of trace metals in seawater and sediment has been studied in lab scale chambers. Seven metals (Al, Cr, Ni, Pb, Cd, Cu, and Zn) were investigated in membrane-filtered seawater samples, and DGT samplers were deployed in water and sediment during the experiment. During the first phase (16 days), "dissolved" (<0.2 microm) concentrations of all elements increased substantially in the water. The increase in dissolved fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb in the CO(2) seepage chamber was respectively 5.1, 3.8, 4.5, 3.2, 1.4, 2.3 and 1.3 times higher than the dissolved concentrations of these metals in the control. During the second phase of the experiment (10 days) with the same sediment but replenished seawater, the dissolved fractions of Al, Cr, Cd, and Zn were partly removed from the water column in the CO(2) chamber. DNi and DCu still increased but at reduced rates, while DPb increased faster than that was observed during the first phase. DGT-labile fractions (Me(DGT)) of all metals increased substantially during the first phase of CO(2) seepage. DGT-labile fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb were respectively 7.9, 2.0, 3.6, 1.7, 2.1, 1.9 and 2.3 times higher in the CO(2) chamber than that of in the control chamber. Al(DGT), Cr(DGT), Ni(DGT), and Pb(DGT) continued to increase during the second phase of the experiment. There was no change in Cd(DGT) during the second phase, while Cu(DGT) and Zn(DGT) decreased by 30% and 25%, respectively in the CO(2) chamber. In the sediment pore water, DGT labile fractions of all the seven elements increased substantially in the CO(2) chamber. Our results show that CO(2) leakage affected the solubility, particle reactivity and transformation rates of the studied metals in sediment and at the sediment-water interface. The metal species released due to CO(2) acidification may have sufficiently long residence time in the seawater to affect bioavailability and toxicity

Diffusive gradients in thin films technique provide robust prediction of metal bioavailability and toxicity in estuarine sediments.

PubMed

Amato, Elvio D; Simpson, Stuart L; Jarolimek, Chad V; Jolley, Dianne F

2014-04-15

Many sediment quality assessment frameworks incorporate contaminant bioavailability as a critical factor regulating toxicity in aquatic ecosystems. However, current approaches do not always adequately predict metal bioavailability to organisms living in the oxidized sediment surface layers. The deployment of the diffusive gradients in thin films (DGT) probes in sediments allows labile metals present in pore waters and weakly bound to the particulate phase to be assessed in a time-integrated manner in situ. In this study, relationships between DGT-labile metal fluxes within 5 mm of the sediment-water interface and lethal and sublethal effects to the amphipod Melita plumulosa were assessed in a range of contaminated estuarine sediments during 10-day laboratory-based bioassays. To account for differing toxicities of metals, DGT fluxes were normalized to water (WQG) or sediment quality guidelines or toxicity thresholds specific for the amphipod. The better dose-response relationship appeared to be the one based on WQG-normalized DGT fluxes, which successfully predicted toxicity despite the wide range of metals and large variations in sediment properties. The study indicated that the labile fraction of metals measured by DGT is useful for predicting metal toxicity to benthic invertebrates, supporting the applicability of this technique as a rapid monitoring tool for sediments quality assessments.

Phaeochromocytoma presenting with labile blood pressures following coronary artery bypass grafting.

PubMed

Roy, James; Akhunji, Zakir; Kushwaha, Virag; Mackie, James; Jepson, Nigel

2016-12-01

Pheochromocytomas have been reported prior to and during coronary artery bypass surgery. We present a patient with an undiagnosed pheochromocytoma who presented with labile hypertension following coronary artery bypass surgery. This case calls attention to the inclusion of an undiagnosed pheochromocytoma in the differential diagnosis for all patients who develop labile hypertension in the postoperative period following cardiac surgery. © 2016 Wiley Periodicals, Inc.

Mechanism of Stabilization of Labile Compounds by Silk Fibroin Proteins

DTIC Science & Technology

2017-04-05

AFRL-AFOSR-VA-TR-2017-0076 Mechanism of Stabilization of Labile Compounds by Silk Fibroin Proteins David Kaplan TRUSTEES OF TUFTS COLEGE INC 169... Proteins 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0015 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) David Kaplan 5d.  PROJECT NUMBER 5e...objective of this research was to elucidate the fundamental mechanisms by which labile compounds are entrapped and stabilized by silk fibroin protein . The

Interspecific variations in mangrove leaf litter decomposition are related to labile nitrogenous compounds

NASA Astrophysics Data System (ADS)

Nordhaus, Inga; Salewski, Tabea; Jennerjahn, Tim C.

2017-06-01

Mangrove leaves form a large pool of carbon, nitrogen and energy that is a major driver of element cycles and detrital food webs inside mangrove forests as well as in adjacent coastal waters. However, there are large gaps in knowledge on the transformation pathways and ultimate fate of leaf nitrogen. Therefore, the main objective of this study was to determine the amount and composition of nitrogenous organic matter and possible species-specific differences during the decomposition of mangrove leaf litter. For that purpose a three month decomposition experiment with litterbags was conducted using leaves of Aegiceras corniculatum, Avicennia alba, Ceriops decandra, Rhizophora apiculata, and Sonneratia caseolaris in the mangrove forest of the Segara Anakan Lagoon, Java, Indonesia. Detrital leaves were analyzed for bulk carbon and total nitrogen (N), stable carbon and nitrogen isotope composition (δ13C, δ15N), total hydrolyzable amino acids (THAA) and total hydrolyzable hexosamines (THHA). Decomposition rates (k d-1) were highest and tM50 values (when 50% of the original mass had been degraded) lowest in S. caseolaris (k = 0.0382 d-1; tM50 = 18 days), followed by A. alba, C. decandra, A. corniculatum, and R. apiculata (k = 0.0098 d-1; tM50 = 71 days). The biochemical composition of detrital leaves differed significantly among species and over time. S. caseolaris and A. alba had higher concentrations of N, THAA and THHA and a lower C/N ratio than the other three species. For most of the species concentrations of N, THAA and THHA increased during decomposition. The hexosamine galactosamine, indicative of bacterial cell walls, was first found in leaves after 5-7 days of decomposition and increased afterwards. Our findings suggest an increasing, but species-specific varying, portion of labile nitrogenous OM and total N in decomposing leaves over time that is partly related to the activity of leaf-colonizing bacteria. Despite a higher relative nitrogen content in the

Influence of life history and sex on metal accumulation in two beetle species (insecta: Coleoptera)

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

Lindqvist, L.; Block, M.

1997-04-01

Insects are important components of most terrestrial environments owing to their great abundance, biomass and diversity. They also make up an important food resource for other animals. Consequently, in many food webs insects constitute important links in metal-transport chains between trophic levels. Therefore trace-metal concentrations in insects have an important influence on the trace-metal distribution in the biosphere. In various insects, Cd, Cu and Zn are usually accumulated to the extent that they reach levels above those of the food, whereas Fe is not. In response to metal pollution, accumulation of nonessential metals was found to increase markedly, whereas essentialmore » metals accumulated less owing to regulating mechanisms in the insects. In polluted environments, metal concentrations were found to be higher in predatory invertebrates than in phytophagous ones in studies where insects were analysed in broad categories such as families. However, no such trend was observed when species were treated separately. The pattern of metal accumulation can differ between species. This is true even for species utilizing the same food resource. For instance, concentrations of Cd, Cu and Fe differed between four species of sawflies feeding on pine needles from the same locality. It is therefore likely that insects with different food sources accumulate metals differently depending on the concentration and chemical form of the metals in the food. There have been few studies aimed at determining whether patterns of metal accumulation differ between males and females of the same species. In one such study on the sawfly Neodiprion sertifer concentrations of Cd, Cu and Fe tended to be higher in males than in females. However, this pattern was not found in two other sawfly species. Target organs for Cd were found to differ between males and females in the grasshopper Aiolopus thalassinus. The testis accumulated Cd to a higher degree than the ovaries.« less

New chemistry of transition metal oxyhydrides

PubMed Central

Kobayashi, Yoji; Hernandez, Olivier; Tassel, Cédric; Kageyama, Hiroshi

2017-01-01

Abstract In this review we describe recent advances in transition metal oxyhydride chemistry obtained by topochemical routes, such as low temperature reduction with metal hydrides, or high-pressure solid-state reactions. Besides the crystal chemistry, magnetic and transport properties of the bulk powder and epitaxial thin film samples, the remarkable lability of the hydride anion is particularly highlighted as a new strategy to discover unprecedented mixed anion materials. PMID:29383042

Effect of exogenous phosphate on the lability and phytoavailability of arsenic in soils.

PubMed

Wang, Jinjin; Zeng, Xibai; Zhang, Hao; Li, Yongtao; Zhao, Shizhen; Su, Shiming; Bai, Lingyu; Wang, Yanan; Zhang, Tuo

2018-04-01

The effect of exogenous phosphate (P, 200 mg⋅kg -1 soil) on the lability and phytoavailability of arsenic (As) was studied using the diffusive gradients in thin films (DGT) technique. Lettuce were grown on the As-amended soils following the stabilization of soil labile As after 90 days incubation. Phosphate (P) application generally facilitated plant growth except one grown on P-sufficient soil. Soil labile As concentration increased in all the soils after P application due to a competition effect. Plant As concentration increased in red soils collected from Hunan Province, while decreases were observed in the other soils. Even though, an overall trend of decrease was obtained in As phytoavailability along with the increase of DGT-measured soil labile P/As molar ratio. The functional equation between P/As and As phytoavailability provided a critical value of 1.7, which could be used as a guidance for rational P fertilization, thus avoiding overfertilization. Copyright © 2018 Elsevier Ltd. All rights reserved.

Forest floor leachate fluxes under six different tree species on a metal contaminated site.

PubMed

Van Nevel, Lotte; Mertens, Jan; De Schrijver, An; Baeten, Lander; De Neve, Stefaan; Tack, Filip M G; Meers, Erik; Verheyen, Kris

2013-03-01

Trees play an important role in the biogeochemical cycling of metals, although the influence of different tree species on the mobilization of metals is not yet clear. This study examined effects of six tree species on fluxes of Cd, Zn, DOC, H(+) and base cations in forest floor leachates on a metal polluted site in Belgium. Forest floor leachates were sampled with zero-tension lysimeters in a 12-year-old post-agricultural forest on a sandy soil. The tree species included were silver birch (Betula pendula), oak (Quercus robur and Q. petraea), black locust (Robinia pseudoacacia), aspen (Populus tremula), Scots pine (Pinus sylvestris) and Douglas fir (Pseudotsuga menziesii). We show that total Cd fluxes in forest floor leachate under aspen were slightly higher than those in the other species' leachates, yet the relative differences between the species were considerably smaller when looking at dissolved Cd fluxes. The latter was probably caused by extremely low H(+) amounts leaching from aspen's forest floor. No tree species effect was found for Zn leachate fluxes. We expected higher metal leachate fluxes under aspen as its leaf litter was significantly contaminated with Cd and Zn. We propose that the low amounts of Cd and Zn leaching under aspen's forest floor were possibly caused by high activity of soil biota, for example burrowing earthworms. Furthermore, our results reveal that Scots pine and oak were characterized by high H(+) and DOC fluxes as well as low base cation fluxes in their forest floor leachates, implying that those species might enhance metal mobilization in the soil profile and thus bear a potential risk for belowground metal dispersion. Copyright © 2013 Elsevier B.V. All rights reserved.

Quantification and characterization of chemically-and thermally-labile and recalcitrant biochar fractions.

PubMed

Bakshi, Santanu; Banik, Chumki; Laird, David A

2018-03-01

The C:N ratios of biochar labile fractions is important for assessing biochar stability and N cycling in soil. Here we compare chemically and thermally labile fractions for nine biochars produced from five biomass feedstocks using four production techniques. Biochar fractionation methods included proximate analysis, hot water extraction, acid and base extractions (0.05 M, 0.5 M, 1 M, 2 M, 3 M, and 6 M of either H 2 SO 4 or NaOH), and oxidation with 15% H 2 O 2 and 0.33 M KMnO 4 (pH 7.2). Results show chemical addition reactions cause underestimation of mass of the labile fraction for chemical extraction and oxidation procedures but not the thermal procedure. Estimates of C and N in labile and recalcitrant fractions were not adversely affected by addition reactions, because solvents were independent of C or N. Results indicate that herbaceous biochars may be a source of N fertility while hardwood biochars may immobilize N during the first few years after biochar application to soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isoelectric focusing of small non-covalent metal species from plants.

PubMed

Köster, Jessica; Hayen, Heiko; von Wirén, Nicolaus; Weber, Günther

2011-03-01

IEF is known as a powerful electrophoretic separation technique for amphoteric molecules, in particular for proteins. The objective of the present work is to prove the suitability of IEF also for the separation of small, non-covalent metal species. Investigations are performed with copper-glutathione complexes, with the synthetic ligand ethylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid (EDDHA) and respective metal complexes (Fe, Ga, Al, Ni, Zn), and with the phytosiderophore 2'-deoxymugineic acid (DMA) and its ferric complex. It is shown that ethylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid and DMA species are stable during preparative scale IEF, whereas copper-glutathione dissociates considerably. It is also shown that preparative scale IEF can be applied successfully to isolate ferric DMA from real plant samples, and that multidimensional separations are possible by combining preparative scale IEF with subsequent HPLC-MS analysis. Focusing of free ligands and respective metal complexes with di- and trivalent metals results in different pIs, but CIEF is usually needed for a reliable estimation of pI values. Limitations of the proposed methods (preparative IEF and CIEF) and consequences of the results with respect to metal speciation in plants are discussed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plant regulation of greenhouse gas emissions and carbon lability in a Neotropical peatland

NASA Astrophysics Data System (ADS)

Girkin, Nicholas; Vane, Christopher; Turner, Benjamin; Ostle, Nicholas; Sjogersten, Sofie

2017-04-01

Tropical peatlands are under significant threat from land use changes but there remains a significant knowledge gap regarding the influences of contrasting plant types on greenhouse gas emissions and belowground carbon dynamics. We investigated differences in surface CO2 and CH4 fluxes and differences in soil organic carbon chemistry under contrasting surface vegetation types, a palm (Raphia taedigera) and a broadleaved evergreen tree (Campnosperma panamensis), in a Neotropical peatland. CO2 and CH4 production differed significantly between species, with higher fluxes measured under R. taedigera. There were significant differences in peat carbon properties under each species as revealed by Rock-Eval pyrolysis. Peat from under each species showed contrasting trends in degradation inside and outside the rooting zone, and strong differences in the presence of the most labile fractions of carbon. These results highlight the strong impacts that surface vegetation can have on surface gas emissions as well as the influences exerted on peat carbon chemistry within a tropical forested peatland, with implications for our understanding of changes in land use type across the tropics.

Modeling Effects of Lability on Microbial Uptake of DOM in River Reaches

NASA Astrophysics Data System (ADS)

Li, A.; Drummond, J. D.; Bowen, J. C.; Cory, R. M.; Kaplan, L.; Packman, A. I.

2017-12-01

Rivers are hotspots for biological degradation of dissolved organic matter (DOM), contributing to 1.8 petagrams of carbon emissions per year. DOM represents approximately 60% of the total mass of organic carbon transported within river networks, fueling stream ecosystem metabolism. Not all DOM is biodegradable, biodegradation rates vary based on lability, and lability decreases with reaction time. Fluorescent fractions of DOM (FDOM) are often used as proxies of DOM lability. Humic-like FDOM, previously considered recalcitrant and thought to contribute minimally to the biodegradable DOM pools, has recently been shown to contribute more than 50% to DOM uptake in bioreactor columns colonized by bacteria in stream water. Protein-like FDOM, a proxy for the biodegradable DOM pool, also contributes to the recalcitrant DOM pool in bioreactors. However, the contribution of different lability pools to DOM uptake at the reach scale remains elusive. Here we combine local-scale results from a bioreactor study and measures of stream geomorphology parameters to model reach-scale DOM uptake in White Clay Creek, a Pennsylvania piedmont stream with an intact, forested riparian zone and inputs from upland agriculture. Steady state modeling of a point-source, continuous injection of FDOM shows that humic-like FDOM contributes up to 80% of the total removal of FDOM at the reach scale, suggesting its importance to in-stream DOM uptake. Tryptophan-like FDOM, a protein-like FDOM, contributes to 80% of the remaining fraction of FDOM at the reach scale that incorporates longer timescales of transport and retention. This is consistent with recent local-scale findings that the lability of tryptophan-like FDOM decreases substantially with reaction time in bioreactors, such that it becomes much more recalcitrant as it travels downstream. Steady state modeling of a distributed source, continuous injection of FDOM shows that contributing sources distribute differently along the river reach for

Trace metals health risk appraisal in fish species of Arabian Sea.

PubMed

Yasmeen, Kousar; Mirza, Muhammad Aslam; Khan, Namra A; Kausar, Nazish; Rehman, Atta-Ur; Hanif, Muddasir

2016-01-01

Fish is a vital food for humans and many animals. We report an environmental monitoring study to assess the trace metals in fish species caught from Arabian Sea and commercially available in the coastal city Karachi, Pakistan. Heavy metals such as copper, iron, lead and cadmium were determined in the skin, fillet and heart of the fish species Pampus argenteus, Epinephelus chlorostigma, Rachycentron canadum, Scomberomorus commerson, Johnius belangerii, Labeo rohita, Lutjanus argentimaculatus, Trachinotus blochii, Pomadsys olivaceum and Acanthopagrus berda by the atomic absorption spectrophotometer. The concentration (mg kg(-1), dry weight) range was: Cd (0.00-0.041), Cu (0.006-0.189), Fe (0.413-4.952) and Pb (0.00-0.569). Cadmium, copper and iron levels were below the tolerable limits whereas concentration of lead in the skins of S. commerson, E. chlorostigma, J. belangerii, A. berda; L. argentimaculatus, fillets of J. belangerii, E. chlorostigma and in the heart of J. belangerii exceeded the recommended limits. Therefore fish skin should be discouraged as food for humans or animals. The results indicate that a number of fish species have higher concentration of heavy metals dangerous for human health. Since the fish P. olivaceum (Dhotar) has the lowest level of trace metals therefore we recommend it for breeding and human consumption.

Childhood Maltreatment, Emotional Lability, and Alcohol Problems in Young Adults At-Risk for ADHD: Testing Moderation and Moderated Moderation.

PubMed

Bunford, Nóra; Wymbs, Brian T; Dawson, Anne E; Shorey, Ryan C

2017-01-01

Childhood maltreatment and alcohol problems are common among young adults with attention-deficit hyperactivity disorder (ADHD). However, little is known about the degree to which maltreatment and alcohol problems are associated; potential pertinent mediating or moderating mechanisms, such as emotional lability; and whether this association varies by sex. We examined, in a sample of adults at risk for ADHD (N = 122, 37% male), the association between childhood maltreatment and alcohol problems, whether emotional lability mediated or moderated this association, and whether either role of emotional lability differed between men and women. Emotional lability moderated the association between emotional neglect and alcohol problems; maltreatment increased risk for alcohol problems for those scoring high tovery high on emotional lability, but not for those with very low-moderate levels. The association between emotional abuse and alcohol problems depended both on emotional lability and sex; emotional abuse decreased the risk for alcohol problems among men very low/low on emotional lability, but not for men who were moderate to very high on emotional lability, or for women. These findings have implications for the way in which targeting maltreatment and emotional lability may be incorporated into prevention and intervention programs to prevent alcohol problems among men and women at risk for ADHD.

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

PubMed

Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted

A Longitudinal Study of Emotion Regulation, Emotion Lability/Negativity, and Internalizing Symptomatology in Maltreated and Nonmaltreated Children

PubMed Central

Kim-Spoon, Jungmeen; Cicchetti, Dante; Rogosch, Fred A.

2013-01-01

The longitudinal contributions of emotion regulation and emotion lability/negativity to internalizing symptomatology were examined in a low-income sample (171 maltreated and 151 nonmaltreated children, from age 7 to 10 years). Latent difference score models indicated that, for both maltreated and nonmaltreated children, emotion regulation was a mediator between emotion lability/negativity and internalizing symptomatology, whereas emotion lability/negativity was not a mediator between emotion regulation and internalizing symptomatology. Early maltreatment was associated with high emotion lability/negativity (age 7) that contributed to poor emotion regulation (age 8), which in turn was predictive of increases in internalizing symptomatology (from age 8 to 9). The results imply important roles of emotion regulation in the development of internalizing symptomatology, especially for children with high emotion lability/negativity. PMID:23034132

Submillimeter-scale heterogeneity of labile phosphorus in sediments characterized by diffusive gradients in thin films and spatial analysis.

PubMed

Meng, Yuting; Ding, Shiming; Gong, Mengdan; Chen, Musong; Wang, Yan; Fan, Xianfang; Shi, Lei; Zhang, Chaosheng

2018-03-01

Sediments have a heterogeneous distribution of labile redox-sensitive elements due to a drastic downward transition from oxic to anoxic condition as a result of organic matter degradation. Characterization of the heterogeneous nature of sediments is vital for understanding of small-scale biogeochemical processes. However, there are limited reports on the related specialized methodology. In this study, the monthly distributions of labile phosphorus (P), a redox-sensitive limiting nutrient, were measured in the eutrophic Lake Taihu by Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) on a two-dimensional (2D) submillimeter level. Geographical information system (GIS) techniques were used to visualize the labile P distribution at such a micro-scale, showing that the DGT-labile P was low in winter and high in summer. Spatial analysis methods, including semivariogram and Moran's I, were used to quantify the spatial variation of DGT-labile P. The distribution of DGT-labile P had clear submillimeter-scale spatial patterns with significant spatial autocorrelation during the whole year and displayed seasonal changes. High values of labile P with strong spatial variation were observed in summer, while low values of labile P with relatively uniform spatial patterns were detected in winter, demonstrating the strong influences of temperature on the mobility and spatial distribution of P in sediment profiles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metal Complexes and Free Radical Toxins Produced by Pfiesteria piscicida

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

Moeller,P.; Beauchesne, K.; Huncik, K.

2007-01-01

Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICP-MS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile inmore » purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.« less

Metal Complexes And Free Radical Toxins Produced By Pfiesteria Piscicida

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

Moeller, P.D.R.; Beauchesne, K.R.; Huncik, K.M.

2009-06-03

Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICPMS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile inmore » purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.« less

Labile dissolved organic carbon supply limits hyporheic denitrification

Treesearch

Jay P. Zarnetske; Roy Haggerty; Steven M. Wondzell; Michelle A. Baker

2012-01-01

We used an in situ steady state 15N-labeled nitrate and acetate well-to-wells injection experiment to determine how the availability of labile dissolved organic carbon as acetate influences microbial denitrification in the hyporheic zone of an upland (third-order) agricultural stream.

Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

PubMed Central

Kitagawa, Hakuba; Ohtsu, Hiroyoshi; Cruz-Cabeza, Aurora J.; Kawano, Masaki

2016-01-01

The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S2) with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S2 was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S2 was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S2 molecules reacted further to produce bent-S3 species as the temperature was increased. Following the thermal evolution of the S2 species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-tri­sulfur dication (cyclo-S3 2+). It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species. PMID:27437110

PTSD, alcohol dependence, and conduct problems: Distinct pathways via lability and disinhibition.

PubMed

Simons, Jeffrey S; Simons, Raluca M; O'Brien, Carol; Stoltenberg, Scott F; Keith, Jessica A; Hudson, Jaime A

2017-01-01

This study tested the role of affect lability and disinhibition in mediating associations between PTSD symptoms and two forms of alcohol-related problems, dependence syndrome symptoms (e.g., impaired control over consumption) and conduct problems (e.g., assault, risk behaviors). Genotype at the serotonin transporter linked polymorphic region (5-HTTLPR) was hypothesized to moderate associations between traumatic stress and PTSD symptoms. In addition, the study tested whether childhood traumatic stress moderated associations between combat trauma and PTSD symptoms. Participants were 270 OIF/OEF/OND veterans. The hypothesized model was largely supported. Participants with the low expression alleles of 5-HTTLPR (S or L G ) exhibited stronger associations between childhood (but not combat) traumatic stress and PTSD symptoms. Affect lability mediated the associations between PTSD symptoms and alcohol dependence symptoms. Behavioral disinhibition mediated associations between PTSD symptoms and conduct related problems. Conditional indirect effects indicated stronger associations between childhood traumatic stress and lability, behavioral disinhibition, alcohol consumption, AUD symptoms, and associated conduct problems via PTSD symptoms among those with the low expression 5-HTTLPR alleles. However, interactions between combat trauma and either childhood trauma or genotype were not significant. The results support the hypothesis that affect lability and behavioral disinhibition are potential intermediate traits with distinct associations with AUD and associated externalizing problems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metals in coastal zones impacted with urban and industrial wastes: Insights on the metal accumulation pattern in fish species

NASA Astrophysics Data System (ADS)

La Colla, Noelia S.; Botté, Sandra E.; Marcovecchio, Jorge E.

2018-05-01

The pollution of aquatic environments is a worldwide problem of difficult solution since these areas are used for the disposal and dilution of anthropogenic wastes. This study evaluated the concentrations of Cd, Cu, Ni and Zn in the gills, liver and muscle tissues of six economically important fish species from the Bahía Blanca estuary in Argentina, a coastal environment that is under anthropogenic pressure. Metal contents in 147 fish samples were determined by digestion and a subsequent analysis with an ICP OES. The concentrations (μg/g, wet weight) of each metal in the fish tissues ranged from below the limit of detection for the four metals to 5.2 in the case of Cd, 340 for Cu, 20 for Ni, and 101 for Zn. The results suggested that metal burden in fishes varied with the species and metal elements, with Cd, Cu and Zn mean maximum accumulation towards the liver tissue. Ni showed a high number of samples with concentrations below the limit of detection. Among species, Cynoscion guatucupa was found to have the highest concentrations of Cu and Zn in the liver tissues, whereas the gills and liver tissues of Mustelus schmitti showed the lowest levels of Ni and Zn. As regards the human health risks, two samples of muscle tissue belonging to C. guatucupa reached to Cd levels that exceeded the permissible levels for human consumption. Moreover, the estimated daily intakes calculated suggest that people would not experience significant health risks from the intake of individual metals through fish consumption.

The role of labile sulfur compounds in thermochemical sulfate reduction

USGS Publications Warehouse

Amrani, A.; Zhang, T.; Ma, Q.; Ellis, G.S.; Tang, Y.

2008-01-01

organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S-O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H2S accumulation in petroleum reservoirs. ?? 2008.

The role of labile sulfur compounds in thermochemical sulfate reduction

NASA Astrophysics Data System (ADS)

Amrani, Alon; Zhang, Tongwei; Ma, Qisheng; Ellis, Geoffrey S.; Tang, Yongchun

2008-06-01

organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S-O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H2S accumulation in petroleum reservoirs.

Metal concentrations in demersal fish species from Santa Maria Bay, Baja California Sur, Mexico (Pacific coast).

PubMed

Jonathan, M P; Aurioles-Gamboa, David; Villegas, Lorena Elizabeth Campos; Bohórquez-Herrera, Jimena; Hernández-Camacho, Claudia J; Sujitha, S B

2015-10-15

Concentrations of 11 trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd, As, Hg) in 40 fish species from Santa Maria Bay, Baja California Sur, Mexico, the strategically important area for marine mammals and organisms were analyzed. Based on their concentrations the ranking of metals Fe>Zn>Ni>Cr>Mn>Pb>Cu>Co>As>Cd>Hg suggests that organism size, metabolism and feeding habits are correlated with metal concentrations. Local geological formations affect the concentrations of different metals in the aquatic environment and are subsequently transferred to fishes. The correlation analysis suggests that metabolism and nurturing habits impact the concentration of metals. Concentrations of Fe and Mn appear to be influenced by scavenging and absorption processes, which vary by species. The considerable variability in the metal concentrations obtained in different species underscores the importance of regular monitoring. Copyright © 2015 Elsevier Ltd. All rights reserved.

Assessment of Affect Lability: Psychometric Properties of the ALS-18.

PubMed

Contardi, Anna; Imperatori, Claudio; Amati, Italia; Balsamo, Michela; Innamorati, Marco

2018-01-01

Affect lability, an important aspect of emotion dysregulation, characterizes several psychiatric conditions. The short Affective Lability Scales (ALS-18) measures three aspects of changeability between euthymia and affect states (Anxiety/Depression, AD; Depression/Elation, DE; and Anger, Ang). The aim of our study was to investigate the psychometric characteristics of an Italian version of the ALS-18 in a sample of adults recruited from the general population. The sample was composed of 494 adults (343 women and 151 men) aged 18 and higher (mean age = 31.73 years, SD = 12.6). All participants were administered a checklist assessing socio-demographic variables, the ALS-18 and measures of depression and difficulties in emotion regulation. Confirmatory factor analyses indicated adequate fit of the three-factor model (RMSEA = 0.061, 95% CI = 0.054/0.069; CFI = 0.99; SRMR = 0.055), and the presence of a higher-order general factor. Internal consistency was satisfactory for all the lower-order dimensions and the general factor (ordinal α > 0.70). The ALS-18 was significantly associated with concurrent measures of depression and difficulties in emotion regulation. These findings indicate that the ALS-18 is a valid and reliable instrument for measuring affect lability, although discriminant validity of subdimensions scores could be problematic.

Short-term acute hypercapnia affects cellular responses to trace metals in the hard clams Mercenaria mercenaria.

PubMed

Ivanina, Anna V; Beniash, Elia; Etzkorn, Markus; Meyers, Tiffany B; Ringwood, Amy H; Sokolova, Inna M

2013-09-15

Estuarine and coastal habitats experience large fluctuations of environmental factors such as temperature, salinity, partial pressure of CO2 ( [Formula: see text] ) and pH; they also serve as the natural sinks for trace metals. Benthic filter-feeding organisms such as bivalves are exposed to the elevated concentrations of metals in estuarine water and sediments that can strongly affect their physiology. The effects of metals on estuarine organisms may be exacerbated by other environmental factors. Thus, a decrease in pH caused by high [Formula: see text] (hypercapnia) can modulate the effects of trace metals by affecting metal bioavailability, accumulation or binding. To better understand the cellular mechanisms of interactions between [Formula: see text] and trace metals in marine bivalves, we exposed isolated mantle cells of the hard clams (Mercenaria mercenaria) to different levels of [Formula: see text] (0.05, 1.52 and 3.01 kPa) and two major trace metal pollutants - cadmium (Cd) and copper (Cu). Elevated [Formula: see text] resulted in a decrease in intracellular pH (pHi) of the isolated mantle cells from 7.8 to 7.4. Elevated [Formula: see text] significantly but differently affected the trace metal accumulation by the cells. Cd uptake was suppressed at elevated [Formula: see text] levels while Cu accumulation has greatly accelerated under hypercapnic conditions. Interestingly, at higher extracellular Cd levels, labile intracellular Cd(2+) concentration remained the same, while intracellular levels of free Zn(2+) increased suggesting that Cd(2+) substitutes bound Zn(2+) in these cells. In contrast, Cu exposure did not affect intracellular Zn(2+) but led to a profound increase in the intracellular levels of labile Cu(2+) and Fe(2+). An increase in the extracellular concentrations of Cd and Cu led to the elevated production of reactive oxygen species under the normocapnic conditions (0.05 kPa [Formula: see text] ); surprisingly, this effect was mitigated in

Ligand lability and chirality inversion in yb heterobimetallic catalysts.

PubMed

Di Bari, Lorenzo; Lelli, Moreno; Salvadori, Piero

2004-09-20

We have investigated the exchange dynamics between the free and bound ligand in K3[Yb[(R)-binol]3], the most active heterobimetallic lanthanoid catalyst for cyclic imine hydrophosphonylation; we found that the Yb-binol bond is labile. The rate constant for this exchange was determined through NMR saturation transfer experiments. Upon addition of (S)-binaphthol, ligand exchange leads to the formation of a small quantity of heterochiral complexes and, in the presence of a molar excess of (S)-binaphthol, to chirality inversion of the whole complex. This demonstrates that, in contrast to other analogous systems, K3[Yb(binol)3] displays a strong chiral discrimination, with the overwhelming preference for ligands of the same configuration. The lability of Yb-binol bond in THF may suggest a ligand-to-substrate exchange as a key step in the catalytic process.

Biosorption of heavy metals by Pseudomonas species isolated from sugar industry.

PubMed

Naz, Tayyaba; Khan, Muhammad Daud; Ahmed, Iftikhar; Rehman, Shafiq Ur; Rha, Eui Shik; Malook, Ijaz; Jamil, Muhammad

2016-09-01

Heavy metal-resistant bacteria can be efficient bioremediators of metals and may provide an alternative or additional method to conventional methods of metal removal. In this study, 10 bacterial isolates were isolated from soil samples of a sugar industry, located at Peshawar, Pakistan. Morphological, physiological, and biochemical characteristics of these isolates were observed. Sequence analysis (16S ribosomal RNA) revealed that isolated strains were closely related to the species belonging to the genera Pseudomonas, Arthrobacter, Exiguobacterium, Citrobacter, and Enterobacter Bacterial isolates were resistant with a minimum inhibitory concentration (500-900 ppm) to lead ion (Pb(2+)), (500-600 ppm) nickel ion (Ni(2+)), (500-800 ppm) copper ion (Cu(2+)), and (600-800 ppm) chromium ion (Cr(3+)) in solid media. Furthermore, biosorption of metals proved considerable removal of heavy metals by isolated metal-resistant strains. Pseudomonas sp. reduced 37% (Pb(2+)), 32% (Ni(2+)), 29% (Cu(2+)), and 32% (Cr(3+)) and was thus found to be most effective, whereas Enterobacter sp. reduced 19% (Pb(2+)), 7% (Ni(2+)), 14% (Cu(2+)), and 21% (Cr(3+)) and was found to be least effective. While average reduction of Pb(2+), Ni(2+), Cu(2+), and Cr(3+) by Citrobacter sp. was found to be 24%, 18%, 23%, and 27%, respectively, among recognized species. This study revealed that Pseudomonas sp. may provide a new microbial community that can be used for enhanced remediation of contaminated environment. © The Author(s) 2015.

Fractionation and potential toxic risk of metals from superficial sediment in Itaipu Lake--boundary between Brazil and Paraguay.

PubMed

Kalwa, Miguel; Quináia, Sueli Pércio; Pletsch, Adelmo L; Techy, Laura; Felsner, Maria Lurdes

2013-01-01

The objective of this study was to evaluate fractions of metals (labile and pseudo-total) extracted from sediment samples collected in Itaipu Lake (boundary between Brazil and Paraguay) and to assess the dynamics and mobility of these fractions by identifying the same bioavailability and ecological risk to metals in the aquatic environment. The concentrations of metal ions were determined by flame atomic absorption spectrometry. There was a correlation between the metal ions, both in the labile and the pseudo-total, with regard to particle size. To assess metals concentrations in sediment, numerical sediment-quality guidelines were applied. The concentrations of aluminum, cadmium, iron, manganese, lead, and zinc in all sediment samples are lower than the proposed probable effects level (PEL), thus possibly indicating that there are no harmful effects from these metals. In contrast, concentrations of copper, chromium, and nickel exceeded the PEL in some samples, thus indicating that these stations are at potential risk. The level of contamination in sediments of Itaipu Lake for all metals was evaluated using contamination factor, degree of contamination, and sum-of-metals toxic unit.

Comprehensive review on phytotechnology: Heavy metals removal by diverse aquatic plants species from wastewater.

PubMed

Rezania, Shahabaldin; Taib, Shazwin Mat; Md Din, Mohd Fadhil; Dahalan, Farrah Aini; Kamyab, Hesam

2016-11-15

Environmental pollution specifically water pollution is alarming both in the developed and developing countries. Heavy metal contamination of water resources is a critical issue which adversely affects humans, plants and animals. Phytoremediation is a cost-effective remediation technology which able to treat heavy metal polluted sites. This environmental friendly method has been successfully implemented in constructed wetland (CWs) which is able to restore the aquatic biosystem naturally. Nowadays, many aquatic plant species are being investigated to determine their potential and effectiveness for phytoremediation application, especially high growth rate plants i.e. macrophytes. Based on the findings, phytofiltration (rhizofiltration) is the sole method which defined as heavy metals removal from water by aquatic plants. Due to specific morphology and higher growth rate, free-floating plants were more efficient to uptake heavy metals in comparison with submerged and emergent plants. In this review, the potential of wide range of aquatic plant species with main focus on four well known species (hyper-accumulators): Pistia stratiotes, Eicchornia spp., Lemna spp. and Salvinia spp. was investigated. Moreover, we discussed about the history, methods and future prospects in phytoremediation of heavy metals by aquatic plants comprehensively. Copyright © 2016. Published by Elsevier B.V.

Peroral Immunization of Rats with Escherichia coli Heat-Labile Enterotoxin Delivered by Microspheres

PubMed Central

Klipstein, Frederick A.; Engert, Richard F.; Sherman, William T.

1983-01-01

The antigenicity of the Escherichia coli heat-labile enterotoxin was not protected against the adverse effect of gastric acidity when the toxin was given together with bicarbonate for peroral immunization to rats, but immunization with the heat-labile enterotoxin encapsulated in pH-dependent microspheres aroused the same strong degree of serum and mucosal antitoxin responses and of protection against challenge as was achieved by peroral immunization after ablation of gastric secretions by pretreatment with cimetidine. PMID:6339378

Native herbaceous plant species with potential use in phytoremediation of heavy metals, spotlight on wetlands - A review.

PubMed

Oyuela Leguizamo, Mayerly Alexandra; Fernández Gómez, Wilmar Darío; Sarmiento, Martha Cecilia Gutiérrez

2017-02-01

Soil, air and water pollution caused by the mobility and solubility of heavy metals significantly damages the environment, human health, plants and animals. One common in situ method used for the decontamination of heavy metals is phytoremediation. This usually involves the use of exotic species. However, these species may exhibit invasive behavior, thereby, affect the environmental and ecological dynamics of the ecosystem into which they are introduced. This paper focuses on some native herbaceous plant species reported on the wetlands of Bogota, Colombia, with potential use in phytoremediation of heavy metals. To do that, the authors identified and searched a bibliography based on key words related to heavy metal decontamination. In addition, authors gathered and analyzed relevant information that allowed the comprehension of the phytoremediation process. This paper suggests the study of 41 native or endemic species regarding their behavior towards heavy metal contamination. From a survey of herbaceous plants reported in Bogota, native and endemic species that belong to predominant families in heavy metal accumulation processes were selected. Although found in Colombian's wetlands, these can also be found worldwide. Therefore, they are of great interest due to their global presence and their potential for use in phytoremediation. The current research about the development of phytoremediation focuses on the identification of new herbaceous species able to decontaminate substratum polluted with heavy metals to contribute with the investigation of the ecology and environment of the nature's remnants in urban wetland ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Bioaccumulation of heavy metals by freshwater algal species of Bhavnagar, Gujarat, India.

PubMed

Jaiswar, Santial; Kazi, Mudassar Anisoddin; Mehta, Shailesh

2015-11-01

The present study investigated copper, cadmium, lead and zinc accumulation in algal species Oedogonium, Cladophora, Oscillatoria and Spirogyra from freshwater habitats of Bhavnagar, India. Eight different locations were periodically sampled during August 2009 to March 2011. The general trend of heavy metal concentrations in all the algal species in present study (except at few stations), were found to be in the following order: Zn > Cu > Pb > Cd. Highest accumulation of Cu was recorded in Oedogonium, while Cladophora showed highest accumulation of Pb signifying a good bioaccumulator. Oscillatoria and Oedogonium were highest Zn accumulating algae which showed significant difference between the means at P < 0.05. ANOVA was performed for comparing significance mean between the groups and within the group for heavy metals in water. The concentration of heavy metals in water was in the following order: Zn > Cu > Pb > Cd. The present study showed that Oedogonium, Cladophora, Oscillatoria and Spirogyra were excellent bioaccumulator and could be utilized as biomonitoring agents in water bodies receiving waste contaminated by metals.

Metals in albatross feathers from Midway Atoll: Influence of species, age, and nest location

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

Burger, J.; Gochfeld, M.

2000-03-01

In this paper the authors examine the concentrations of metals (heavy metals, mercury, lead, cadmium, chromium, manganese, tin; and metalloids, arsenic and selenium), in the down and contour (body) feathers of half-grown young albatrosses, and contour feathers of one of their parents. They collected feathers from Laysan Diomedea immutabilis and black-footed Diomedea nigripes albatrosses from Midway Atoll in the central Pacific Ocean. The authors test the null hypotheses that there is no difference in metal levels as a function of species, age, feather type, and location on the island. Using linear regression they found significant models accounting for the variationmore » in the concentrations of mercury, lead, cadmium, selenium, chromium, and manganese (but not arsenic or tin) as a function of feather type (all metals), collection location (all metals but lead), species (selenium only), and interactions between these factors. Most metals (except mercury, arsenic, and tin) were significantly higher in down than in the contour feathers of either chicks or adults. Comparing the two species, black-footed albatross chicks had higher levels of most elements (except arsenic) in their feathers and/or down. Black-footed adults had significantly higher levels of mercury and selenium. They also collected down and feathers from Laysan albatross chicks whose nests were close to buildings, including buildings with flaking lead paint and those that had been lead-abated.« less

Application of SEC-ICP-MS for comparative analyses of metal-containing species in cancerous and healthy human thyroid samples.

PubMed

Boulyga, Sergei F; Loreti, Valeria; Bettmer, Jörg; Heumann, Klaus G

2004-09-01

Size exclusion chromatography (SEC) was coupled on-line to inductively coupled plasma mass spectrometry (ICP-MS) for speciation study of trace metals in cancerous thyroid tissues in comparison to healthy thyroids aimed to estimation of changes in metalloprotein speciation in pathological tissue. The study showed a presence of species binding Cu, Zn, Cd and Pb in healthy thyroid tissue with a good reproducibility of chromatographic results, whereas the same species could not be detected in cancerous tissues. Thus, remarkable differences with respect to metal-binding species were revealed between healthy and pathological thyroid samples, pointing out a completely different distribution of trace metals in cancerous tissues. The metal-binding species could not be identified in the frame of this work because of a lack of appropriate standards. Nevertheless, the results obtained confirm the suitability of SEC-ICP-MS for monitoring of changes in trace metal distribution in cancerous tissue and will help to better understand the role of metal-containing species in thyroid pathology.

Electrodermal lability as an indicator for subjective sleepiness during total sleep deprivation.

PubMed

Michael, Lars; Passmann, Sven; Becker, Ruth

2012-08-01

The present study addresses the suitability of electrodermal lability as an indicator of individual vulnerability to the effects of total sleep deprivation. During two complete circadian cycles, the effects of 48h of total sleep deprivation on physiological measures (electrodermal activity and body temperature), subjective sleepiness (measured by visual analogue scale and tiredness symptom scale) and task performance (reaction time and errors in a go/no go task) were investigated. Analyses of variance with repeated measures revealed substantial decreases of the number of skin conductance responses, body temperature, and increases for subjective sleepiness, reaction time and error rates. For all changes, strong circadian oscillations could be observed as well. The electrodermal more labile subgroup reported higher subjective sleepiness compared with electrodermal more stable participants, but showed no differences in the time courses of body temperature and task performance. Therefore, electrodermal lability seems to be a specific indicator for the changes in subjective sleepiness due to total sleep deprivation and circadian oscillations, but not a suitable indicator for vulnerability to the effects of sleep deprivation per se. © 2011 European Sleep Research Society.

Assessment of mechanisms of metal-induced reproductive toxicity in aquatic species as a biomarker of exposure

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

Anderson, M.; George, W.; Preslan, J.

1996-05-02

This project discusses the following studies: identification and quantitation of heavy metals and petroleum products present in Bayou Trepagnier relative to control sites; assessment of the uptake and bioaccumulation of metals and organic contaminants of interest in aquatic species; establishment and use of polarographic methods for use in metal speciation studies to identify specific chemical forms present in sediments, waters and organism; and evaluation of contaminants on reproductive function of aquatic species as potential biomarkers of exposure. 14 refs.

Heavy metals in sediment and their accumulation in commonly consumed fish species in Bangladesh.

PubMed

Islam, Md Saiful; Ahmed, Md Kawser; Habibullah-Al-Mamun, Md

2017-01-02

Six heavy metals (chromium [Cr], nickel [Ni], copper [Cu], arsenic [As], cadmium [Cd], and lead [Pb]) were measured in sediments and soft tissues of eleven commonly consumed fish species collected from an urban river in the northern part of Bangladesh. The abundance of heavy metals in sediments varied in the decreasing order of Cr > Ni > Cu > Pb > As > Cd. The ranges of mean metal concentrations in fish species, in mg/kg wet weight (ww), were as follows: Cr, 0.11-0.46; Ni, 0.77-2.6; Cu, 0.57-2.1; As, 0.43-1.7; Cd, 0.020-0.23; and Pb, 0.15-1.1. Target hazard quotients (THQs) and target carcinogenic risk (TR) showed the intake of As and Pb through fish consumption were higher than the recommended values, indicating the consumption of these fish species is associated with noncarcinogenic and carcinogenic health risks.

THE IMPORTANCE OF ORGANIC MATTER DISTRIBUTION AND EXTRACT SOIL:SOLUTION RATIO ON THE DESORPTION OF HEAVY METALS FROM SOILS

EPA Science Inventory

The lability (mobility and bioavailability) of metals varies significantly with soil properties for similar total soil metal concentrations. We studied desorption of Cu, Ni and Zn, from 15 diverse, unamended soils. These studies included evaluation of the effects of soil:solution...

Behavior of native species Arrhenatherum elatius (Poaceae) and Sonchus transcaspicus (Asteraceae) exposed to a heavy metal-polluted field: plant metal concentration, phytotoxicity, and detoxification responses.

PubMed

Lu, Yan; Li, Xinrong; He, Mingzhu; Zeng, Fanjiang

2013-01-01

The application of vegetation cover for the phytomanagement of heavy metal-polluted soils needs prior investigation on the suitability of plant species. In this study, behaviors of Arrhenatherum elatius and Sonchus transcaspicus, two native perennial grasses that currently grow in a mine tailing, were investigated through plant metal concentration, phytotoxicity and their detoxification responses. Both of the species accumulated Ni, Cu, Cd, Co, Mn, Pb, Cr, and Zn in shoots far below criterion concentration as a hyperaccumulators; thus, neither of them were found to be hyperaccumulators. A. elatius accumulated metals in roots and then in shoots, on the contrary, in S. transcaspicus metals were preferentially accumulated in shoots. Plants exposure to such metals resulted in oxidative stress in the considered organs as indicated by the changes in chlorophyll fluorescence, chlorophyll contents, malondialdehyde (MDA) levels and antioxidative enzyme activities. A. elatius seemed to be more affected by metal-induced oxidative stress than S. transcaspicus. Correspondingly, S. transcaspicus showed a greater capacity to adapt to metal-induced oxidative stress, depending on more effective antioxidative defense mechanisms to protect itself from oxidative damage. These findings allowed us to conclude that both of these plant species could be suitable for the phytostabilization of metal-polluted soils.

Estimating soil labile organic carbon and potential turnover rates using a sequential fumigation–incubation procedure.

Treesearch

X.M. Zoua; H.H. Ruanc; Y. Fua; X.D. Yanga; L.Q. Sha

2005-01-01

Labile carbon is the fraction of soil organic carbon with most rapid turnover times and its oxidation drives the flux of CO2 between soils and atmosphere. Available chemical and physical fractionation methods for estimating soil labile organic carbon are indirect and lack a clear biological definition. We have modified the well-established Jenkinson and Powlson’s...

Metal contamination and fractionation in sediments from the lower basin of the Vale do Ribeira (SE, Brazil).

PubMed

Bonnail, Estefanía; Buruaem, Lucas M; Morais, Lucas G; Abessa, Denis M S; Sarmiento, Aguasanta M; DelValls, T Ángel

2017-06-01

The sediment quality of Ribeira de Iguape River is affected by former Pb extraction mining. Some studies affirm the restoration status of the basin, however, mobility of metals and its associated risk is still questioned. This study integrates the metal concentrations in the lower part of the basin with different contamination source to determine the existence of risks associated with the mobile fractions of the geochemical matrix. Despite concentrations of metals were low and the environmental risk factor values were negative, our results indicated that As, Mn, Pb, and V were present in the most labile forms. The multivariate analysis conducted using metal concentrations, environmental risk factor values and speciation suggested that any risk would be associated with the labile fractions of the analyzed elements, especially for Pb. The station from Registro was stressed by Co, Pb and Zn; with Pb under the reactive fraction that could be associated with high mobility and potential bioavailability.

Impact of trace metal concentrations on coccolithophore growth and morphology: species-specific responses in past and present ocean

NASA Astrophysics Data System (ADS)

Faucher, Giulia; Hoffmann, Linn; Bach, Lennart Thomas; Bottini, Cinzia; Erba, Elisabetta; Riebesell, Ulf

2017-04-01

The Cretaceous witnessed intervals of profound perturbation named "Oceanic Anoxic Events (OAEs)" characterized by volcanic injection of large amounts of CO2, ocean anoxia, eutrophication, and introduction of biologically relevant metals. Some of these extreme events were characterized by size reduction and/or morphological changes of a number of nannofossil species. To detect the cause/s of such changes in the fossil record is challenging. Evidence of a correspondence between intervals of high trace metals concentrations and nannofossil dwarfism may be suggestive for a negative effect of these elements on nannoplankton biocalcification process. In order to verify the hypothesis that anomalously high quantities of essential and/or toxic metals were the cause of coccolith dwarfism, we explored the toxicities of a mixture of trace metals on four living coccolithophores species, namely Emiliania huxleyi, Gephyrocapsa oceanica, Pleurochrysis carterae and Coccolithus pelagicus. The trace metals tested were chosen based upon concentration peaks identified in the geological record and upon known trace metal interaction with living coccolithophores algae. Our results demonstrate a species-specific response to trace metal enrichment in living coccolithophores: E. huxleyi, G. oceanica and C. pelagicus showed a decrease in their growth rate with progressively and exponentially increased trace metal concentrations, while P. carterae is unresponsive to trace metal content. Furthermore, E. huxleyi, G. oceanica and C. pelagicus evidenced a decrease in the cell diameter. Smaller coccoliths were detected in E. huxleyi and C. pelagicus, while coccolith of G. oceanica showed a decrease in size only at the highest trace metal concentrations tested. P. carterae size was unresponsive for changing trace metal concentration. Our results on living coccolithophore algae, demonstrate that elevated trace metal concentrations not only affect growth but also coccolith size and/or weight and that

Biotic and abiotic controls on diurnal fluctuations in labile soil phosphorus of a wet tropical forest.

PubMed

Vandecar, Karen L; Lawrence, Deborah; Wood, Tana; Oberbauer, Steven F; Das, Rishiraj; Tully, Katherine; Schwendenmann, Luitgard

2009-09-01

The productivity of many tropical wet forests is generally limited by bioavailable phosphorus (P). Microbial activity is a key regulator of P availability in that it determines both the supply of P through organic matter decomposition and the depletion of bioavailable P through microbial uptake. Both microbial uptake and mineralization occur rapidly, and their net effect on P availability varies with soil moisture, temperature, and soil organic matter quantity and quality. Exploring the mechanisms driving P availability at fine temporal scales can provide insight into the coupling of carbon, water, and nutrient cycles, and ultimately, the response of tropical forests to climate change. Despite the recognized importance of P cycling to the dynamics of wet tropical forests and their potential sensitivity to short-term fluctuations in bioavailable P, the diurnal pattern of P remains poorly understood. This study quantifies diurnal fluctuations in labile soil P and evaluates the importance of biotic and abiotic factors in driving these patterns. To this end, measurements of labile P were made every other hour in a Costa Rican wet tropical forest oxisol. Spatial and temporal variation in Bray-extractable P were investigated in relation to ecosystem carbon flux, soil CO2 efflux, soil moisture, soil temperature, solar radiation, and sap-flow velocity. Spatially averaged bi-hourly (every two hours) labile P ranged from 0.88 to 2.48 microg/g across days. The amplitude in labile P throughout the day was 0.61-0.82 microg/g (41-54% of mean P concentrations) and was characterized by a bimodal pattern with a decrease at midday. Labile P increased with soil CO2 efflux and soil temperature and declined with increasing sap flow and solar radiation. Together, soil CO2 efflux, soil temperature, and sap flow explained 86% of variation in labile P.

Protective Effect of Active Immunization with Purified Escherichia coli Heat-Labile Enterotoxin in Rats

PubMed Central

Klipstein, Frederick A.; Engert, Richard F.

1979-01-01

The protective effect of active immunization by different routes with a purified preparation of the polymyxin-release form of Escherichia coli heat-labile toxin was evaluated in rats. Immunized animals were challenged by placing toxin into ligated ileal loops at dosages which produced either 50% or the maximum secretory response in unimmunized rats. Immunization exclusively by the parenteral route yielded significant protection. Rats were also protected when parenteral priming was followed by boosting given either directly into the duodenum or perorally 2 h after intragastric cimetidine, but not when the peroral boosts were given with bicarbonate. Immunization administered entirely by the peroral route with cimetidine yielded protection but only when the immunizing dosage was fivefold greater than that found effective in the parenteral-peroral approach. Rats immunized exclusively by the parenteral route and those boosted perorally with cimetidine were also tested, and found to be protected, against challenge with viable organisms of strains that produce either heat-labile toxin alone or both heat-labile and heat-stable toxin, but they were not protected against a strain which produces just heat-stable toxin. Geometric mean serum antibody titers were increased by 16-fold or more over control values in those groups of rats in which protection was achieved, with the exception of those immunized exclusively by the peroral route. These observations demonstrate that (i) active immunization with purified E. coli heat-labile toxin results in significant protection against both this toxin as well as viable organisms which produce it, but not against viable strains which produce heat-stable toxin only, and (ii) concomitant ablation of gastric secretion by the use of cimetidine renders the peroral route of immunization effective. They suggest that prophylactic immunization against diarrheal disease caused by heat-labile toxin-producing strains of E. coli may be feasible in

Cross-species transcriptional network analysis reveals conservation and variation in response to metal stress in cyanobacteria

PubMed Central

2013-01-01

Background As one of the most dominant bacterial groups on Earth, cyanobacteria play a pivotal role in the global carbon cycling and the Earth atmosphere composition. Understanding their molecular responses to environmental perturbations has important scientific and environmental values. Since important biological processes or networks are often evolutionarily conserved, the cross-species transcriptional network analysis offers a useful strategy to decipher conserved and species-specific transcriptional mechanisms that cells utilize to deal with various biotic and abiotic disturbances, and it will eventually lead to a better understanding of associated adaptation and regulatory networks. Results In this study, the Weighted Gene Co-expression Network Analysis (WGCNA) approach was used to establish transcriptional networks for four important cyanobacteria species under metal stress, including iron depletion and high copper conditions. Cross-species network comparison led to discovery of several core response modules and genes possibly essential to metal stress, as well as species-specific hub genes for metal stresses in different cyanobacteria species, shedding light on survival strategies of cyanobacteria responding to different environmental perturbations. Conclusions The WGCNA analysis demonstrated that the application of cross-species transcriptional network analysis will lead to novel insights to molecular response to environmental changes which will otherwise not be achieved by analyzing data from a single species. PMID:23421563

Trace metal mobilization by organic soil amendments: insights gained from analyses of solid and solution phase complexation of cadmium, nickel and zinc.

PubMed

Welikala, Dharshika; Hucker, Cameron; Hartland, Adam; Robinson, Brett H; Lehto, Niklas J

2018-05-01

The accumulation of Cd in soils worldwide has increased the demand for methods to reduce the metal's plant bioavailability. Organic matter rich soil amendments have been shown to be effective in achieving this. However, it is not known how long these amendments can retain the Cd, and whether dissolved organic matter (DOM) released from them can enhance the metal's mobility in the environment. In this study we sought to test the Cd binding capacity of various organic soil amendments, and evaluate differences in characteristics of the DOM released to see if they can explain the lability of the Cd-DOM complexes. We collected ten organic soil amendments from around New Zealand: five different composts, biosolids from two sources, two types of peat and spent coffee grounds. We characterised the amendments' elemental composition and their ability to bind the Cd. We then selected two composts and two peats for further tests, where we measured the sorption of Ni or Zn by the amendments. We analysed the quality of the extracted DOM from the four amendments using 3D Excitation Emission Matrix analysis, and tested the lability of the metal-DOM complexes using an adapted diffusive gradients in thin-films (DGT) method. We found that composts bound the most Cd and that the emergent Cd-DOM complexes were less labile than those from the peats. Ni-DOM complexes were the least labile. The aromaticity of the extracted DOM appears to be an important factor in determining the lability of Ni complexes, but less so for Zn and Cd. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metals in Some Edible Fish and Shrimp Species Collected in Dry Season from Subarnarekha River, India.

PubMed

Giri, Soma; Singh, Abhay Kumar

2015-08-01

The concentration of As, Cd, Cu, Fe, Pb, Ni, Zn, Cr, Co and Sr were determined in five fish and one shrimp species collected from the Subarnarekha River during pre-monsoon season using inductively coupled plasma-mass spectrometry for a risk assessment and source apportionment study. Concentrations of metals in the fish and shrimp exceeded the recommended food standards for As, Cu, Ni, Cd and Zn in many samples. Principal component analysis suggested both innate and anthropogenic activities as contributing sources of metal in the fish and shrimp. The calculated target hazard quotients and hazard indices indicated that high concentrations of metals in some species at some locations present an appreciable risk to the health of consumers of these species.

Metals in albatross feathers from midway atoll: influence of species, age, and nest location.

PubMed

Burger, J; Gochfeld, M

2000-03-01

Female birds sequester some heavy metals in their eggs, which are then transferred to the developing embryo. Semiprecocial birds such as albatrosses are fully covered with down at hatching, but are dependent on their parents for food for many weeks. At hatching, levels of metals in the chick's down represent exposure from the female via egg, while levels in fully formed feathers at fledgling, several months later, represent mainly exposure from food provided by their parents. In this paper we examine the concentrations of "metals" (heavy metals, mercury, lead, cadmium, chromium, manganese, tin; and metalloids, arsenic and selenium), in the down and contour (body) feathers of half-grown young albatrosses, and contour feathers of one of their parents. We collected feathers from Laysan Diomedea immutabilis and black-footed Diomedea nigripes albatrosses from Midway Atoll in the central Pacific Ocean. We test the null hypotheses that there is no difference in metal levels as a function of species, age, feather type, and location on the island. Using linear regression we found significant models accounting for the variation in the concentrations of mercury, lead, cadmium, selenium, chromium, and manganese (but not arsenic or tin) as a function of feather type (all metals), collection location (all metals but lead), species (selenium only), and interactions between these factors. Most metals (except mercury, arsenic, and tin) were significantly higher in down than in the contour feathers of either chicks or adults. Comparing the two species, black-footed albatross chicks had higher levels of most elements (except arsenic) in their feathers and/or down. Black-footed adults had significantly higher levels of mercury and selenium. We also collected down and feathers from Laysan albatross chicks whose nests were close to buildings, including buildings with flaking lead paint and those that had been lead-abated. Lead levels in the down and feathers of chicks close to nonabated

A new class of high-contrast Fe(II) selective fluorescent probes based on spirocyclized scaffolds for visualization of intracellular labile iron delivered by transferrin.

PubMed

Niwa, Masato; Hirayama, Tasuku; Okuda, Kensuke; Nagasawa, Hideko

2014-09-14

Iron is an essential metal nutrient that plays physiologically and pathologically important roles in biological systems. However, studies on the trafficking, storage, and functions of iron itself in living samples have remained challenging due to the lack of efficient methods for monitoring labile intracellular iron. Herein, we report a new class of Fe(2+)-selective fluorescent probes based on the spirocyclization of hydroxymethylrhodamine and hydroxymethylrhodol scaffolds controlled by using our recently established N-oxide chemistry as a Fe(2+)-selective switch of fluorescence response. By suppressing the background signal, the spirocyclization strategy improved the turn-on rate dramatically, and reducing the size of the substituents of the N-oxide group enhanced the reaction rate against Fe(2+), compared with the first generation N-oxide based Fe(2+) probe, RhoNox-1. These new probes showed significant enhancements in the fluorescence signal against not only the exogenously loaded Fe(2+) but also the endogenous Fe(2+) levels. Furthermore, we succeeded in monitoring the accumulation of labile iron in the lysosome induced by transferrin-mediated endocytosis with a turn-on fluorescence response.

Interspecific differences in the antioxidant capacity of two Laridae species exposed to metals.

PubMed

Espín, Silvia; Martínez-López, Emma; Jiménez, Pedro; María-Mojica, Pedro; García-Fernández, Antonio J

2016-05-01

The main aim of the present study was to assess the concentration of metals (Pb, Cd, Hg, Cu and Zn) in blood, and elucidate their potential effects on oxidative stress biomarkers in red blood cells of Audouin's gull (Ichthyaetus audouinii) and Slender-billed gull (Chroicocephalus genei) chicks in Southeastern Spain. For this purpose, total glutathione (GSH) content, antioxidant enzymes activities (glutathione peroxidase, GPx; superoxide dismutase, SOD; catalase, CAT and glutathione-S-transferase, GST), and lipid peroxidation (TBARS) were analyzed. In general, metal exposure in both species can be considered low, except for Hg in Audouin's gull. Our findings show higher antioxidant levels in Audouin's gull than in Slender-billed gull; probably due to a combination of different basal antioxidant capacity between species, and to an up-regulation of the antioxidant system in Audouin's gull as a response to the higher Hg, Cu and Zn concentrations. This could reduce the production of TBARS keeping them at lower levels than those found in Slender-billed gull. In spite of this, the significantly higher Hg levels found in Audouin's gull (13.6µg/dl wet weight) in comparison to Slender-billed gull (2.7µg/dl), likely related to their different diet and the former consuming discarded fish, were able to produce lipid peroxidation in this species. The positive effect of Hg on SOD activity in Slender-billed gull, and of Pb on GSH levels in Audouin's gull, could reflect the necessity of the organism to upregulate these antioxidants to balance the increased oxidative stress caused by metals. The degree of metal exposure seems to be essential in the response of the antioxidant system, which may suffer up or down-regulations depending on metal concentrations. This study supports the interactive effects of metals on oxidative stress biomarkers, the complexity of the antioxidant system and the close cooperation between antioxidants, which requires the study of several metals and

Metal concentration in water, sediment and four fish species from Lake Titicaca reveals a large-scale environmental concern.

PubMed

Monroy, Mario; Maceda-Veiga, Alberto; de Sostoa, Adolfo

2014-07-15

Although intensive mining activity and urban sewage discharge are major sources of metal inputs to Lake Titicaca, the risk posed by metal pollution to wildlife and human populations has been poorly studied. In this study we compared the concentrations of Cu, Zn, Cd, Hg, Pb, Co, and Fe in water, sediment, and two tissues (liver and muscle) of four fish species (Odontesthes bonariensis, Orestias luteus, Orestias agassii, and Trichomycterus rivulatus) across important fishery areas in Lake Titicaca. The concentration of Pb in water at the discharge sites of the main rivers and of most elements, with the exception of Co and Fe, in all fish collected in this study exceeded the safety thresholds established by international legislation. The highest metal concentrations were observed in benthopelagic species, and liver tissue was identified as the main depository for all metals with the exception of mercury. The metal bioaccumulation pattern in fish was weakly related to the metal concentrations in the environment with the exception of Hg at the most polluted location, partly explained by the different metabolic role of essential and non-essential elements and the influence of other factors such as species' ecology and individual traits in the bioaccumulation of most metals. As metal pollution extended across the study area and high metal concentrations were detected in all four fish species, we urge the authorities to enforce legislation for water and fish consumption and to evaluate the effects of metal pollution on fish health. Copyright © 2014 Elsevier B.V. All rights reserved.

Metal immobilization in hazardous contaminated minesoils after marble slurry waste application. A field assessment at the Tharsis mining district (Spain).

PubMed

Fernández-Caliani, J C; Barba-Brioso, C

2010-09-15

A one-year field trial was conducted at the abandoned mine site of Tharsis (Spain) in order to assess the potential value of waste sludge generated during the processing of marble stone, as an additive for assisting natural remediation of heavily contaminated acid mine soils. An amendment of 22 cmol(c) of lime per kilogram of soil was applied to raise the pH level from 3.2 to above 6. The amendment application was effective in reducing concentrations of Al, Fe, Mn, sulfate and potentially hazardous trace elements (mainly Cu, Pb, Zn and Cd) in the most labile metal pools (water-soluble and EDTA-extractable fractions). Geochemical equilibrium calculations indicate that sulfate complexes and free metal ions were the dominant aqueous species in the soil solution. Metal coprecipitation with nanocrystalline ferric oxyhydroxides may be the major chemical mechanism of amendment-induced immobilization. The alleviating effect of the soil amendment on the metal bioavailability and phytotoxicity showed promise for assisting natural revegetation of the mine land. Copyright 2010 Elsevier B.V. All rights reserved.

Impact of temperamental mood lability on depressive mixed state.

PubMed

Benazzi, Franco

2006-01-01

Cyclothymic temperament (which includes mood lability) is common in bipolar II disorder (BP-II). Depressive mixed state (DMX), a major depressive episode (MDE) mixed with intra-episode hypomanic symptoms (3 or more, according to a recently validated definition), was found to be common in BP-II and not uncommon in major depressive disorder (MDD). The study aim was to find the impact of temperamental mood lability (TML) on DMX. Consecutive 148 BP-II and 117 MDD outpatients presenting for MDE treatment were interviewed by the Structured Clinical Interview for DSM-IV as modified by Benazzi and Akiskal to reduce the false negative BP-II. Intra-MDE hypomanic symptoms were systematically assessed. Kraepelin, Angst, and Akiskal's definitions of temperamental mood lability (i.e., frequent up and down fluctuations of mood between major mood episodes since young age) were followed. DMX was present in 61.5%, TML in 52.8%. In the DMX sample, TML was present in 57.6%, and in the non-DMX sample TML was present in 45.0% (OR = 1.6, 95% CI = 1.0-2.7). In the DMX sample, independent predictors of DMX with TML were BP-II and young age at onset. Intra-MDE hypomanic symptoms, and MDE, melancholic and atypical symptoms were not significantly different between DMX patients with TML and DMX patients without TML, apart from more temperamental interpersonal sensitivity in DMX patients with TML (OR = 2.0, 95% CI = 1.0-3.8). DMX patients with TML had a younger onset age, suggesting that TML may facilitate the onset of DMX or that it may be a precursor of DMX. The association of BP-II with DMX, TML, and interpersonal sensitivity can make the course of BP-II more unstable and its treatment more complex.

On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

Distributions of typical contaminant species in urban short-term storm runoff and their fates during rain events: a case of Xiamen City.

PubMed

Wei, Qunshan; Zhu, Gefu; Wu, Peng; Cui, Li; Zhang, Kaisong; Zhou, Jingjing; Zhang, Wenru

2010-01-01

The pollutants in urban storm runoff, which lead to an non-point source contamination of water environment around cities, are of great concerns. The distributions of typical contaminants and the variations of their species in short term storm runoff from different land surfaces in Xiamen City were investigated. The concentrations of various contaminants, including organic matter, nutrients (i.e., N and P) and heavy metals, were significantly higher in parking lot and road runoff than those in roof and lawn runoff. The early runoff samples from traffic road and parking lot contained much high total nitrogen (TN 6-19 mg/L) and total phosphorus (TP 1-3 mg/L). A large proportion (around 60%) of TN existed as total dissolved nitrogen (TDN) species in most runoff. The percentage of TDN and the percentage of total dissolved phosphorus remained relatively stable during the rain events and did not decrease as dramatically as TN and TP. In addition, only parking lot and road runoff were contaminated by heavy metals, and both Pb (25-120 microg/L) and Zn (0.1-1.2 mg/L) were major heavy metals contaminating both runoff. Soluble Pb and Zn were predominantly existed as labile complex species (50%-99%), which may be adsorbed onto the surfaces of suspended particles and could be easily released out when pH decreased. This would have the great impact to the environment.

Measurement of labile copper in wine by medium exchange stripping potentiometry utilising screen printed carbon electrodes.

PubMed

Clark, Andrew C; Kontoudakis, Nikolaos; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R

2016-07-01

The presence of copper in wine is known to impact the reductive, oxidative and colloidal stability of wine, and techniques enabling measurement of different forms of copper in wine are of particular interest in understanding these spoilage processes. Electrochemical stripping techniques developed to date require significant pretreatment of wine, potentially disturbing the copper binding equilibria. A thin mercury film on a screen printed carbon electrode was utilised in a flow system for the direct analysis of labile copper in red and white wine by constant current stripping potentiometry with medium exchange. Under the optimised conditions, including an enrichment time of 500s and constant current of 1.0μA, the response range was linear from 0.015 to 0.200mg/L. The analysis of 52 red and white wines showed that this technique generally provided lower labile copper concentrations than reported for batch measurement by related techniques. Studies in a model system and in finished wines showed that the copper sulfide was not measured as labile copper, and that loss of hydrogen sulfide via volatilisation induced an increase in labile copper within the model wine system. Copyright © 2016 Elsevier B.V. All rights reserved.

Simultaneous quantification of soil phosphorus labile pool and desorption kinetics using DGTs and 3D-DIFS

NASA Astrophysics Data System (ADS)

Menezes-Blackburn, Daniel; Sun, Jiahui; Lehto, Niklas; Zhang, Hao; Stutter, Marc; Giles, Courtney D.; Darch, Tegan; George, Timothy S.; Shand, Charles; Lumsdon, David; Blackwell, Martin; Wearing, Catherine; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Haygarth, Philip M.

2017-04-01

The phosphorus (P) labile pool and desorption kinetics were simultaneously evaluated in ten representative UK soils using the technique of Diffusive gradients in thin films (DGT). The DGT-induced fluxes in soil and sediments model (DIFS) was fitted to the time series of DGT deployment (1h to 240h). The desorbable P concentration (labile P) was obtained by multiplying the fitted Kd by the soil solution P concentration obtained using Diffusive Equilibration in Thin Films (DET) devices. The labile P was then compared to several soil P extracts including Olsen P, Resin P, FeO-P and water extractable P, in order to assess if these analytical procedures can be used to represent the labile P across different soils. The Olsen P, commonly used as a representation of the soil labile P pool, overestimated the desorbable P concentration by a seven fold factor. The use of this approach for the quantification of soil P desorption kinetics parameters was somewhat unprecise, showing a wide range of equally valid solutions for the response of the system P equilibration time (Tc). Additionally, the performance of different DIFS model versions (1D, 2D and 3D) was compared. Although these models had a good fit to experimental DGT time series data, the fitted parameters showed a poor agreement between different model versions. The limitations of the DIFS model family are associated with the assumptions taken in the modelling approach and the 3D version is here considered to be the most precise among them.

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.

Do constructed wetlands remove metals or increase metal bioavailability?

PubMed

Xu, Xiaoyu; Mills, Gary L

2018-07-15

The H-02 wetland was constructed to treat building process water and storm runoff water from the Tritium Processing Facility on the Department of Energy's Savannah River Site (Aiken, SC). Monthly monitoring of copper (Cu) and zinc (Zn) concentrations and water quality parameters in surface waters continued from 2014 to 2016. Metal speciation was modeled at each sampling occasion. Total Cu and Zn concentrations released to the effluent stream were below the NPDES limit, and the average removal efficiency was 65.9% for Cu and 71.1% for Zn. The metal-removal processes were found out to be seasonally regulated by sulfur cycling indicated by laboratory and model results. High temperature, adequate labile organic matter, and anaerobic conditions during the warm months (February to August) favored sulfate reduction that produced sulfide minerals to significantly remove metals. However, the dominant reaction in sulfur cycling shifted to sulfide oxidation during the cool months (September to next March). High concentrations of metal-organic complexes were observed, especially colloidal complexes of metal and fulvic acid (FA), demonstrating adsorption to organic matter became the primary process for metal removal. Meanwhile, the accumulation of metal-FA complexes in the wetland system will cause negative effects to the surrounding environment as they are biologically reactive, highly bioavailable, and can be easily taken up and transferred to ecosystems by trophic exchange. Copyright © 2018 Elsevier Ltd. All rights reserved.

Development and Lability in the Parent-Child Relationship During Adolescence: Associations With Pubertal Timing and Tempo

PubMed Central

Marceau, Kristine; Ram, Nilam; Susman, Elizabeth

2014-01-01

Adolescents' and parents' reactions to pubertal development are hypothesized to contribute to changes in family dynamics. Using 7-year longitudinal data from the NICHD-SECCYD (488 boys, 475 girls) we examined relations between pubertal development (timing, tempo) and trajectories (developmental change and year-to-year lability) of parent-child conflict and closeness from age 8.5 to 15.5 years. Changes were mostly characterized by year-to-year fluctuations – lability. Parent-child conflict increased and closeness decreased some with age. Pubertal timing and tempo were more consistently associated with lability in parent-child relationships than with long-term trends, although faster tempo was associated with steeper decreases in parent-child closeness. Findings provide a platform for examining how puberty contributes to both long-term and transient changes in adolescents' relationships and adjustment. PMID:26321856

Evolution and stabilization of subnanometric metal species in confined space by in situ TEM

DOE PAGES

Liu, Lichen; Zakharov, Dmitri N.; Arenal, Raul; ...

2018-02-08

Understanding the behavior and dynamic structural transformation of subnanometric metal species under reaction conditions will be helpful for understanding catalytic phenomena and for developing more efficient and stable catalysts based on single atoms and clusters.In this work,the evolution and stabilization of subnanometric Pt species confined in MCM-22 zeolite has been studied by in situ transmission electron microscopy (TEM). By correlating the results from in situ TEM studies and the results obtained in a continuous fix-bed reactor,it has been possible to delimitate the factors that control the dynamic agglomeration and redispersion behavior of metal species under reaction conditions. Here, the dynamicmore » reversible transformation between atomically dispersed Pt species and clusters/nanoparticles during CO oxidation at different temperatures has been elucidated.Ithas also been confirmed that subnanometric Pt clusters can be stabilized in MCM-22 crystallites during NO reduction with CO and H 2.« less

Evolution and stabilization of subnanometric metal species in confined space by in situ TEM

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

Liu, Lichen; Zakharov, Dmitri N.; Arenal, Raul

Understanding the behavior and dynamic structural transformation of subnanometric metal species under reaction conditions will be helpful for understanding catalytic phenomena and for developing more efficient and stable catalysts based on single atoms and clusters.In this work,the evolution and stabilization of subnanometric Pt species confined in MCM-22 zeolite has been studied by in situ transmission electron microscopy (TEM). By correlating the results from in situ TEM studies and the results obtained in a continuous fix-bed reactor,it has been possible to delimitate the factors that control the dynamic agglomeration and redispersion behavior of metal species under reaction conditions. Here, the dynamicmore » reversible transformation between atomically dispersed Pt species and clusters/nanoparticles during CO oxidation at different temperatures has been elucidated.Ithas also been confirmed that subnanometric Pt clusters can be stabilized in MCM-22 crystallites during NO reduction with CO and H 2.« less

Heavy metal accumulation imparts structural differences in fragrant Rosa species irrigated with marginal quality water.

PubMed

Ahsan, Muhammad; Younis, Adnan; Jaskani, Muhammad Jafar; Tufail, Aasma; Riaz, Atif; Schwinghamer, Timothy; Tariq, Usman; Nawaz, Fahim

2018-09-15

Wastewater is an alternative to traditional sources of renewable irrigation water in agriculture, particularly in water-scarce regions. However, the possible risks due to heavy metals accumulation in plant tissues are often overlooked by producers. The present study aimed to identify heavy metals-induced structural modifications to roots of scented Rosa species that were irrigated with water of marginal quality. The chemical and mineral contents from the experimental irrigation canal water (control) and treated wastewater were below the limits recommended by the Pakistan Environmental Protection Agency (Pak-EPA) for medicinal plants. The experimentally untreated wastewater contained electrical conductivity (EC), chemical oxygen demand (COD), biological oxygen demand (BOD), and heavy metals (Co, Cu, Cd, Pb) that were above the recommended limits. The responses by wastewater-treated Rosa species (Rosa damascena, R. bourboniana, R. Gruss-an-Teplitz, and R. centifolia) were evaluated. The experimental data revealed that treated wastewater significantly increased the thickness of collenchyma (cortex and pith) and parenchyma tissues (vascular bundle, xylem, and phloem) of R. Gruss-an-Teplitz. Root dermal tissues (epidermis) of R. bourboniana also responded to treated wastewater. R. damascena and R. centifolia were the least affected species, under the experimental irrigation conditions. Collenchyma and dermal tissues were thicker in R. damascena and R. Gruss-an-Teplitz under untreated wastewater conditions. In parenchyma tissues, vascular bundles were thicker in R. damascena in untreated wastewater conditions, while the xylem and phloem of R. Gruss-an-Teplitz were thicker where treated wastewater was applied. In tissues other than the vascular bundle, the differences in anatomical metrics due to the experimental irrigation treatments were greater during the second year of the experiment than in the first year. The contents of metals other than chromium in the roots and

Heavy Metal Detoxification by Different Bacillus Species Isolated from Solar Salterns

PubMed Central

Syed, Shameer; Chinthala, Paramageetham

2015-01-01

The biosorption mechanism is an alternative for chemical precipitation and ultrafiltration which have been employed to treat heavy metal contamination with a limited success. In the present study, three species of Bacillus which were isolated from solar salterns were screened for their detoxification potential of the heavy metals, lead, chromium, and copper, by biosorption. Biosorption potential of each isolate was determined by Atomic Absorption Spectroscopy (AAS), Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), and Energy Dispersive Spectroscopy (EDS) as the amount of metal present in the medium after the treatment with the isolates. Bacterial isolates, Bacillus licheniformis NSPA5, Bacillus cereus NSPA8, and Bacillus subtilis NSPA13, showed significant level of lead biosorption with maximum of 87–90% by Bacillus cereus NSPA8. The biosorption of copper and chromium was relatively low in comparison with lead. With the obtained results, we have concluded that the bacterial isolates are potential agents to treat metal contamination in more efficient and ecofriendly manner. PMID:26525498

Expression of the B subunit of Escherichia coli heat-labile enterotoxin as a fusion protein in transgenic tomato.

PubMed

Walmsley, A M; Alvarez, M L; Jin, Y; Kirk, D D; Lee, S M; Pinkhasov, J; Rigano, M M; Arntzen, C J; Mason, H S

2003-06-01

Epitopes often require co-delivery with an adjuvant or targeting protein to enable recognition by the immune system. This paper reports the ability of transgenic tomato plants to express a fusion protein consisting of the B subunit of the Escherichia coli heat-labile enterotoxin (LTB) and an immunocontraceptive epitope. The fusion protein was found to assemble into pentamers, as evidenced by its ability to bind to gangliosides, and had an average expression level of 37.8 microg g(-1) in freeze-dried transgenic tissues. Processing of selected transgenic fruit resulted in a 16-fold increase in concentration of the antigen with minimal loss in detectable antigen. The species-specific nature of this epitope was shown by the inability of antibodies raised against non-target species to detect the LTB fusion protein. The immunocontraceptive ability of this vaccine will be tested in future pilot mice studies.

Substrate lability and plant activity controls greenhouse gas release from Neotropical peatland

NASA Astrophysics Data System (ADS)

Sjogersten, Sofie; Hoyos, Jorge; Lomax, Barry; Turner, Ben; Wright, Emma

2014-05-01

Almost one third of global CO2 emissions resulting from land use change and substantial CH4 emissions originate from tropical peatlands. However, our understanding of the controls of CO2 and CH4 release from tropical peatlands are limited. The aim of this study was to investigate the role of peat lability and the activity of the vegetation on gas release using a combination of field and laboratory experiments. We demonstrated that peat lability constrained CH4 production to the surface peat under anaerobic conditions. The presence of plants shifted the C balance from a C source to a C sink with respect to CO2 while the activity of the root system strongly influenced CH4 emissions through its impact on soil O2 inputs. Both field and laboratory data suggest a coupling between the photosynthetic activity of the vegetation and the release of both CO2 and CH4 following the circadian rhythm of the dominant plant functional types. Forest clearance for agriculture resulted in elevated CH4 release, which we attribute in part to the cessation of root O2 inputs to the peat. We conclude that high emissions of CO2 and CH4 from forested tropical peatlands are likely driven by labile C inputs from the vegetation but that root O2 release may limit CH4 emissions.

Effects of processing on the proximate and metal contents in three fish species from Nigerian coastal waters

PubMed Central

Bassey, Francisca I; Oguntunde, Fehintola C; Iwegbue, Chukwujindu M A; Osabor, Vincent N; Edem, Christopher A

2014-01-01

The effects of culinary practices such as boiling, frying, and grilling on the proximate compositions and concentrations of metals (Cd, Pb, Cr, Zn, Fe, Cu, Mn, Ni, and Hg) in commonly consumed fish species from the Nigerian coastal waters were investigated. The selected fish species were Polydactylus quadratifilis, Chrysicthys nigrodigitatus and Cynoglossus senegalensis. The culinary practices lead to increased protein, fat, and ash contents and decreased moisture contents of these fish species. The culinary practices resulted significant increase in the concentrations of most of the studied metals and decrease in the concentrations of Fe, Cr, and Pb in some fish types. The concentrations and estimated dietary intakes of Cd, Pb, Cr, Zn, Fe, Cu, Mn, Ni, and Hg from consumption of the processed fish were within their statutory safe limits. The individual metal target hazard quotient (THQ) values and the total THQs were less than 1 which indicates that no health risks would arise from the long-term consumption of these fish species. PMID:24936297

In situ Identification of Labile Precursor Compounds and their Short-lived Intermediates in Plants using in vivo Nanospray High-resolution Mass Spectrometry.

PubMed

Chang, Qing; Peng, Yue'e; Shi, Bin; Dan, Conghui; Yang, Yijun; Shuai, Qin

2016-05-01

Many secondary metabolites in plants are labile compounds which under environmental stress, are difficult to detect and track due to the lack of rapid in situ identification techniques, making plant metabolomics research difficult. Therefore, developing a reliable analytical method for rapid in situ identification of labile compounds and their short-lived intermediates in plants is of great importance. To develop under atmospheric pressure, a rapid in situ method for effective identification of labile compounds and their short-lived intermediates in fresh plants. An in vivo nanospray high-resolution mass spectrometry (HR-MS) method was used for rapid capture of labile compounds and their short-lived intermediates in plants. A quartz capillary was partially inserted into fresh plant tissues, and the liquid flowed out through the capillary tube owing to the capillary effect. A high direct current (d.c.) voltage was applied to the plant to generate a spray of charged droplets from the tip of the capillary carrying bioactive molecules toward the inlet of mass spectrometer for full-scan and MS/MS analysis. Many labile compounds and short-lived intermediates were identified via this method: including glucosinolates and their short-lived intermediates (existing for only 10 s) in Raphanus sativus roots, alliin and its conversion intermediate (existing for 20 s) in Allium sativum and labile precursor compound chlorogenic acid in Malus pumila Mill. The method is an effective approach for in situ identification of internal labile compounds and their short-lived intermediates in fresh plants and it can be used as an auxiliary tool to explore the degradation mechanisms of new labile plant compounds. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Heavy-metal concentrations in small mammals from a diffusely polluted floodplain: importance of species- and location-specific characteristics.

PubMed

Wijnhoven, S; Leuven, R S E W; van der Velde, G; Jungheim, G; Koelemij, E I; de Vries, F T; Eijsackers, H J P; Smits, A J M

2007-05-01

The soil of several floodplain areas along large European rivers shows increased levels of heavy metals as a relict from past sedimentation of contaminants. These levels may pose risks of accumulation in food webs and toxicologic effects on flora and fauna. However, for floodplains, data on heavy-metal concentrations in vertebrates are scarce. Moreover, these environments are characterised by periodical flooding cycles influencing ecologic processes and patterns. To investigate whether the suggested differences in accumulation risks for insectivores and carnivores, omnivores, and herbivores are reflected in the actual heavy-metal concentrations in the species, we measured the current levels of Zn, Cu, Pb, and Cd in 199 specimens of 7 small mammal species (voles, mice, and shrews) and in their habitats in a diffusely polluted floodplain. The highest metal concentrations were found in the insectivorous and carnivorous shrew, Sorex araneus. Significant differences between the other shrew species, Crocidura russula, and the vole and mouse species was only found for Cd. The Cu concentration in Clethrionomys glareolus, however, was significantly higher than in several other vole and mouse species. To explain the metal concentrations found in the specimens, we related them to environmental variables at the trapping locations and to certain characteristics of the mammals. Variables taken into account were soil total and CaCl(2)-extractable metal concentrations at the trapping locations; whether locations were flooded or nonflooded; the trapping season; and the life stage; sex; and fresh weight of the specimens. Correlations between body and soil concentrations and location or specimen characteristics were weak. Therefore; we assumed that exposure of small mammals to heavy-metal contamination in floodplains is significantly influenced by exposure time, which is age related, as well as by dispersal and changes in foraging and feeding patterns under influence of periodic

Pollution Problem in River Kabul: Accumulation Estimates of Heavy Metals in Native Fish Species

PubMed Central

Ahmad, Habib; Yousafzai, Ali Muhammad; Siraj, Muhammad; Ahmad, Rashid; Ahmad, Israr; Nadeem, Muhammad Shahid; Ahmad, Waqar; Akbar, Nazia; Muhammad, Khushi

2015-01-01

The contamination of aquatic systems with heavy metals is affecting the fish population and hence results in a decline of productivity rate. River Kabul is a transcountry river originating at Paghman province in Afghanistan and inters in Khyber Pakhtunkhwa province of Pakistan and it is the major source of irrigation and more than 54 fish species have been reported in the river. Present study aimed at the estimation of heavy metals load in the fish living in River Kabul. Heavy metals including chromium, nickel, copper, zinc, cadmium, and lead were determined through atomic absorption spectrophotometer after tissue digestion by adopting standard procedures. Concentrations of these metals were recorded in muscles and liver of five native fish species, namely, Wallago attu, Aorichthys seenghala, Cyprinus carpio, Labeo dyocheilus, and Ompok bimaculatus. The concentrations of chromium, nickel, copper, zinc, and lead were higher in both of the tissues, whereas the concentration of cadmium was comparatively low. However, the concentration of metals was exceeding the RDA (Recommended Dietary Allowance of USA) limits. Hence, continuous fish consumption may create health problems for the consumers. The results of the present study are alarming and suggest implementing environmental laws and initiation of a biomonitoring program of the river. PMID:26339622

Pollution Problem in River Kabul: Accumulation Estimates of Heavy Metals in Native Fish Species.

PubMed

Ahmad, Habib; Yousafzai, Ali Muhammad; Siraj, Muhammad; Ahmad, Rashid; Ahmad, Israr; Nadeem, Muhammad Shahid; Ahmad, Waqar; Akbar, Nazia; Muhammad, Khushi

2015-01-01

The contamination of aquatic systems with heavy metals is affecting the fish population and hence results in a decline of productivity rate. River Kabul is a transcountry river originating at Paghman province in Afghanistan and inters in Khyber Pakhtunkhwa province of Pakistan and it is the major source of irrigation and more than 54 fish species have been reported in the river. Present study aimed at the estimation of heavy metals load in the fish living in River Kabul. Heavy metals including chromium, nickel, copper, zinc, cadmium, and lead were determined through atomic absorption spectrophotometer after tissue digestion by adopting standard procedures. Concentrations of these metals were recorded in muscles and liver of five native fish species, namely, Wallago attu, Aorichthys seenghala, Cyprinus carpio, Labeo dyocheilus, and Ompok bimaculatus. The concentrations of chromium, nickel, copper, zinc, and lead were higher in both of the tissues, whereas the concentration of cadmium was comparatively low. However, the concentration of metals was exceeding the RDA (Recommended Dietary Allowance of USA) limits. Hence, continuous fish consumption may create health problems for the consumers. The results of the present study are alarming and suggest implementing environmental laws and initiation of a biomonitoring program of the river.

[Character of brain interhemispheric relation in children at forming labile arterial hypertension].

PubMed

Koroleva, N V; Kolesnikov, S I; Bugun, O V; Dolgikh, V V

2010-01-01

Electroencephalography investigations were carried out twice in 26 schoolchildren in the age of 7-8 years and in the age of 9-10 years. The control group included healthy children: the research group included children in whom in the age of 7-8 years the normal level of arterial pressure was registered, and in whom in the age of 9-10 years labile arterial hypertension was revealed. It is revealed, that in children of younger school age forming of the labile form of arterial hypertension is connected whit infringement of processes of age changes of intercortical and cortical-subcortical interrelations and forming of rigidly integrated system of interhemispheric relations. Its mechanism of realization is carried out due to hyperactivation of the right hemisphere and it is incorporated on preclinical stage.

Evaluating Multiple Drivers of Soil Organic Matter Lability and Structure in a Sub-Alpine Forest Ecosystem

NASA Astrophysics Data System (ADS)

Hall, E.; Fegel, T. S., II; Boot, C. M.

2014-12-01

Aeolian deposition of reactive nitrogen (N) is reaching even the most remote ecosystems. There has been an abundance of research investigating how these subsidies of reactive N may alter fundamental ecosystem characteristics such as soil organic matter (SOM) pool size. Previous studies have reported that additions of reactive N have the potential to both increase and decrease SOM content. While there are a series of different variables that may affect the size of the SOM pool it has been suggested that the lability or recalcitrance of the SOM may be related to its chemical composition (kind and relative abundance of constituent molecules). To address this we sampled 6 experimental plots in a sub-alpine forest in Rocky Mountain National Park (3 control and 3 treated with reactive N for 18 years) during two months in the summers of 2011 and 2012. We found the SOM content of the control plots was greater than that of the experimental plots. To assess lability of each SOM sample we extracted the SOM from each plot with water and incubated the dissolved organic carbon with a common aquatic microbial community from a lake within the watershed. To assess structure of the SOM pool we used ultra performance liquid chromatography (UPLC) coupled with MS of each extract before incubation with the bacterial community. The dissolved component of the SOM showed clear differences in lability both in total quantity and rate of decomposition during incubation with aquatic microorganisms. Principle components analysis indicated season was a stronger driver of DOM composition than fertilization, describing the majority of the variability between July and September 2012. When samples were considered within a season and year there were additional differences in both lability and composition of DOM. Here we evaluate the relative influence of inter- and intra-annual variability and reactive N on both the characteristics and composition of SOM. By linking UPLC-MS with a functional assay of

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

2015-01-01

phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface. PMID:26549929

Electronic tuning of the lability of Pt(II) complexes through pi-acceptor effects. Correlations between thermodynamic, kinetic, and theoretical parameters.

PubMed

Hofmann, Andreas; Jaganyi, Deogratius; Munro, Orde Q; Liehr, Günter; van Eldik, Rudi

2003-03-10

pi-Acceptor effects are often used to account for the unusual high lability of [Pt(terpy)L]((2)(-)(n)+) (terpy = 2,2':6',2' '-terpyridine) complexes. To gain further insight into this phenomenon, the pi-acceptor effect was varied systematically by studying the lability of [Pt(diethylenetriamine)OH(2)](2+) (aaa), [Pt(2,6-bis-aminomethylpyridine)OH(2)](2+) (apa), [Pt(N-(pyridyl-2-methyl)-1,2-diamino-ethane)OH(2)](2+) (aap), [Pt(bis(2-pyridylmethyl)amine)OH(2)](2+) (pap), [Pt(2,2'-bipyridine)(NH(3))(OH(2))](2+) (app), and [Pt(terpy)OH(2)](2+) (ppp). The crystal structure of the apa precursor [Pt(2,6-bis-aminomethylpyridine)Cl]Cl.H(2)O was determined. The substitution of water by a series of nucleophiles, viz. thiourea, N,N-dimethylthiourea, N,N,N',N'-tetramethylthiourea, I(-), and SCN(-), was studied under pseudo-first-order conditions as a function of concentration, pH, temperature, and pressure, using stopped-flow techniques. The data enable an overall comparison of the substitution behavior of these complexes, emphasizing the role played by the kinetic cis and trans pi-acceptor effects. The results indicate that the cis pi-acceptor effect is larger than the trans pi-acceptor effect, and that the pi-acceptor effects are multiplicative. DFT calculations at the B3LYP/LACVP level of theory show that, by the addition of pi-acceptor ligands to the metal, the positive charge on the metal center increases, and the energy separation of the frontier molecular orbitals (E(LUMO) - E(HOMO)) of the ground state Pt(II) complexes decreases. The calculations collectively support the experimentally observed additional increase in reactivity when two pi-accepting rings are adjacent to each other (app and ppp), which is ascribed to "electronic communication" between the pyridine rings. The results furthermore indicate that the pK(a) value of the platinum bound water molecule is controlled by the pi-accepting nature of the chelate system and reflects the electron density around the

Heavy metal contamination and health risk assessment in three commercial fish species in the Persian Gulf.

PubMed

Keshavarzi, Behnam; Hassanaghaei, Mina; Moore, Farid; Rastegari Mehr, Meisam; Soltanian, Siyavash; Lahijanzadeh, Ahmad Reza; Sorooshian, Armin

2018-04-01

Five heavy metals/metalloids and related potential health risks were investigated in three commercially important fish species (Anodontostoma chacunda, Belangerii, and Cynoglossurs arel) in Musa Estuary and Mahshahr Harbour of the Persian Gulf. A total of 116 fish samples were collected, and their liver and muscle organs were separately analyzed using ICP-MS. Results revealed that studied metals concentrations (with some exceptions) varied among sampling stations, fish species and their organs. Human health risk is evaluated using different indices. The results indicated that arsenic and mercury are the most hazardous elements. Estimated daily intake (EDI) for the metals exceeded the provisional tolerable daily intake (PTDI) for all studied fish species. Also, target risk (TR) of arsenic indicated that consumption over a long period of time may result in a carcinogenic effect. The results are expected to create awareness among the public on the safety of consuming food products grown in particular areas. Copyright © 2018. Published by Elsevier Ltd.

Photoinitiated Electron Collection in Mixed-Metal Supramolecular Complexes: Development of Photocatalysts for Hydrogen Production. Final Report of Progress August 2017

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

Tanko, James M.

Mixed-metal supramolecular complexes containing one or two RuII light absorbing subunits coupled through polyazine bridging ligands to a RhIII reactive metal center were prepared for use as photocatalysts for the production of solar H 2 fuel from H 2O. The electrochemical, photophysical, and photochemical properties upon variation of the monodentate, labile ligands coordinated to the Rh reactive metal center were investigated.

Metal forms in sediments from Arctic coastal environments in Kandalaksha Bay, White Sea, under separation processes

NASA Astrophysics Data System (ADS)

Koukina, S. E.; Vetrov, A. A.

2013-09-01

This study focuses on sediments from small restricted exchange environments along the Karelian shore of Kandalaksha Bay (White Sea, Russian Arctic), which are known as separating basins and are characterised by contrasting oxidising conditions within the water column and the occurrence of anoxia. In the basins that were studied, no significant contamination by trace heavy metals (Pb, Cu, Zn and Cr, in particular) was detected. The comparative study of the two most bioavailable metal forms, namely, labile (acid soluble) and organically bound (alkali soluble) forms, indicated that acetic acid and sodium pyrophosphate released 3-11% and 2-12%, respectively, of the total metal content from sediments. The most bioavailable parts of metals are weakly bound to organic matter and, to a greater extent, associated with easily soluble amorphous Fe-oxides. Among the studied elements, most of the bioavailable Zn and Cu was most likely bound to organic substances, whereas bioavailable Cr and Mn were controlled to a greater extent by the formation of Fe-oxyhydroxide. The elements studied could be arranged in the following decreasing order of average potential bioavailability: Cu > Zn > Mn > Fe > Cr > Pb. In the separating basins, the relative proportion of labile bioavailable metals is enhanced in relation to the neighbouring open coastal sea.

Protein degradation by ubiquitin–proteasome system in formation and labilization of contextual conditioning memory

PubMed Central

Sol Fustiñana, María; de la Fuente, Verónica; Federman, Noel; Freudenthal, Ramiro

2014-01-01

The ubiquitin–proteasome system (UPS) of protein degradation has been evaluated in different forms of neural plasticity and memory. The role of UPS in such processes is controversial. Several results support the idea that the activation of this system in memory consolidation is necessary to overcome negative constrains for plasticity. In this case, the inhibition of the UPS during consolidation impairs memory. Similar results were reported for memory reconsolidation. However, in other cases, the inhibition of UPS had no effect on memory consolidation and reconsolidation but impedes the amnesic action of protein synthesis inhibition after retrieval. The last finding suggests a specific action of the UPS inhibitor on memory labilization. However, another interpretation is possible in terms of the synthesis/degradation balance of positive and negative elements in neural plasticity, as was found in the case of long-term potentiation. To evaluate these alternative interpretations, other reconsolidation-interfering drugs than translation inhibitors should be tested. Here we analyzed initially the UPS inhibitor effect in contextual conditioning in crabs. We found that UPS inhibition during consolidation impaired long-term memory. In contrast, UPS inhibition did not affect memory reconsolidation after contextual retrieval but, in fact, impeded memory labilization, blocking the action of drugs that does not affect directly the protein synthesis. To extend these finding to vertebrates, we performed similar experiments in contextual fear memory in mice. We found that the UPS inhibitor in hippocampus affected memory consolidation and blocked memory labilization after retrieval. These findings exclude alternative interpretations to the requirement of UPS in memory labilization and give evidence of this mechanism in both vertebrates and invertebrates. PMID:25135196

A Double Blind Trial of Divalproex Sodium for Affective Lability and Alcohol Use Following Traumatic Brain Injury

DTIC Science & Technology

2010-10-01

comparable to lithium in treating acutely manic bipolar patients, and the FDA approved it in 1995 for this indication. Also, it is used in conjunction with...A Double Blind Trial of Divalproex Sodium for Affective Lability and Alcohol Use Following Traumatic Brain Injury PRINCIPAL INVESTIGATOR...Lability and Alcohol Use Following Traumatic Brain Injury 5b. GRANT NUMBER W81XWH-08-2-0652 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S

The effects of metal ions on the DNA damage induced by hydrogen peroxide.

PubMed

Kobayashi, S; Ueda, K; Komano, T

1990-01-01

The effects of metal ions on DNA damage induced by hydrogen peroxide were investigated using two methods, agarose-gel electrophoretic analysis of supercoiled DNA and sequencing-gel analysis of single end-labeled DNA fragments of defined sequences. Hydrogen peroxide induced DNA damage when iron or copper ion was present. At least two classes of DNA damage were induced, one being direct DNA-strand cleavage, and the other being base modification labile to hot piperidine. The investigation of the damaged sites and the inhibitory effects of radical scavengers revealed that hydroxyl radical was the species which attacked DNA in the reaction of H2O2/Fe(II). On the other hand, two types of DNA damage were induced by H2O2/Cu(II). Type I damage was predominant and inhibited by potassium iodide, but type II was not. The sites of the base-modification induced by type I damage were similar to those by lipid peroxidation products and by ascorbate in the presence of Cu(II), suggesting the involvement of radical species other than free hydroxyl radical in the damaging reactions.

Heavy-metal-induced reactive oxygen species: phytotoxicity and physicochemical changes in plants.

PubMed

Shahid, Muhammad; Pourrut, Bertrand; Dumat, Camille; Nadeem, Muhammad; Aslam, Muhammad; Pinelli, Eric

2014-01-01

As a result of the industrial revolution, anthropogenic activities have enhanced there distribution of many toxic heavy metals from the earth's crust to different environmental compartments. Environmental pollution by toxic heavy metals is increasing worldwide, and poses a rising threat to both the environment and to human health.Plants are exposed to heavy metals from various sources: mining and refining of ores, fertilizer and pesticide applications, battery chemicals, disposal of solid wastes(including sewage sludge), irrigation with wastewater, vehicular exhaust emissions and adjacent industrial activity.Heavy metals induce various morphological, physiological, and biochemical dysfunctions in plants, either directly or indirectly, and cause various damaging effects. The most frequently documented and earliest consequence of heavy metal toxicity in plants cells is the overproduction of ROS. Unlike redox-active metals such as iron and copper, heavy metals (e.g, Pb, Cd, Ni, AI, Mn and Zn) cannot generate ROS directly by participating in biological redox reactions such as Haber Weiss/Fenton reactions. However, these metals induce ROS generation via different indirect mechanisms, such as stimulating the activity of NADPH oxidases, displacing essential cations from specific binding sites of enzymes and inhibiting enzymatic activities from their affinity for -SH groups on the enzyme.Under normal conditions, ROS play several essential roles in regulating the expression of different genes. Reactive oxygen species control numerous processes like the cell cycle, plant growth, abiotic stress responses, systemic signalling, programmed cell death, pathogen defence and development. Enhanced generation of these species from heavy metal toxicity deteriorates the intrinsic antioxidant defense system of cells, and causes oxidative stress. Cells with oxidative stress display various chemical,biological and physiological toxic symptoms as a result of the interaction between ROS and

Comparison between numeric and approximate analytic solutions for the prediction of soil metal uptake by roots. Example of cadmium.

PubMed

Schneider, André; Lin, Zhongbing; Sterckeman, Thibault; Nguyen, Christophe

2018-04-01

The dissociation of metal complexes in the soil solution can increase the availability of metals for root uptake. When it is accounted for in models of bioavailability of soil metals, the number of partial differential equations (PDEs) increases and the computation time to numerically solve these equations may be problematic when a large number of simulations are required, for example for sensitivity analyses or when considering root architecture. This work presents analytical solutions for the set of PDEs describing the bioavailability of soil metals including the kinetics of complexation for three scenarios where the metal complex in solution was fully inert, fully labile, or partially labile. The analytical solutions are only valid i) at steady-state when the PDEs become ordinary differential equations, the transient phase being not covered, ii) when diffusion is the major mechanism of transport and therefore, when convection is negligible, iii) when there is no between-root competition. The formulation of the analytical solutions is for cylindrical geometry but the solutions rely on the spread of the depletion profile around the root, which was modelled assuming a planar geometry. The analytical solutions were evaluated by comparison with the corresponding PDEs for cadmium in the case of the French agricultural soils. Provided that convection was much lower than diffusion (Péclet's number<0.02), the cumulative uptakes calculated from the analytic solutions were in very good agreement with those calculated from the PDEs, even in the case of a partially labile complex. The analytic solutions can be used instead of the PDEs to predict root uptake of metals. The analytic solutions were also used to build an indicator of the contribution of a complex to the uptake of the metal by roots, which can be helpful to predict the effect of soluble organic matter on the bioavailability of soil metals. Copyright © 2017 Elsevier B.V. All rights reserved.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species

The interactive effects of affect lability, negative urgency, and sensation seeking on young adult problematic drinking.

PubMed

Karyadi, Kenny; Coskunpinar, Ayca; Dir, Allyson L; Cyders, Melissa A

2013-01-01

Prior studies have suggested that affect lability might reduce the risk for problematic drinking among sensation seekers by compensating for their deficiencies in emotional reactivity and among individuals high on negative urgency by disrupting stable negative emotions. Due to the high prevalence of college drinking, this study examined whether affect lability interacted with sensation seeking and negative urgency to influence college student problematic drinking. 414 college drinkers (mean age: 20, 77% female, and 74% Caucasian) from a US Midwestern University completed self-administered questionnaires online. Consistent with our hypotheses, our results indicated that the effects of sensation seeking and negative urgency on problematic drinking weakened at higher levels of affect lability. These findings emphasize the importance of considering specific emotional contexts in understanding how negative urgency and sensation seeking create risk for problematic drinking among college students. These findings might also help us better understand how to reduce problematic drinking among sensation seekers and individuals high on negative urgency.

The Interactive Effects of Affect Lability, Negative Urgency, and Sensation Seeking on Young Adult Problematic Drinking

PubMed Central

Karyadi, Kenny; Coskunpinar, Ayca; Dir, Allyson L.; Cyders, Melissa A.

2013-01-01

Prior studies have suggested that affect lability might reduce the risk for problematic drinking among sensation seekers by compensating for their deficiencies in emotional reactivity and among individuals high on negative urgency by disrupting stable negative emotions. Due to the high prevalence of college drinking, this study examined whether affect lability interacted with sensation seeking and negative urgency to influence college student problematic drinking. 414 college drinkers (mean age: 20, 77% female, and 74% Caucasian) from a US Midwestern University completed self-administered questionnaires online. Consistent with our hypotheses, our results indicated that the effects of sensation seeking and negative urgency on problematic drinking weakened at higher levels of affect lability. These findings emphasize the importance of considering specific emotional contexts in understanding how negative urgency and sensation seeking create risk for problematic drinking among college students. These findings might also help us better understand how to reduce problematic drinking among sensation seekers and individuals high on negative urgency. PMID:24826366

Boechera Species Exhibit Species-Specific Responses to Combined Heat and High Light Stress

PubMed Central

Gallas, Genna; Waters, Elizabeth R.

2015-01-01

As sessile organisms, plants must be able to complete their life cycle in place and therefore tolerance to abiotic stress has had a major role in shaping biogeographical patterns. However, much of what we know about plant tolerance to abiotic stresses is based on studies of just a few plant species, most notably the model species Arabidopsis thaliana. In this study we examine natural variation in the stress responses of five diverse Boechera (Brassicaceae) species. Boechera plants were exposed to basal and acquired combined heat and high light stress. Plant response to these stresses was evaluated based on chlorophyll fluorescence measurements, induction of leaf chlorosis, and gene expression. Many of the Boechera species were more tolerant to heat and high light stress than A. thaliana. Gene expression data indicates that two important marker genes for stress responses: APX2 (Ascorbate peroxidase 2) and HsfA2 (Heat shock transcription factor A2) have distinct species-specific expression patterns. The findings of species-specific responses and tolerance to stress indicate that stress pathways are evolutionarily labile even among closely related species. PMID:26030823

Analysis and modeling of heat-labile enterotoxins of Escherichia coli suggests a novel space with insights into receptor preference.

PubMed

Krishna Raja, M; Ghosh, Asit Ranjan; Vino, S; Sajitha Lulu, S

2015-01-01

Features of heat-labile enterotoxins of Escherichia coli which make them fit to use as novel receptors for antidiarrheals are not completely explored. Data-set of 14 different serovars of enterotoxigenic Escherichia coli producing heat-labile toxins were taken from NCBI Genbank database and used in the study. Sequence analysis showed mutations in different subunits and also at their interface residues. As these toxins lack crystallography structures, homology modeling using Modeller 9.11 led to the structural approximation for the E. coli producing heat-labile toxins. Interaction of modeled toxin subunits with proanthocyanidin, an antidiarrheal showed several strong hydrogen bonding interactions at the cost of minimized energy. The hits were subsequently characterized by molecular dynamics simulation studies to monitor their binding stabilities. This study looks into novel space where the ligand can choose the receptor preference not as a whole but as an individual subunit. Mutation at interface residues and interaction among subunits along with the binding of ligand to individual subunits would help to design a non-toxic labile toxin and also to improve the therapeutics.

Heavy metals accumulation in wood tissues of the forest-forming species growed in the Steppe technogenic landscapes in Ukraine

NASA Astrophysics Data System (ADS)

Lovinska, Viktoriia; Wiche, Oliver

2016-04-01

Territory of Steppe in Ukraine is affected by significant anthropogenic impact caused with mining, metallurgical, chemicalplants and heat power stations. The priority pollutants of the region emissions of these enterprises are presented such heavy metals as Cd, Pb, Cu, Zn, Ni, Mn. The regional forest ecosystems can be considered as potential concentrators of pollutants borned with different technogenic impact. It is necessary to study an ability of forests wood to accumulate heavy metals because accumulated toxins are eliminated from biogeochemical cycle in forest ecosystem for a long time. This study goal is to determine the accumulation properties of forest-forming species - Pinus sylvestris (Scots pine) and Robinia pseudoacacia (black locust) difference age group in relation to heavy metals. It was considerable also to assess the heavy metal distribution in the wood tissue of referred species.Heavy metals content were determined with atomic absorption spectrophotometer using. Scots pine and black locust are the main forest-forming species of natural and artificial forests within Northern Steppe.They can be seen as transformers of the heavy metals cycle and selective concentrators of toxic elements, under the conditions of their excessive concentrations in the environment.It was established that wood tissue of Scots pine and black locust accumulated cadmium in high concentrations according to the age in both species. Indexes of zinc accumulation in the wood of Scots pine exceeded the maximal value in the wood tissue of black locust. The results of our research demonstrated antagonistic interaction of cadmium and zinc. The highest copper concentrations was found for the trees at the age of 45 years. Lead has been identified in wood sample of all ages. Accumulation maximum was fixed in the oldest samples. The trend of concentration increasing of metal didn't find for both species. As for nickel there was established the opposite tendention for both studied species

Towards a More Complete Picture: Dissimilatory Metal Reduction by Anaeromyxobacter Species

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

Loeffler, Frank E.

2005-06-01

Towards a More Complete Picture: Dissimilatory Metal Reduction by Anaeromyxobacter Species The overarching goal of this 3-year project is to explore uranium reduction in Anaeromyxobacter species. Specifically, we explore the physiological requirements of available Anaeromyxobacter isolates, design molecular biology tools to detect and quantify Anaeromyxobacter in pure cultures, consortia, and environmental samples, assess their diversity, distribution, and abundance in the environment, including DOE sites, and attempt the isolation of additional Anaeromyxobacter species from the Oak Ridge Field Research Center (FRC). The performers on this project include Frank Loeffler (PI), Robert Sanford (Co-PI), Qingzhong Wu (postdoc), Sara Henry (graduate student withmore » fellowship, no charges to NABIR project), Ivy Thomson (graduate student, no charges to NABIR project), and Ryan Wagner (''Special Topics'' bioinformatics undergraduate student, no charges to NABIR project). Exploratory MALDI-TOF MS experiments for the specific detection of Anaeromyxobacter species were performed by Kerry Preston (graduate student, no charges to NABIR project).« less

Biochar Mechanisms of Heavy Metal Sorption and Potential Utility

NASA Astrophysics Data System (ADS)

Ippolito, J.

2015-12-01

Mining-affected lands are a global issue; in the USA alone there are an estimated 500,000 abandoned mines encompassing hundreds of thousands of hectares. Many of these sites generate acidic mine drainage that causes release of heavy metals, and subsequently degradation in environmental quality. Because of its potential liming characteristics, biochar may play a pivotal role as a soil amendment in future mine land reclamation. However, to date, most studies have focused on the use of biochar to sorb metals from solution. Previous studies suggest that metals are complexed by biochar surface function groups (leading to ion exchange, complexation), coordination with Pi electrons (C=C) of carbon, and precipitation of inorganic mineral phases. Several recent studies have focused on the use of biochar for amending mine land soils, showing that biochar can indeed reduce heavy metal lability, yet the mechanism(s) behind labile metal reduction have yet to be established. In a proof-of-concept study, we added lodgepole pine, tamarisk, and switchgrass biochar (0, 5, 10, 15% by weight; 500 oC) to four different western US mine land soils affected by various heavy metals (Cd, Cu, Mn, Pb, Zn). Extraction with 0.01M CaCl2 showed that increasing biochar application rate significantly decreased 'bioaccessible' metals in almost all instances. A concomitant increase in solution pH was observed, suggesting that metals may be rendered bio-inaccessible through precipitation as carbonate or (hydr)oxide phases, or sorbed onto mineral surfaces. However, this was only supposition and required further research. Thus, following the 0.01M CaCl2 extraction, biochar-soil mixtures were air-dried and metals were further extracted using the four-step BCR sequential removal procedure. Results from selective extraction suggest that, as compared to the controls, most metals in the biochar-amended mine land soils were associated with exchange sites, carbonate, and oxide phases. Biochar may play a

Heavy metal concentrations in redeveloping soil of mine spoil under plantations of certain native woody species in dry tropical environment, India.

PubMed

Singh, Anand N; Zeng, De-hui; Chen, Fu-sheng

2005-01-01

Total concentration of heavy metals (Cd, Cr, Cu, Fe, Pb, Ni, Mn and Zn) was estimated in the redeveloping soil of mine spoil under 5-yr old plantations of four woody species namely: Albizia lebbeck, Albizia procera, Tectona grandis and Dendrocalamus strictus. The data recorded in the present study were compared with other unplanted coal mine spoil colliery, which was around to the study site and adjoining area of dry tropical forest. Among all the heavy metals, the maximum concentration was found for Fe and minimum for Cd. However, among all four species, total concentrations of these heavy metals were recorded maximally in the plantation plots of T. grandis except for Fe, while minimally in A. lebbeck except for Zn, whereas, the maximum concentration of Fe and Zn was in the plantation plots of D. strictus and A. procera. Statistical analysis revealed significant differences due to species for all the heavy metals except Cu. Among four species, A. lebbeck, A. procera and D. strictus showed more efficient for reducing heavy metal concentrations whereas T. grandis was not more effective to reduce heavy metal concentrations in redeveloping soil of mine spoil.

Catalytic and regulatory roles of species involved in metal-nucleotide equilibriums in human pyridoxal kinase.

PubMed

Navarro, Freddy; Ramírez-Sarmiento, César A; Guixé, Victoria

2013-10-01

Pyridoxal 5'-phosphate is the active form of vitamin B6 and its deficiency is directly related with several human disorders, which make human pyridoxal kinase (hPLK) an important pharmacologic target. In spite of this, a carefully kinetic characterization of hPLK including the main species that regulates the enzymatic activity is at date missing. Here we analyse the catalytic and regulatory mechanisms of hPLK as a function of a precise determination of the species involved in metal-nucleotide equilibriums and describe new regulatory mechanisms for this enzyme. hPLK activity is supported by several metals, being Zn(2+) the most effective, although the magnitude of the effect observed is highly dependent on the relative concentrations of metal and nucleotide used. The true substrate for the reaction catalyzed by hPLK is the metal nucleotide complex, while ATP(4-) and HATP(3-) did not affect the activity. The enzyme presents substrate inhibition by both pyridoxal (PL) and ZnATP(2-), although the latter behaves as a weakly inhibitor. Our study also established, for the first time, a dual role for free Zn(2+); as an activator at low concentrations (19 μM optimal concentration) and as a potent inhibitor with a IC50 of 37 μM. These results highlighted the importance of an accurate estimation of the actual concentration of the species involved in metal-nucleotide equilibriums in order to obtain reliable values for the kinetic parameters, and for determine the true regulators of the PLK activity. They also help to explain the dissimilar kinetic parameters reported in the literature for this enzyme.

The ongoing search for small molecules to study metal-associated amyloid-β species in Alzheimer's disease.

PubMed

Savelieff, Masha G; DeToma, Alaina S; Derrick, Jeffrey S; Lim, Mi Hee

2014-08-19

The development of a cure for Alzheimer's disease (AD) has been impeded by an inability to pinpoint the root cause of this disorder. Although numerous potential pathological factors have been indicated, acting either individually or mutually, the molecular mechanisms leading to disease onset and progression have not been clear. Amyloid-β (Aβ), generated from proteolytic processing of the amyloid precursor protein (APP), and its aggregated forms, particularly oligomers, are suggested as key pathological features in AD-affected brains. Historically, highly concentrated metals are found colocalized within Aβ plaques. Metal binding to Aβ (metal-Aβ) generates/stabilizes potentially toxic Aβ oligomers, and produces reactive oxygen species (ROS) in vitro (redox active metal ions; plausible contribution to oxidative stress). Consequently, clarification of the relationship between Aβ, metal ions, and toxicity, including oxidative stress via metal-Aβ, can lead to a deeper understanding of AD development. To probe the involvement of metal-Aβ in AD pathogenesis, rationally designed and naturally occurring molecules have been examined as chemical tools to target metal-Aβ species, modulate the interaction between the metal and Aβ, and subsequently redirect their aggregation into nontoxic, off-pathway unstructured aggregates. These ligands are also capable of attenuating the generation of redox active metal-Aβ-induced ROS to mitigate oxidative stress. One rational design concept, the incorporation approach, installs a metal binding site into a framework known to interact with Aβ. This approach affords compounds with the simultaneous ability to chelate metal ions and interact with Aβ. Natural products capable of Aβ interaction have been investigated for their influence on metal-induced Aβ aggregation and have inspired the construction of synthetic analogues. Systematic studies of these synthetic or natural molecules could uncover relationships between chemical

Speciation in Metal Toxicity and Metal-Based Therapeutics

PubMed Central

Templeton, Douglas M.

2015-01-01

Metallic elements, ions and compounds produce varying degrees of toxicity in organisms with which they come into contact. Metal speciation is critical to understanding these adverse effects; the adjectives “heavy” and “toxic” are not helpful in describing the biological properties of individual elements, but detailed chemical structures are. As a broad generalization, the metallic form of an element is inert, and the ionic salts are the species that show more significant bioavailability. Yet the salts and other chelates of a metal ion can give rise to quite different toxicities, as exemplified by a range of carcinogenic potential for various nickel species. Another important distinction comes when a metallic element is organified, increasing its lipophilicity and hence its ability to penetrate the blood brain barrier, as is seen, for example, with organic mercury and tin species. Some metallic elements, such as gold and platinum, are themselves useful therapeutic agents in some forms, while other species of the same element can be toxic, thus focusing attention on species interconversions in evaluating metal-based drugs. The therapeutic use of metal-chelating agents introduces new species of the target metal in vivo, and this can affect not only its desired detoxification, but also introduce a potential for further mechanisms of toxicity. Examples of therapeutic iron chelator species are discussed in this context, as well as the more recent aspects of development of chelation therapy for uranium exposure. PMID:29056656

Influence of taxa, trophic level, and location on bioaccumulation of toxic metals in bird's feathers: a preliminary biomonitoring study using multiple bird species from Pakistan.

PubMed

Abbasi, Naeem Akhtar; Jaspers, Veerle Leontina Bernard; Chaudhry, Muhammad Jamshed Iqbal; Ali, Sakhawat; Malik, Riffat Naseem

2015-02-01

Increasing concentrations of heavy metals in the environment and their effects on ecosystems and biota is still an imminent threat, particularly in developing parts of the globe. The aim of the present study was to screen the heavy metal concentrations in multiple bird species across Pakistan and to preliminary evaluate the influence of taxa, trophic level, and geographical location on heavy metal accumulation in various bird species. For this purpose, we measured the concentration of 9 heavy metals (Pb, Cd, Cr, Ni, Co, Cu, Fe, Zn and Mn) in feathers of 48 bird species from different localities in Pakistan. Species exhibited heterogeneous levels of heavy metals in feathers with marked inter and intra specific variations. Mean concentrations of studied metals in feathers followed the trend Fe>Zn>Cu>Pb>Mn>Cr>Ni>Co>Cd. Species belonging to closely related taxa (families) showed comparable metal concentrations in their feathers, inferring potential phylogenetic similarities in metal exposure or accumulation. In general, concentrations of metals were greatest in carnivorous species followed by omnivorous and insectivorous birds, and granivores showing minimal levels (p<0.000). Furthermore, concentrations of metals varied significantly between locations (p<0.000) exhibiting highest concentrations in Punjab province and Baluchistan, probably due to higher industrial and agricultural activity and runoff, respectively. With certain limitation, influence of trophic level, taxonomic affiliation and sampling location of birds on toxic metal accumulation was also statistically corroborated through principal component analysis (PCA). This study highlights that despite restricted emissions, heavy metals persist in the local environment and may pose elevated risks for the studied bird species in Pakistan. Copyright © 2014 Elsevier Ltd. All rights reserved.

Evaluation of Trace Metal Levels in Tissues of Two Commercial Fish Species in Kapar and Mersing Coastal Waters, Peninsular Malaysia

PubMed Central

Bashir, Fathi Alhashmi; Shuhaimi-Othman, Mohammad; Mazlan, A. G.

2012-01-01

This study is focused on evaluating the trace metal levels in water and tissues of two commercial fish species Arius thalassinus and Pennahia anea that were collected from Kapar and Mersing coastal waters. The concentrations of Fe, Zn, Al, As, Cd and Pb in these coastal waters and muscle, liver and gills tissues of the fishes were quantified. The relationship among the metal concentrations and the height and weight of the two species were also examined. Generally, the iron has the highest concentrations in both water and the fish species. However, Cd in both coastal waters showed high levels exceeding the international standards. The metal level concentration in the sample fishes are in the descending order livers > gills > muscles. A positive association between the trace metal concentrations and weight and length of the sample fishes was investigated. Fortunately the level of these metal concentrations in fish has not exceeded the permitted level of Malaysian and international standards. PMID:22046193

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

PubMed

Kalis, Erwin J J; Temminghoff, Erwin J M; Town, Raewyn M; Unsworth, Emily R; van Riemsdijk, Willem H

2008-01-01

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.

Mechanism-based design of labile precursors for chromium(I) chemistry

DOE PAGES

Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

2015-08-27

Here, we report that dinitrogen complexes of the type Tp R,RCr–N 2–CrTp R,R are not the most labile precursors for Cr(I) chemistry, as they are sterically protected from obligatory associative ligand substitution. A mononuclear alkyne complex – Tp tBu,MeCr(η 2-C 2(SiMe 3) 2) – proved to be much more reactive.

Immunologic Interrelationships of Coliform Heat-Labile and Heat-Stable Enterotoxins

DTIC Science & Technology

1980-01-15

PUBLICATIONS Supported by Contract No. DAMD 17-77-C-7032 1. Klipstein FA, Engert RF: Immunological interrelationships between cholera toxin and the...heat-labile and heat-stable enterotoxins of coliform bacteria. Infec Immun 18:110, 1977 2. Klipstein FA, Engert RF: Immunological relationship of...different preparations of coliform enterotoxins. Infec Immun 21:771, 1978 3. Klipstein FA, Engert RF: Reversal of jejunal water secretion by glucose in

Immunological Interrelationships of Coliform Heat-Labile and Heat-Stable Enterotoxins

DTIC Science & Technology

1981-01-01

FA, Engert RF: Immunological interrelationships between cholera toxin and the heat-labile and heat-stable enterotoxins of coliforn, bacteria. Infec...Irnmun 18:110, 1977 2. Klipstein FA, Engert RF: Immunological relaticnsh~p of different preparations of coliform enterotoxins. Infec Immun 21:771, 1918...3 Klipstein FA, Engert RF: Reversal of jejunal water secretion by glucose in rats exposed to coliform enterotoxcins. Gastroenterology 75:255, 1978 4

Immunological Interrelationships of Coliform Heat-Labile and Heat-Stable Enterotoxins

DTIC Science & Technology

1981-09-01

FA, Engert RF: Immunological interrelationships between cholera toxin and the heat -labile and hoat-stable enterotoxins of coliform bacteria. Infec...Immun 18:110, 1977 2. Klipstein FA, Engert RF: Immunological relationship of different preparations of coliform enterotoxins. Infec Immun 21:771, 1978...3. Klipstein FA, Engert RF: Reversal of jejunal water secretion by glucose in rats exposed to coliform enterotoxins. Gastroenteroloj y 75:255, 1978 4

Molecular insights into the microbial formation of marine dissolved organic matter: recalcitrant or labile?

NASA Astrophysics Data System (ADS)

Koch, B. P.; Kattner, G.; Witt, M.; Passow, U.

2014-08-01

The degradation of marine dissolved organic matter (DOM) is an important control variable in the global carbon cycle. For our understanding of the kinetics of organic matter cycling in the ocean, it is crucial to achieve a mechanistic and molecular understanding of its transformation processes. A long-term microbial experiment was performed to follow the production of non-labile DOM by marine bacteria. Two different glucose concentrations and dissolved algal exudates were used as substrates. We monitored the bacterial abundance, concentrations of dissolved and particulate organic carbon (DOC, POC), nutrients, amino acids and transparent exopolymer particles (TEP) for 2 years. The molecular characterization of extracted DOM was performed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) after 70 days and after ∼2 years of incubation. Although glucose quickly degraded, a non-labile DOC background (5-9% of the initial DOC) was generated in the glucose incubations. Only 20% of the organic carbon from the algal exudate degraded within the 2 years of incubation. The degradation rates for the non-labile DOC background in the different treatments varied between 1 and 11 μmol DOC L-1 year-1. Transparent exopolymer particles, which are released by microorganisms, were produced during glucose degradation but decreased back to half of the maximum concentration within less than 3 weeks (degradation rate: 25 μg xanthan gum equivalents L-1 d-1) and were below detection in all treatments after 2 years. Additional glucose was added after 2 years to test whether labile substrate can promote the degradation of background DOC (co-metabolism; priming effect). A priming effect was not observed but the glucose addition led to a slight increase of background DOC. The molecular analysis demonstrated that DOM generated during glucose degradation differed appreciably from DOM transformed during the degradation of the algal exudates. Our

Microbial control of soil organic matter mineralization responses to labile carbon in subarctic climate change treatments.

PubMed

Rousk, Kathrin; Michelsen, Anders; Rousk, Johannes

2016-12-01

Half the global soil carbon (C) is held in high-latitude systems. Climate change will expose these to warming and a shift towards plant communities with more labile C input. Labile C can also increase the rate of loss of native soil organic matter (SOM); a phenomenon termed 'priming'. We investigated how warming (+1.1 °C over ambient using open top chambers) and litter addition (90 g m -2  yr -1 ) treatments in the subarctic influenced the susceptibility of SOM mineralization to priming, and its microbial underpinnings. Labile C appeared to inhibit the mineralization of C from SOM by up to 60% within hours. In contrast, the mineralization of N from SOM was stimulated by up to 300%. These responses occurred rapidly and were unrelated to microbial successional dynamics, suggesting catabolic responses. Considered separately, the labile C inhibited C mineralization is compatible with previously reported findings termed 'preferential substrate utilization' or 'negative apparent priming', while the stimulated N mineralization responses echo recent reports of 'real priming' of SOM mineralization. However, C and N mineralization responses derived from the same SOM source must be interpreted together: This suggested that the microbial SOM-use decreased in magnitude and shifted to components richer in N. This finding highlights that only considering SOM in terms of C may be simplistic, and will not capture all changes in SOM decomposition. The selective mining for N increased in climate change treatments with higher fungal dominance. In conclusion, labile C appeared to trigger catabolic responses of the resident microbial community that shifted the SOM mining to N-rich components; an effect that increased with higher fungal dominance. Extrapolating from these findings, the predicted shrub expansion in the subarctic could result in an altered microbial use of SOM, selectively mining it for N-rich components, and leading to a reduced total SOM-use. © 2016 John Wiley

Trauma exposure and heavy drinking and drug use among college students: Identifying the roles of negative and positive affect lability in a daily diary study.

PubMed

Weiss, Nicole H; Bold, Krysten W; Contractor, Ateka A; Sullivan, Tami P; Armeli, Stephen; Tennen, Howard

2018-04-01

Trauma exposure is linked to heavy drinking and drug use among college students. Extant research reveals positive associations between negative affect lability and both trauma exposure and alcohol use. This study aimed to extend past research by using daily diary methods to test whether (a) individuals with (versus without) trauma exposure experience greater negative and positive affect lability, (b) negative and positive affect lability are associated with heavy drinking and drug use, and (c) negative and positive affect lability mediate the relations between trauma exposure and heavy drinking and drug use. Participants were 1640 college students (M age=19.2, 54% female, 80% European American) who provided daily diary data for 30days via online surveys. Daily diaries assessed negative and positive affect and substance use (i.e., percent days of heavy drinking, percent days of drug use, total number of drugs used). Individuals with (versus without) a history of trauma exposure demonstrated higher levels of negative and positive affect lability. Negative, but not positive, affect lability was associated with percent days of heavy drinking, percent days of drug use, and total number of drugs used, and mediated the associations between trauma exposure and heavy drinking and drug use outcomes. Findings provide support for the underlying role of negative affect lability in the relations between trauma exposure and heavy drinking and drug use among college students, suggesting that treatments targeting negative affect lability may potentially serve to reduce heavy drinking and drug use among trauma-exposed college students. Copyright © 2017 Elsevier Ltd. All rights reserved.

DETERMINATION OF APPARENT QUANTUM YIELD SPECTRA FOR THE FORMATION OF BIOLOGICALLY LABILE PHOTOPRODUCTS

EPA Science Inventory

Quantum yield spectra for the photochemical formation of biologically labile photoproducts from dissolved organic matter (DOM) have not been available previously, although they would greatly facilitate attempts to model photoproduct formation rates across latitudinal, seasonal, a...

The Role of Reactive Oxygen Species (ROS) in the Biological Activities of Metallic Nanoparticles

PubMed Central

Abdal Dayem, Ahmed; Hossain, Mohammed Kawser; Lee, Soo Bin; Kim, Kyeongseok; Saha, Subbroto Kumar; Yang, Gwang-Mo; Choi, Hye Yeon; Cho, Ssang-Goo

2017-01-01

Nanoparticles (NPs) possess unique physical and chemical properties that make them appropriate for various applications. The structural alteration of metallic NPs leads to different biological functions, specifically resulting in different potentials for the generation of reactive oxygen species (ROS). The amount of ROS produced by metallic NPs correlates with particle size, shape, surface area, and chemistry. ROS possess multiple functions in cellular biology, with ROS generation a key factor in metallic NP-induced toxicity, as well as modulation of cellular signaling involved in cell death, proliferation, and differentiation. In this review, we briefly explained NP classes and their biomedical applications and describe the sources and roles of ROS in NP-related biological functions in vitro and in vivo. Furthermore, we also described the roles of metal NP-induced ROS generation in stem cell biology. Although the roles of ROS in metallic NP-related biological functions requires further investigation, modulation and characterization of metallic NP-induced ROS production are promising in the application of metallic NPs in the areas of regenerative medicine and medical devices. PMID:28075405

Oribatid communities and heavy metal bioaccumulation in selected species associated with lichens in a heavily contaminated habitat.

PubMed

Skubała, Piotr; Rola, Kaja; Osyczka, Piotr

2016-05-01

The study examines oribatid communities and heavy metal bioaccumulation in selected species associated with different microhabitats of a post-smelting dump, i.e. three lichen species of Cladonia with various growth forms and the slag substrate. The abundance of oribatids collected from the substrate was significantly lower than observed in lichen thalli. The morphology and chemical properties of lichens, and to some extent varying concentrations of heavy metals in thalli, are probably responsible for significant differences in oribatid communities inhabiting different Cladonia species. Some oribatids demonstrate the ability to accumulate zinc and cadmium with unusual efficiency, whereas lead is the most effectively regulated element by all species. A positive correlation was found between Zn content in all studied oribatids and their microhabitats. Oribatids exploring different food resources, i.e. fungivorous and non-fungivorous grazers, show considerable differences in bioconcentrations of certain elements.

Labile dissolved organic carbon supply limits hyporheic denitrification

NASA Astrophysics Data System (ADS)

Zarnetske, Jay P.; Haggerty, Roy; Wondzell, Steven M.; Baker, Michelle A.

2011-12-01

We used an in situ steady state 15N-labeled nitrate (15NO3-) and acetate (AcO-) well-to-wells injection experiment to determine how the availability of labile dissolved organic carbon (DOC) as AcO-influences microbial denitrification in the hyporheic zone of an upland (third-order) agricultural stream. The experimental wells receiving conservative (Cl- and Br) and reactive (15NO3-) solute tracers had hyporheic median residence times of 7.0 to 13.1 h, nominal flowpath lengths of 0.7 to 3.7 m, and hypoxic conditions (<1.5 mg O2 L-1). All receiving wells demonstrated 15N2 production during ambient conditions, indicating that the hyporheic zone was an environment with active denitrification. The subsequent addition of AcO- stimulated more denitrification as evidenced by significant δ15N2 increases by factors of 2.7 to 26.1 in receiving wells and significant decreases of NO3- and DO in the two wells most hydrologically connected to the injection. The rate of nitrate removal in the hyporheic zone increased from 218 kg ha-1 yr-1 to 521 kg ha-1 yr-1 under elevated AcO- conditions. In all receiving wells, increases of bromide and 15N2 occurred without concurrent increases in AcO-, indicating that 100% of AcO- was retained or lost in the hyporheic zone. These results support the hypothesis that denitrification in anaerobic portions of the hyporheic zone is limited by labile DOC supply.

New applications in EPA’s ECOTOX Knowledge System: Assimilating relative potencies of metals across chemical and biological species from literature-based toxicity effects data.

EPA Science Inventory

Toxicity of metals in field settings can vary widely among ionic chemical species and across biological receptors. Thus, a challenge often found in developing TRVs for the risk assessment of metals is identifying the most appropriate metal and biological species combinations for...

[Impact of Land Utilization Pattern on Distributing Characters of Labile Organic Carbon in Soil Aggregates in Jinyun Mountain].

PubMed

Li, Rui; Jiang, Chang-sheng; Hao, Qing-ju

2015-09-01

Four land utilization patterns were selected for this study in Jinyun mountain, including subtropical evergreen broad-leaved forest (abbreviation: forest), sloping farmland, orchard and abandoned land. Soil samples were taken every 10 cm in the depth of 60 cm soil and proportions of large macroaggregates (> 2 mm), small macroaggregates (0. 25-2 mm), microaggregates (0. 053 - 0. 25 mm) and silt + clay (<0. 053 mm) were obtained by wet sieving method to measure the content of organic carbon and labile organic carbon in each aggregate fraction and analyze impacts of land uses on organic carbon and labile organic carbon of soil aggregates. LOC content of four soil aggregates were significantly reduced with the increase of soil depth; in layers of 0-60 cm soil depth, our results showed that LOC contents of forest and abandoned land were higher than orchard and sloping farmland. Reserves of labile organic carbon were estimated by the same soil quality, it revealed that forest (3. 68 Mg.hm-2) > abandoned land (1. 73 Mg.hm-2) > orchard (1. 43 Mg.hm-2) >sloping farmland (0.54 Mg.hm-2) in large macroaggregates, abandoned land (7.77, 5. 01 Mg.hm-2) > forest (4. 96, 2.71 Mg.hm-2) > orchard (3. 33, 21. 10 Mg.hm-2) > sloping farmland (1. 68, 1. 35 Mg.hm-2) in small macroaggregates and microaggregates, and abandoned land(4. 32 Mg.hm-2) > orchard(4. 00 Mg.hm-2) > forest(3. 22 Mg.hm-2) > sloping farmland (2.37 Mg.hm-2) in silt + clay, forest and abandoned land were higher than orchard and sloping farmland in other three soil aggregates except silt + clay. It was observed that the level of organic carbon and labile organic carbon were decreased when bringing forest under cultivation to orchard or farmland, and augments on organic carbon and labile organic carbon were found after exchanging farmland to abandoned land. The most reverses of forest and abandoned land emerged in small macroaggregates, orchard and sloping farmland were in microaggregates. That was, during the

Argon direct analysis in real time mass spectrometry in conjunction with makeup solvents: a method for analysis of labile compounds.

PubMed

Yang, Hongmei; Wan, Debin; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

2013-02-05

Helium direct analysis in real time (He-DART) mass spectrometry (MS) analysis of labile compounds usually tends to be challenging because of the occurrence of prominent fragmentation, which obscures the assigning of an ion to an independent species or merely a fragment in a mixture. In the present work, argon DART (Ar-DART) MS in conjunction with makeup solvents has been demonstrated to analyze a variety of labile compounds including nucleosides, alkaloids, glucose, and other small molecules. The results presented here confirm that Ar-DART can generate significantly less energetic ions than conventional He-DART and is able to produce the intact molecular ions with little or no fragmentation in both positive and negative ion modes. Adding a makeup solvent (absolute ethyl alcohol, methanol, fluorobenzene, or acetone) to the argon gas stream at the exit of the DART ion source can result in 1-2 orders of magnitude increase in detection signals. The sensitivity attainable by Ar-DART was found to be comparable to that by He-DART. The investigation of influence of solvents improves our understanding of the fundamental desorption and ionization processes in DART. The practical application of this rapid and high throughput method is demonstrated by the successful analysis of a natural product (Crude Kusnezoff Monkshood) extract, demonstrating the great potential in mixture research.

Affective lability mediates the association between childhood trauma and suicide attempts, mixed episodes and co-morbid anxiety disorders in bipolar disorders.

PubMed

Aas, M; Henry, C; Bellivier, F; Lajnef, M; Gard, S; Kahn, J-P; Lagerberg, T V; Aminoff, S R; Bjella, T; Leboyer, M; Andreassen, O A; Melle, I; Etain, B

2017-04-01

Many studies have shown associations between a history of childhood trauma and more severe or complex clinical features of bipolar disorders (BD), including suicide attempts and earlier illness onset. However, the psychopathological mechanisms underlying these associations are still unknown. Here, we investigated whether affective lability mediates the relationship between childhood trauma and the severe clinical features of BD. A total of 342 participants with BD were recruited from France and Norway. Diagnosis and clinical characteristics were assessed using the Diagnostic Interview for Genetic Studies (DIGS) or the Structured Clinical Interview for DSM-IV Axis I disorders (SCID-I). Affective lability was measured using the short form of the Affective Lability Scale (ALS-SF). A history of childhood trauma was assessed using the Childhood Trauma Questionnaire (CTQ). Mediation analyses were performed using the SPSS process macro. Using the mediation model and covariation for the lifetime number of major mood episodes, affective lability was found to statistically mediate the relationship between childhood trauma experiences and several clinical variables, including suicide attempts, mixed episodes and anxiety disorders. No significant mediation effects were found for rapid cycling or age at onset. Our data suggest that affective lability may represent a psychological dimension that mediates the association between childhood traumatic experiences and the risk of a more severe or complex clinical expression of BD.

A comparative study on capability of different tree species in accumulating heavy metals from soil and ambient air.

PubMed

Alahabadi, Ahmad; Ehrampoush, Mohammad Hassan; Miri, Mohammad; Ebrahimi Aval, Hamideh; Yousefzadeh, Samira; Ghaffari, Hamid Reza; Ahmadi, Ehsan; Talebi, Parvaneh; Abaszadeh Fathabadi, Zeynab; Babai, Fatemeh; Nikoonahad, Ali; Sharafi, Kiomars; Hosseini-Bandegharaei, Ahmad

2017-04-01

Heavy metals (HMs) in the urban environment can be bio-accumulated by plant tissues. The aim of this study was to compare fourteen different tree species in terms of their capability to accumulate four airborne and soilborne HMs including; zinc (Zn), copper (Cu), lead (Pb), and cadmium (Cd). Samplings were performed during spring, summer, and fall seasons. To compare bioaccumulation ability, bio-concentration factor (BCF), comprehensive bio-concentration index (CBCI), and metal accumulation index (MAI) were applied. Species with the highest accumulation for single metal which shown using BCF did not have the highest CBCI and MAI. Based on CBCI and MAI, Pinus eldarica (7.74), Wistaria sinensis (8.82), Morus alba (8.7), and Nigral morus (27.15) had the highest bioaccumulation capacity of HMs, respectively. Therefore, these species can be used for phytoextraction of HMs pollution and green and buffer zone in the urban. Copyright © 2017 Elsevier Ltd. All rights reserved.

Stabilization of cationic and anionic metal species in contaminated soils using sludge-derived biochar.

PubMed

Fang, Shen'en; Tsang, Daniel C W; Zhou, Fengsha; Zhang, Weihua; Qiu, Rongliang

2016-04-01

Currently, sludge pyrolysis has been considered as a promising technology to solve disposal problem of municipal sewage sludge, recover sludge heating value, sequester carbon and replenish nutrients in farmland soils. The resultant sludge-derived biochar (SDBC) is potentially an excellent stabilizing agent for metal species. This study applied the SDBC into four soils that had been contaminated in field with cationic Pb(II) and Cd(II)/Ni(II), and anionic Cr(VI) and As(III), respectively. The performance of metal stabilization under various operational and environmental conditions was evaluated with acid batch extraction and column leaching tests. Results indicated the SDBC could effectively stabilize these metals, which was favored by elevated temperature and longer aging. Periodic temperature decrease from 45 to 4 °C resulted in the release of immobilized Cr(VI) and As(III) but not Pb(II). However, a longer aging time offset such metal remobilization. This was possibly because more Pb was strongly bound and even formed stable precipitates, as shown by XRD and sequential extraction results. With increasing time, Cr(VI) was sorbed and partly reduced to Cr(III), while immobilized As(III) was co-oxidized to As(V) as indicated by XPS spectra. Column tests revealed that adding SDBC as a separate layer was unfavorable because the concentrated Cd(II) and Ni(II) in localized positions increased the peak levels of metal release under continuous acid leaching. In contrast, uniformly mixed SDBC could effectively delay the metal breakthrough and reduce their released amounts. Yet, a long-term monitoring may be required for evaluating the potential leaching risks and bioavailability/toxicity of these immobilized and transformed species in the SDBC-amended soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of interfacial species on shear strength of metal-sapphire contacts

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1979-01-01

The interfacial shear strength of the metal-insulator system has been studied by means of the coefficient of static friction of copper, nickel, or gold contacts on sapphire in ultrahigh vacuum. The effect on contact strength of adsorbed oxygen, nitrogen, chlorine, and carbon monoxide on the metal surfaces is reported. It was found that exposures as low as 1 L of O2 on Ni produced observable increases in contact strength, whereas exposures of 3 L of Cl2 lead to a decrease in contact strength. These results imply that submonolayer concentrations of these species at the interface of a thin Ni film on Al2O3 should affect film adhesion similarly. The atomic mechanism by which these surface or interface phases affect interfacial strength is not yet understood.

Stand-scale correspondence in empirical and simulated labile carbohydrates in loblolly pine

Treesearch

David A. Sampson; Kurt H. Johnsen; Kim H. Ludovici; Timothy J. Albaugh; Chris A. Maier

2001-01-01

As investment into intensive forestry increases, the potential trade-offs between productivity and sustainability should be scrutinized. Because of their important role in internal carbon (C) budgets, labile C pools may provide a measure of the potential ability of trees and stands to respond to stress. We modified the process model BIOMASS to...

Metal-Organic Framework-Templated Porous Carbon for Highly Efficient Catalysis: The Critical Role of Pyrrolic Nitrogen Species.

PubMed

Huang, Gang; Yang, Li; Ma, Xiao; Jiang, Jun; Yu, Shu-Hong; Jiang, Hai-Long

2016-03-01

Metal-free catalysts are of great importance and alternative candidates to conventional metal-based catalysts for many reactions. Herein, several types of metal-organic frameworks have been exploited as templates/precursors to afford porous carbon materials with various nitrogen dopant forms and contents, degrees of graphitization, porosities, and surface areas. Amongst these materials, the PCN-224-templated porous carbon material optimized by pyrolysis at 700 °C (denoted as PCN-224-700) is composed of amorphous carbon coated with well-defined graphene layers, offering a high surface area, hierarchical pores, and high nitrogen content (mainly, pyrrolic nitrogen species). Remarkably, as a metal-free catalyst, PCN-224-700 exhibits a low activation energy and superior activity to most metallic catalysts in the catalytic reduction of 4-nitrophenol to 4-aminophenol. Theoretical investigations suggest that the content and type of the nitrogen dopant play crucial roles in determining the catalytic performance and that the pyrrolic nitrogen species makes the dominant contribution to this activity, which explains the excellent efficiency of the PCN-224-700 catalyst well. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Affective lability and difficulties with regulation are differentially associated with amygdala and prefrontal response in women with Borderline Personality Disorder

PubMed Central

Silvers, Jennifer A.; Hubbard, Alexa D.; Biggs, Emily; Shu, Jocelyn; Fertuck, Eric; Chaudhury, Sadia; Grunebaum, Michael F.; Weber, Jochen; Kober, Hedy; Chesin, Megan; Brodsky, Beth S.; Koenigsberg, Harold; Ochsner, Kevin N.; Stanley, Barbara

2016-01-01

The present neuroimaging study investigated two aspects of difficulties with emotion associated with Borderline Personality Disorder (BPD1): affective lability and difficulty regulating emotion. While these two characteristics have been previously linked to BPD symptomology, it remains unknown whether individual differences in affective lability and emotion regulation difficulties are subserved by distinct neural substrates within a BPD sample. To address this issue, sixty women diagnosed with BPD were scanned while completing a task that assessed baseline emotional reactivity as well as top-down emotion regulation. More affective instability, as measured by the Affective Lability Scale (ALS2), positively correlated with greater amygdala responses on trials assessing emotional reactivity. Greater difficulties with regulating emotion, as measured by the Difficulties with Emotion Regulation Scale (DERS3), was negatively correlated with left inferior frontal gyrus (IFG4) recruitment on trials assessing regulatory ability. These findings suggest that, within a sample of individuals with BPD, greater bottom-up amygdala activity is associated with heightened affective lability. By contrast, difficulties with emotion regulation are related to reduced IFG recruitment during emotion regulation. These results point to distinct neural mechanisms for different aspects of BPD symptomology. PMID:27379614

How do low doses of desferrioxamine B and EDTA affect the phytoextraction of metals in sunflower?

PubMed

Cornu, J Y; Dépernet, C; Garnier, C; Lenoble, V; Braud, A; Lebeau, T

2017-08-15

The aim of this study was to compare the efficiency of siderophore desferrioxamine B (DFOB) and EDTA in increasing the phytoextraction of metals in sunflower. A 28-day pot experiment was conducted in a metal-contaminated soil supplied with 200μmolkg -1 of DFOB or EDTA. Pore water was collected and pseudo-polarographic analyses were conducted to assess the impact of the two chelators on the mobility and speciation of metals in the liquid phase. Our results showed that DFOB is not an efficient mobilizing agent of divalent metals in soil. Adding DFOB selectively increased the mobility of trivalent metals while the supply of EDTA simultaneously increased the mobility of both trivalent and divalent metals. EDTA significantly reduced the labile fractions of Cd, Cu, (Pb) and Zn measured in the porewater. The labile concentration of Cd and Zn measured in presence of EDTA was even less than that measured in the control. As expected from the pore water analysis, the addition of DFOB did not affect the phytoextraction of any divalent metals. In contrast, the addition of EDTA enhanced Cu and Ni phytoextraction in sunflower 2.0 to 2.8 fold for Cu and 1.3 to 2.3 fold for Ni, depending on the cultivar. This result supports different hypotheses regarding the forms and the related pathways in which metals are taken up in presence of EDTA. Based on the results obtained for Ni, whose uptake is rate limited by its internalization across the cell membrane, the direct uptake of metal-EDTA complexes via the non-selective apoplastic pathway is hypothesized to contribute the most to the overall uptake of metals in presence of EDTA, even added at "low" concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

Temporal and spatial distribution of metallic species in the upper atmosphere

NASA Astrophysics Data System (ADS)

Correira, John Thomas

2009-06-01

Every day the Earth is bombarded by approximately 100 tons of meteoric material. Much of this material is completely ablated on atmospheric entry, resulting in a layer of atomic metals in the upper atmosphere between 70 km - 150 km. These neutral atoms are ionized by solar radiation and charge exchange. Metal ions have a long lifetime against recombination loss, allowing them to be redistributed globally by electromagnetic forces, especially when lifted to altitudes >150 km. UV radiances from the Global Ozone Monitoring Experiment (GOME) spectrometer are used to determine long-term dayside variations of the total vertical column density below 795 km of the meteoric metal species Mg and Mg + in the upper atmosphere. A retrieval algorithm developed to determine magnesium column densities was applied to all available data from the years 1996-2001. Long term results show middle latitude dayside Mg + peaks in vertical content during the summer, while neutral Mg demonstrates a much more subtle maximum in summer. Atmospheric metal concentrations do not correlate strongly solar activity. An analysis of spatial variations shows geospatial distributions are patchy, with local regions of increased column density. To study short term variations and the role of meteor showers a time dependent mass flux rate is calculated using published estimates of meteor stream mass densities and activity profiles. An average daily mass flux rate is also calculated and used as a baseline against which shower mass flux rates are compared. These theoretical mass flux rates are then compared with GOME derived metal column densities. There appears to be little correlation between modeled meteor shower mass flux rates and changes in the observed neutral magnesium and Mg + metal column densities.

Effect of EDTA washing of metal polluted garden soils. Part I: Toxicity hazards and impact on soil properties.

PubMed

Jelusic, Masa; Lestan, Domen

2014-03-15

We applied a multi-level approach assessing the quality, toxicity and functioning of Pb, Zn and Cd contaminated/remediated soil from a vegetable garden in Meza Valley, Slovenia. Contaminated soil was extracted with EDTA and placed into field experimental plots equipped with lysimeters. Soil properties were assessed by standard pedological analysis. Fractionation and leachability of toxic metals were analyzed by sequential extraction and TCLP and metal bioaccessibility by UBM tests. Soil respiration and enzyme activities were measured as indicators of soil functioning. Remediation reduced the metal burden by 80, 28 and 72% for Pb, Zn and Cd respectively, with a limited impact on soil pedology. Toxic metals associated with labile soil fractions were largely removed. No shifts between labile and residual fractions were observed during the seven months of the experiment. Initial metal leaching measured through lysimeters eventually ceased. However, remediation significantly diminished potential soil enzyme activity and no trends were observed of the remediated soil recovering its biological properties. Soil washing successfully removed available forms of Pb, Zn and Cd and thus lowered the human and environmental hazards of the remediated soil; however, remediation also extracted the trace elements essential for soil biota. In addition to reduced water holding capacity, soil health was not completely restored. Copyright © 2013 Elsevier B.V. All rights reserved.

Antioxidant activities, metal contents, total phenolics and flavonoids of seven Morchella species.

PubMed

Gursoy, Nevcihan; Sarikurkcu, Cengiz; Cengiz, Mustafa; Solak, M Halil

2009-09-01

Seven Morchella species were analyzed for their antioxidant activities in different test systems namely beta-carotene/linoleic acid, DPPH, reducing power, chelating effect and scavenging effect (%) on the stable ABTS*(+), in addition to their heavy metals, total phenolic and flavonoid contents. In beta-carotene/linoleic acid system, the most active mushrooms were M. esculenta var. umbrina and M.angusticeps. In the case of DPPH, methanol extract of M. conica showed high antioxidant activity. The reducing power of the methanol extracts of mushrooms increased with concentration. Chelating capacity of the extracts was also increased with the concentration. On the other hand, in 40 microg ml(-1) concentration, methanol extract of M. conica, exhibited the highest radical scavenging activity (78.66+/-2.07%) when reacted with the ABTS*(+) radical. Amounts of seven elements (Cu, Mn, Co, Zn, Fe, Ca, and Mg) and five heavy metals (Ni, Pb, Cd, Cr, and Al) were also determined in all species. M. conica was found to have the highest phenolic content among the samples. Flavonoid content of M. rotunda was also found superior (0.59+/-0.01 microg QEs/mg extract).

Heavy-metal-contaminated industrial soil: Uptake assessment in native plant species from Brazilian Cerrado.

PubMed

Meyer, Sylvia Therese; Castro, Samuel Rodrigues; Fernandes, Marcus Manoel; Soares, Aylton Carlos; de Souza Freitas, Guilherme Augusto; Ribeiro, Edvan

2016-08-02

Plants of the Cerrado have shown some potential for restoration and/or phytoremediation projects due to their ability to grow in and tolerate acidic soils rich in metals. The aim of this study is to evaluate the tolerance and accumulation of metals (Cd, Cu, Pb, and Zn) in five native tree species of the Brazilian Cerrado (Copaifera langsdorffii, Eugenia dysenterica, Inga laurina, Cedrela fissilis, Handroanthus impetiginosus) subjected to three experiments with contaminated soils obtained from a zinc processing industry (S1, S2, S3) and control soil (S0). The experimental design was completely randomized (factorial 5 × 4 × 3) and conducted in a greenhouse environment during a 90-day experimentation time. The plant species behavior was assessed by visual symptoms of toxicity, tolerance index (TI), translocation factor (TF), and bioaccumulation factor (BF). C. fissilis has performed as a Zn accumulator by the higher BFs obtained in the experiments, equal to 3.72, 0.88, and 0.41 for S1, S2, and S3 respectively. This species had some ability of uptake control as a defense mechanism in high stress conditions with the best behavior for phytoremediation and high tolerance to contamination. With economical and technical benefits, this study may support a preliminary analysis necessary for using native tree species in environmental projects.

Reusable Oxidation Catalysis Using Metal-Monocatecholato Species in a Robust Metal–Organic Framework

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

Fei, Honghan; Shin, JaeWook; Meng, Ying Shirley

2014-04-02

An isolated metal-monocatecholato moiety has been achieved in a highly robust metal–organic framework (MOF) by two fundamentally different postsynthetic strategies: postsynthetic deprotection (PSD) and postsynthetic exchange (PSE). Compared with PSD, PSE proved to be a more facile and efficient functionalization approach to access MOFs that could not be directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing in the MOFs resulted in unprecedented Fe-monocatecholato and Cr-monocatecholato species, which were characterized by X-ray absorption spectroscopy, X-band electron paramagnetic resonance spectroscopy, and ⁵⁷Fe Mössbauer spectroscopy. The resulting materials are among the first examples of Zr(IV)-based UiO MOFs (UiO = Universitymore » of Oslo) with coordinatively unsaturated active metal centers. Importantly, the Cr-metalated MOFs are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates. Catalysis could be achieved with very low metal loadings (0.5–1 mol %). Unlike zeolite-supported, Cr-exchange oxidation catalysts, the MOF-based catalysts reported here are completely recyclable and reusable, which may make them attractive catalysts for ‘green’ chemistry processes.« less

Shifts in Climate Foster Exceptional Opportunities for Species Radiation: The Case of South African Geraniums

PubMed Central

Martínez-Cabrera, Hugo I.; Peres-Neto, Pedro R.

2013-01-01

Climate change is often assumed to be a major driver of biodiversity loss. However, it can also set the stage for novel diversification in lineages with the evolutionary ability to colonize new environments. Here we tested if the extraordinary evolutionary success of the genus Pelargonium was related to the ability of its species to capitalize on the climate niche variation produced by the historical changes in southern Africa. We evaluated the relationship between rates of climate niche evolution and diversification rates in the main Pelargonium lineages and disentangled the roles of deep and recent historical events in the modification of species niches. Pelargonium clades exhibiting higher ecological differentiation along summer precipitation (SPP) gradients also experienced higher diversification rates. Faster rates of niche differentiation in spatially structured variables, along with lower levels of niche overlap among closely related species, suggest recent modification in species niches (e.g. dispersal or range shift) and niche lability. We suggest that highly structured SPP gradients established during the aridification process within southern Africa, in concert with niche lability and low niche overlap, contributed to species divergence. These factors are likely to be responsible for the extensive diversification of other lineages in this diversity hot spot. PMID:24358250

Burkholderia metalliresistens sp. nov., a multiple metal-resistant and phosphate-solubilising species isolated from heavy metal-polluted soil in Southeast China.

PubMed

Guo, Jun Kang; Ding, Yong Zhen; Feng, Ren Wei; Wang, Rui Gang; Xu, Ying Ming; Chen, Chun; Wei, Xiu Li; Chen, Wei Min

2015-06-01

A metal-resistant and phosphate-solubilising bacterium, designated as strain D414(T), was isolated from heavy metal (Pb, Cd, Cu and Zn)-polluted paddy soils at the surrounding area of Dabao Mountain Mine in Southeast China. The minimum inhibitory concentrations of heavy metals for strain D414(T) were 2000 mg L(-1) (Cd), 800 mg L(-1) (Pb), 150 mg L(-1) (Cu) and 2500 mg L(-1) (Zn). The strain possessed plant growth-promoting properties, such as 1-aminocyclopropane-1-carboxylate assimilation, indole production and phosphate solubilisation. Analysis of 16S rRNA gene sequence indicated that the isolate is a member of the genus Burkholderia where strain D414(T) formed a distinct phyletic line with validly described Burkholderia species. Strain D414(T) is closely related to Burkholderia tropica DSM 15359(T), B. bannensis NBRC E25(T) and B. unamae DSM 17197(T), with 98.5, 98.3 and 98.3 % sequence similarities, respectively. Furthermore, less than 34 % DNA-DNA relatedness was detected between strain D414(T) and the type strains of the phylogenetically closest species of Burkholderia. The dominant fatty acids of strain D414(T) were C14:0, C16:0, C17:0 cyclo and C18:1 ω7c. The DNA G+C content was 62.3 ± 0.5 mol%. On the basis of genotypic, phenotypic and phylogenetic data, strain D414(T) represents a novel species, for which the name Burkholderia metalliresistens sp. nov. is proposed, with D414(T) (=CICC 10561(T) = DSM 26823(T)) as the type strain.

Biomonitoring of heavy metals in feathers of eleven common bird species in urban and rural environments of Tiruchirappalli, India.

PubMed

Manjula, Menon; Mohanraj, R; Devi, M Prashanthi

2015-05-01

Heavy metals continue to remain as a major environmental concern in spite of emission control measures. In this study, we analyzed the concentrations of heavy metals (Fe, Cr, Mn, Ni, Cu, Zn, and Cd) in the feathers of 11 species of birds collected from urban and rural areas of Tiruchirappalli, Southern India. Metal concentrations followed the order: Fe > Cu > Zn > Cr > Mn > Ni > Cd. Irrespective of sample locations, heavy metals such as Fe, Cr, Ni, Zn, and Cu were detected in high concentrations, while Cd and Mn were observed in lower concentrations. In contrary to our assumption, there were no statistically significant intraspecific and urban-rural differences in the metal concentrations except for Zn. Pairwise comparisons among species irrespective of metal type showed significant interspecific differences between Acridotheres tristis and Centropus phasianinus, A. tristis and Milvus migrans, C. phasianinus and M. migrans, M. migrans and Eudynamys scolopaceus, and Psittacula krameri and E. scolopaceus. Principal component analysis carried out for urban data extracted Ni, Mn, Zn, Fe, and Cu accounting for 48% variance implying dietary intake and external contamination as important sources for metals. In the rural, association of Zn, Cd, Ni, and Cr suggests the impact of metal fabrication industries and leather tanning operations.

Hemorrhagic Shock and Surgical Stress Alter Distribution of Labile Zinc within High and Low Molecular Weight Plasma Fractions

PubMed Central

Kelly, Edward; Mathew, Jeff; Kohler, Jonathan E.; Blass, Amy L.; Soybel, David I.

2012-01-01

Zinc ions (Zn2+) are essential for tissue repair following injury or stress. We hypothesize that during such stresses Zn2+ is redistributed to labile pools in plasma components. Here we tested this hypothesis utilizing a novel assay to monitor labile Zn2+ in plasma in hemorrhagic shock. Adult rats in the Shock (S) group underwent hemorrhage and resuscitation. Blood samples were drawn at baseline, 1 hr, 4 hrs and 24 hrs. The Surgical Control (SC) group was anesthetized and instrumented, but not bled. Albumin, total Zn2+, and labile Zn2+ levels were assayed in plasma. Binding capacity for Zn2+ was assessed in high (HMW) and low (LMW) molecular weight pools. Significant decreases in total Zn2+ were observed by 24 hrs, in both S and SC groups. Albumin levels were significantly reduced in the S group at 1 hr and 4 hr but restored at 24 hrs; significant changes were not observed in other groups. In whole plasma, labile Zn2+ levels were stable initially in the S and SC groups, but declined at 24 hrs. In the HMW pool, marked and significant impairment of binding was noted throughout all time periods following the shock period in the S group. Such changes were observed in the SC group of less intensity and duration. These experiments suggest that Shock alters affinity of plasma proteins for Zn2+, promoting delivery to peripheral tissues during periods of increased Zn2+ utilization. PMID:22744307

Hemorrhagic shock and surgical stress alter distribution of labile zinc within high- and low-molecular-weight plasma fractions.

PubMed

Kelly, Edward; Mathew, Jeff; Kohler, Jonathan E; Blass, Amy L; Soybel, And David I

2012-08-01

Zinc ions (Zn) are essential for tissue repair following injury or stress. We hypothesize that during such stresses Zn is redistributed to labile pools in plasma components. Here we tested this hypothesis using a novel assay to monitor labile Zn in plasma in hemorrhagic shock. Adult rats in the shock group (S group) underwent hemorrhage and resuscitation. Blood samples were drawn at baseline and at 1, 4, and 24 h. The surgical control group (SC group) was anesthetized and instrumented, but not bled. Albumin, total Zn, and labile Zn levels were assayed in plasma. Binding capacity for Zn was assessed in high- and low-molecular-weight pools. Significant decreases in total Zn were observed by 24 h, in both S and SC groups. Albumin levels were significantly reduced in the S group at 1 and 4 h but restored at 24 h; significant changes were not observed in other groups. In whole plasma, labile Zn levels were stable initially in the S and SC groups, but declined at 24 h. In the high-molecular-weight pool, marked and significant impairment of binding was noted throughout all time periods following the shock period in the S group. Such changes were observed in the SC group of less intensity and duration. These experiments suggest that shock alters affinity of plasma proteins for Zn, promoting delivery to peripheral tissues during periods of increased Zn utilization.

Bioremoval capacity of three heavy metals by some microalgae species (Egyptian Isolates)

PubMed Central

Shanab, Sanaa; Essa, Ashraf; Shalaby, Emad

2012-01-01

Three fresh water microalgal isolates [Phormidium ambiguum (Cyanobacterium), Pseudochlorococcum typicum and Scenedesmus quadricauda var quadrispina (Chlorophyta)] were tested for tolerance and removal of mercury (Hg2+), lead (Pb2+) and cadmium (Cd2+) in aqueous solutions as a single metal species at conc. 5–100 mg / L under controled laboratory conditions. The obtained results showed that Hg2+ was the most toxic of the three metal ions to the test algae even at low concentration (< 20 mg/L). While lower concentration of Pb2+ and Cd2+ (5–20 mg / L) enhanced the algal growth (chlorophyll a and protein), elevated concentrations (40–100 mg / L) were inhibitory to the growth. The results also revealed that Ph. ambiguum was the most sensitive alga to the three metal ions even at lower concentrations (5 and 10 mg / L) while P. typicum and S. quadricauda were more tolerant to high metal concentrations up to 100 mg / L. The bioremoval of heavy metal ions (Hg2+, Pb2+ and Cd2+) by P. typicum from aqueous solution showed that the highest percentage of metal bioremoval occurred in the first 30 min of contact recording 97% (Hg2+), 86% (Cd2+) and 70% (Pb2+). Transmission electron microscopy (TEM) was used to study the interaction between heavy metal ions and P. typicum cells. At ultrastructural level, an electron dense layers were detected on the algal cell surfaces when exposed to Cd, Hg and Pb. At the same time, dark spherical electron dense bodies were accumulated in the vacuoles of the algal cells exposed to Pb. Excessive accumulation of starch around the pyrenoids were recorded as well as deteriorations of the algal cell organelles exposed to the three metal ions. PMID:22476461

A feasibility study of perennial/annual plant species to restore soils contaminated with heavy metals

NASA Astrophysics Data System (ADS)

Zacarías, Montserrat; Beltrán, Margarita; Gilberto Torres, Luis; González, Abelardo

A feasibility study was carried out to evaluate the application of perennial/annual plant species in a phytoextraction process of a previously washed industrial urban soil contaminated by nickel, arsenic and cupper. The plant species selected for this study were Ipomea (Ipomea variada); grass (Poa pratensis); grass mixture (Festuca rubra, Cynodon dactylon, Lolium multiforum, Pennisetum sp.); Monks Cress (Tropaeolum majus); ficus (Ficus benajamina) and fern (Pteris cretica). Soil was characterized and it presented the following heavy metals concentrations (dry weight): 80 mg of Ni/kg, 456-656 mg of As/kg and 1684-3166 mg of Cu/kg. Germination and survival in contaminated soil tests were conducted, from these, P. pratensis was discarded and the rest of plant species tested were used for the phytoextraction selection test. After 4 months of growth, biomass production was determined, and content of Ni, As and Cu was analyzed in plant’s tissue. Metal biological absorption coefficient (BAC), bio-concentration factor (BCF) and translocation factor (TF), were calculated. Regarding to biomass generation it was observed, in every case, an inhibition of the plant growth compared with blanks sown in a non contaminated soil; inhibition ranged from 22.5% for the Monk cress to 98% for Ipomea. Even though the later presented high BAC, BCF and TF, its growth was severely inhibited, and therefore, due its low biomass generation, it is not recommended for phytoextraction under conditions for this study. Heavy metals concentrations in plant’s tissue (dry weight) were as high as 866 mg Cu/kg and 602 mg As/kg for grass mixture; and 825 mg As/kg was observed for Monks cress. Grass mixture and monks cress had high BAC, BCF and TF, also they had high metal concentrations in its plants tissues and the lowest growth inhibition rates; hence the application in phytoextraction processes of these plants is advisable.

Metal concentrations in three species of passerine birds breeding in the Hackensack Meadowlands of New Jersey

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

Tsipoura, Nellie; Burger, Joanna; Environmental and Occupational Health Sciences Institute, Piscataway, NJ 08854

2008-06-15

The New Jersey Meadowlands is an important natural area, a diverse mosaic of wetland habitats positioned within the heavily urbanized NY City Metropolitan area and the NY/NJ Harbor. Persistent contaminants may pose threats to wildlife inhabiting these habitats, affecting reproduction, egg hatchability, nestling survivorship, and neurobehavioral development. Metals of concern in the Meadowlands include arsenic, cadmium, chromium, lead, and mercury. These metals were analyzed in feathers and blood of three passerine birds breeding in wetland habitats, including red-winged blackbirds (Agelaius phoeniceus), marsh wrens (Cistothorus palustris), and tree swallow (Tachycineta bicolor), as well as eggs of the first two species. Thesemore » widespread species are abundant in wetland habitats across the Meadowlands District, and eat insects and other invertebrates. Lead levels were low in eggs, higher in feathers and very elevated in blood in all species compared to those that have been reported for other bird species. Lead levels were especially high in blood of marsh wren (mean of 0.8 ppm) and swallow (mean of 0.94 ppm, wet weight). Levels of lead in the blood for all three species sampled were higher than the negative impact threshold of 0.4 ppm. Mercury levels, while below the levels considered biologically harmful, were higher in eggs (mean of 0.2, wet weight) and feathers (3.2 ppm, dry weight) of marsh wren from Meadowlands than those seen in other passerines, and even some fish-eating birds. Furthermore, unhatched wren eggs had higher mercury levels (0.3 ppm, wet weight) than eggs randomly selected before hatch (0.18 ppm, wet weight). Blood tissue levels of mercury were low in all three species (mean of less than 0.035 ppm, wet weight). Chromium levels were relatively high in eggs and in blood, but lower in feathers when compared to those reported in the literature. Cadmium and arsenic levels were generally low for all tissues and in all species studied compared to

Lability of Secondary Organic Particulate Matter

DOE PAGES

Liu, Pengfei; Li, Yong Jie; Wang, Yan; ...

2016-10-24

Accurate simulations of the consenctrations of atmospheric organic particulate matter (PM) are needed for predicting energy flow in the Earth’s climate system. In the past, simulations of organic PM widely assume equilibrium partitioning of semivolatile organic compounds (SVOCs) between the PM and surrounding vapor. Herein, we test this assumption by measuring evaporation rates and associated vapor mass concentration of organic films representative of atmospheric PM. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH), indicating equilibrium partitioning above a transition RH but not below. In contrast for films representing biogenic PM,more » no threshold was observed, indicating equilibrium partitioning at all RHs. The results suggest that the mass lability of atmospheric organic PM can differ in consequential ways among Earth’s natural biomes, polluted regions, and regions of land-use change, and these differences need to be considered when simulating atmospheric organic PM.« less

Assessing SOC labile fractions through respiration test, density-size fractionation and thermal analysis - A comparison of methods

NASA Astrophysics Data System (ADS)

Soucemarianadin, Laure; Cécillon, Lauric; Chenu, Claire; Baudin, François; Nicolas, Manuel; Savignac, Florence; Barré, Pierre

2017-04-01

Soil organic matter (SOM) is the biggest terrestrial carbon reservoir, storing 3 to 4 times more carbon than the atmosphere. However, despite its major importance for climate regulation SOM dynamics remains insufficiently understood. For instance, there is still no widely accepted method to assess SOM lability. Soil respiration tests and particulate organic matter (POM) obtained by different fractionation schemes have been used for decades and are now considered as classical estimates of very labile and labile soil organic carbon (SOC), respectively. But the pertinence of these methods to characterize SOM turnover can be questioned. Moreover, they are very time-consuming and their reproducibility might be an issue. Alternate ways of determining the labile SOC component are thus well-needed. Thermal analyses have been used to characterize SOM among which Rock-Eval 6 (RE6) analysis of soil has shown promising results in the determination of SOM biogeochemical stability (Gregorich et al., 2015; Barré et al., 2016). Using a large set of samples of French forest soils representing contrasted pedoclimatic conditions, including deep samples (up to 1 m depth), we compared different techniques used for SOM lability assessment. We explored whether results from soil respiration test (10-week laboratory incubations), SOM size-density fractionation and RE6 thermal analysis were comparable and how they were correlated. A set of 222 (respiration test and RE6), 103 (SOM fractionation and RE6) and 93 (respiration test, SOM fractionation and RE6) forest soils samples were respectively analyzed and compared. The comparison of the three methods (n = 93) using a principal component analysis separated samples from the surface (0-10 cm) and deep (40-80 cm) layers, highlighting a clear effect of depth on the short-term persistence of SOC. A correlation analysis demonstrated that, for these samples, the two classical methods of labile SOC determination (respiration and SOM fractionation

Effects of the essential metals copper and zinc in two freshwater detritivores species: Biochemical approach.

PubMed

Quintaneiro, C; Ranville, J; Nogueira, A J A

2015-08-01

The input of metals into freshwater ecosystems from natural and anthropogenic sources impairs water quality and can lead to biological alterations in organisms and plants, compromising the structure and the function of these ecosystems. Biochemical biomarkers may provide early detection of exposure to contaminants and indicate potential effects at higher levels of biological organisation. The effects of 48h exposures to copper and zinc on Atyaephyra desmarestii and Echinogammarus meridionalis were evaluated with a battery of biomarkers of oxidative stress and the determination of ingestion rates. The results showed different responses of biomarkers between species and each metal. Copper inhibited the enzymatic defence system of both species without signs of oxidative damage. Zinc induced the defence system in E. meriodionalis with no evidence of oxidative damage. However, in A. desmarestii exposed to zinc was observed oxidative damage. In addition, only zinc had significantly reduced the ingestion rate and just for E. meridionalis. The value of the integrated biomarkers response increased with concentration of both metals, which indicates that might be a valuable tool to interpretation of data as a whole, as different parameters have different weight according to type of exposure. Copyright © 2015 Elsevier Inc. All rights reserved.

Suppression of inflammation in a mouse model of rheumatoid arthritis using targeted lipase-labile fumagillin prodrug nanoparticles.

PubMed

Zhou, Hui-Fang; Yan, Huimin; Senpan, Angana; Wickline, Samuel A; Pan, Dipanjan; Lanza, Gregory M; Pham, Christine T N

2012-11-01

Nanoparticle-based therapeutics are emerging technologies that have the potential to greatly impact the treatment of many human diseases. However, drug instability and premature release from the nanoparticles during circulation currently preclude clinical translation. Herein, we use a lipase-labile (Sn 2) fumagillin prodrug platform coupled with a unique lipid surface-to-surface targeted delivery mechanism, termed contact-facilitated drug delivery, to counter the premature drug release and overcome the inherent photo-instability of fumagillin, an established anti-angiogenic agent. We show that α(v)β(3)-integrin targeted fumagillin prodrug nanoparticles, administered at 0.3 mg of fumagillin prodrug/kg of body weight suppress the clinical disease indices of KRN serum-mediated arthritis in a dose-dependent manner when compared to treatment with the control nanoparticles with no drug. This study demonstrates the effectiveness of this lipase-labile prodrug nanocarrier in a relevant preclinical model that approximates human rheumatoid arthritis. The lipase-labile prodrug paradigm offers a translatable approach that is broadly applicable to many targeted nanosystems and increases the translational potential of this platform for many diseases. Copyright © 2012 Elsevier Ltd. All rights reserved.

Assessment of trace metal concentrations in muscle tissue of certain commercially available fish species from Kayseri, Turkey.

PubMed

Duran, Ali; Tuzen, Mustafa; Soylak, Mustafa

2014-07-01

Regular consumption of fish has been widely recommended by health authorities. However, it is known that some species accumulate high levels of contaminants including heavy metals (e.g., Hg, Cd, Pb, and As). In this study, Cu, Pb, Co, Ni, Cr, Mn, Cd, and Fe were determined in the muscle tissue of 11 commercially available fish species (Sparus auratus, Dicentrarchus labrax, Mullus barbatus, Belone belone, Psetta maxima, Epinephelus aeneus, Salmothymus, Soleidae, Pomatomus saltatrix, Engraulis encrasicolus, and Sarda sarda) supplied from retailers in Kayseri, Turkey. Determinations were carried out by flame atomic absorption spectrometry after the wet digestion method. The average metal concentrations of the 11 species were determined in the range of 0.54-1.79, 0.82-1.40, 2.38-4.54, 1.23-3.67, 5.01-5.97, 0.77-3.59, 0.48-1.06, and 5.05-122.8 μg/g wet weight for Cu, Pb, Co, Ni, Cr, Mn, Cd, and Fe, respectively. The permissible tolerable daily intake (PTDI) and calculated daily intake (CDI) values were compared, and the calculated daily intake values of the samples were found to be below the established values. Correlations between the metal contents in samples were investigated by performing correlation tests with SPSS 13.0 for windows.

Correlation between some selected trace metal concentrations in six species of fish from the Arabian Sea

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

Ashraf, M.; Jaffar, M.

1988-07-01

The role of trace metals in marine ecosystems has been keenly investigated during recent years. It is known that abundance of essential trace metals regulates the metal content in the organisms by homeostatic control mechanisms, which when cease to function cause essential trace metals to act in an either acutely or chronically toxic manner. Therefore, a correlation study based on essential and non-essential trace metal concentrations is imperative for extending the existing knowledge of bioaccumulation of trace metals in marine organisms. An attempt has been made in the present investigation to bring out quantitative correlations between the concentrations of iron,more » copper, lead and zinc in the edible muscle tissue of six species of marine fish: Salmon (salmon sole); tuna (thunnus thynnus); pomfret silver (pampus argenteus); Pomfret black (formioniger); long tail tuna (thynnus tonggel) and Indian oil sardine (sardinella longiceps). These fish are abundantly available in Pakistan along the coastal line of the Arabian Sea and have great commercial value. The computational analysis on the trace metal correlation was conducted using an MSTAT statistical package.« less

Labile Dissolved Organic Carbon Availability Controls Hyporheic Denitrification: a 15N Tracer Study

NASA Astrophysics Data System (ADS)

Zarnetske, J. P.; Haggerty, R.; Wondzell, S. M.; Baker, M. A.

2009-12-01

We used an in situ 15N-labeled nitrate (15NO3-) and acetate injection experiment to determine how the availability of labile dissolved organic carbon (DOC) as acetate influences microbial denitrification in the hyporheic zone (HZ) of an upland (3rd-order) agricultural stream. A 48 h steady-state injection of a conservative tracer, chloride, and 15NO3- was used to quantify ambient HZ denitrification via 15N2 production. Following ambient plateau measurements of denitrification during the first 24 h, a second conservative tracer, bromide, and labile DOC source, acetate, were co-injected for an additional 24 h to measure HZ denitrification under increased DOC supply. Conservative tracers were observed at 4 of the 6 down gradient wells. Receiving wells represented HZ median residence times of 7.0 to 13.1 h, nominal flowpath lengths of 0.7 to 3.7 m, and hypoxic conditions (7.5 to 9.3 mg-O2 L-1 deficit). All 4 receiving wells demonstrated 15N2 production during ambient conditions indicating that the HZ was an active denitrification environment. Acetate addition stimulated significant increases in 15N2 production by factors of 2.7 to 26.1 in all receiving wells, and significant decreases of NO3- and DOC aromaticity (via SUVA254) in the two wells most hydrologically connected to the injection. In all receiving wells, increases of bromide and 15N2 production occurred without concurrent increases in acetate indicating that 100% of acetate was retained in the HZ, a portion of which is due to biological consumption. These results support our hypothesis that microbial denitrification in anaerobic portions of the hyporheic zone is limited by labile DOC supply.

Novel diffusive gradients in thin films technique to assess labile sulfate in soil.

PubMed

Hanousek, Ondrej; Mason, Sean; Santner, Jakob; Chowdhury, Md Mobaroqul Ahsan; Berger, Torsten W; Prohaska, Thomas

2016-09-01

A novel diffusive gradients in thin films (DGT) technique for sampling labile soil sulfate was developed, based on a strong basic anion exchange resin (Amberlite IRA-400) for sulfate immobilization on the binding gel. For reducing the sulfate background on the resin gels, photopolymerization was applied instead of ammonium persulfate-induced polymerization. Agarose cross-linked polyacrylamide (APA) hydrogels were used as diffusive layer. The sulfate diffusion coefficient in APA gel was determined as 9.83 × 10(-6) ± 0.35 × 10(-6) cm(2) s(-1) at 25 °C. The accumulated sulfate was eluted in 1 mol L(-1) HNO3 with a recovery of 90.9 ± 1.6 %. The developed method was tested against two standard extraction methods for soil sulfate measurement. The obtained low correlation coefficients indicate that DGT and conventional soil test methods assess differential soil sulfate pools, rendering DGT a potentially important tool for measuring labile soil sulfate.

Can acid volatile sulfides (AVS) influence metal concentrations in the macrophyte Myriophyllum aquaticum?

PubMed

Teuchies, Johannes; De Jonge, Maarten; Meire, Patrick; Blust, Ronny; Bervoets, Lieven

2012-08-21

The difference between the molar concentrations of simultaneously extracted metals (SEM) and acid volatile sulfides (AVS) is widely used to predict metal availability toward invertebrates in hypoxic sediments. However, this model is poorly investigated for macrophytes. The present study evaluates metal accumulation in roots and stems of the macrophyte Myriophyllum aquaticum during a 54 day lab experiment. The macrophytes, rooting in metal contaminated, hypoxic, and sulfide rich field sediments were exposed to surface water with 40% or 90% oxygen. High oxygen concentrations in the 90% treatment resulted in dissolution of the metal-sulfide complexes and a gradual increase in labile metal concentrations during the experiment. However, the general trend of increasing availability in the sediment with time was not translated in rising M. aquaticum metal concentrations. Processes at the root-sediment interface, e.g., radial oxygen loss (ROL) or the release of organic compounds by plant roots and their effect on metal availability in the rhizosphere may be of larger importance for metal accumulation than the bulk metal mobility predicted by the SEM-AVS model.

Leaching and uptake of heavy metals by ten different species of plants during an EDTA-assisted phytoextraction process.

PubMed

Chen, Yahua; Li, Xiangdong; Shen, Zhenguo

2004-10-01

In a pot experiment, the potential use of 10 plant species, including six dicotyledon species and four monocotyledon species, was investigated for the EDTA-enhanced phytoextraction of Pb from contaminated soil. Mung bean and buckwheat had a higher sensitivity to the EDTA treatment in soils. In the 2.5 and 5.0 mmol kg(-1) EDTA treatments, the Pb concentrations in the shoots of the six dicotyledon species ranged from 1,000 to 3,000 mg kg(-1) of dry matter, which were higher than those of the monocotyledon species. The highest amount of phytoextracted Pb (2.9 mg Pb pot(-1)) was achieved in sunflowers, due to the high concentration of Pb in their shoots and large biomass, followed by corns (1.8 mg Pb pot(-1)) and peas (1.1 mg Pb pot(-1)). The leaching behavior of heavy metals as a result of applying EDTA to the surface of the soil was also investigated using short soil-leaching columns (9.0-cm diameter, 20-cm height) by the percolation of artificial rainfall. About 3.5%, 15.8%, 13.7% and 20.6% of soil Pb, Cu, Zn and Cd, respectively, were leached from the soil columns after the application of 5.0 mmol kg(-1) of EDTA. The growth of sunflowers in the soil columns had little effect on the amount of metals that were leached out. This was probably due to the shallowness of the layer of soil, the short time-span of the uptake of metals by the plant and the plant's simple root systems.

Fraction of organic carbon predicts labile desorption rates of chlorinated organic pollutants in laboratory-spiked geosorbents.

PubMed

Ginsbach, Jake W; Killops, Kato L; Olsen, Robert M; Peterson, Brittney; Dunnivant, Frank M

2010-05-01

The resuspension of large volumes of sediments that are contaminated with chlorinated pollutants continues to threaten environmental quality and human health. Whereas kinetic models are more accurate for estimating the environmental impact of these events, their widespread use is substantially hampered by the need for costly, time-consuming, site-specific kinetics experiments. The present study investigated the development of a predictive model for desorption rates from easily measurable sorbent and pollutant properties by examining the relationship between the fraction of organic carbon (fOC) and labile release rates. Duplicate desorption measurements were performed on 46 unique combinations of pollutants and sorbents with fOC values ranging from 0.001 to 0.150. Labile desorption rate constants indicate that release rates predominantly depend upon the fOC in the geosorbent. Previous theoretical models, such as the macro-mesopore and organic matter (MOM) diffusion model, have predicted such a relationship but could not accurately predict the experimental rate constants collected in the present study. An empirical model was successfully developed to correlate the labile desorption rate constant (krap) to the fraction of organic material where log(krap)=0.291-0.785 . log(fOC). These results provide the first experimental evidence that kinetic pollution releases during resuspension events are governed by the fOC content in natural geosorbents. Copyright (c) 2010 SETAC.

Heavy metals in wild marine fish from South China Sea: levels, tissue- and species-specific accumulation and potential risk to humans.

PubMed

Liu, Jin-Ling; Xu, Xiang-Rong; Ding, Zhen-Hua; Peng, Jia-Xi; Jin, Ming-Hua; Wang, You-Shao; Hong, Yi-Guo; Yue, Wei-Zhong

2015-10-01

Heavy metal pollution in marine fish has become an important worldwide concern, not only because of the threat to fish in general, but also due to human health risks associated with fish consumption. To investigate the occurrence of heavy metals in marine fish species from the South China Sea, 14 fish species were collected along the coastline of Hainan China during the spring of 2012 and examined for species- and tissue-specific accumulation. The median concentrations of Cd, Cr, Cu, Zn, Pb and As in muscle tissue of the examined fish species were not detectable (ND), 2.02, 0.24, 2.64, 0.025, and 1.13 mg kg(-1) wet weight, respectively. Levels of Cu, Zn, Cd and Cr were found to be higher in the liver and gills than in muscle, while Pb was preferentially accumulated in the gills. Differing from other heavy metals, As did not exhibit tissue-specific accumulation. Inter-species differences of heavy metal accumulation were attributed to the different habitat and diet characteristics of marine fish. Human dietary exposure assessment suggested that the amounts of both Cr and As in marine wild fish collected from the sites around Hainan, China were not compliant with the safety standard of less than 79.2 g d(-1) for wild marine fish set by the Joint FAO/WHO Expert Committee on Food Additives. Further research to identify the explicit sources of Cr and As in marine fish from South China Sea should be established.

Copper(II) and zinc(II) dinuclear enzymes model compounds: The nature of the metal ion in the biological function

NASA Astrophysics Data System (ADS)

Ferraresso, L. G.; de Arruda, E. G. R.; de Moraes, T. P. L.; Fazzi, R. B.; Da Costa Ferreira, A. M.; Abbehausen, C.

2017-12-01

First series transition metals are used abundantly by nature to perform catalytic transformations of several substrates. Furthermore, the cooperative activity of two proximal metal ions is common and represents a highly efficient catalytic system in living organisms. In this work three dinuclear μ-phenolate bridged metal complexes were prepared with copper(II) and zinc(II), resulting in a ZnZn, CuCu and CuZn with the ligand 2-ethylaminodimethylamino phenol (saldman) as model compounds of superoxide dismutase (CuCu and CuZn) and metallo-β-lactamases (ZnZn). Metals are coordinated in a μ-phenolate bridged symmetric system. Cu(II) presents a more distorted structure, while zinc is very symmetric. For this reason, [CuCu(saldman)] shows higher water solubility and also higher lability of the bridge. The antioxidant and hydrolytic beta-lactamase-like activity of the complexes were evaluated. The lability of the bridge seems to be important for the antioxidant activity and is suggested to because of [CuCu(saldman)] presents a lower antioxidant capacity than [CuZn(saldman)], which showed to present a more stable bridge in solution. The hydrolytic activity of the bimetallic complexes was assayed using nitrocefin as substrate and showed [ZnZn(saldman)] as a better catalyst than the Cu(II) analog. The series demonstrates the importance of the nature of the metal center for the biological function and how the reactivity of the model complex can be modulated by coordination chemistry.

Orbitrap-MS and FT-ICR-MS of Free and Labile Organic Matter from Carbonaceous Chondrites

NASA Astrophysics Data System (ADS)

Orthous-Daunay, F.-R.; Thissen, R.; Vuitton, V.; Somogyi, A.; Mespoulede, M.; Beck, P.; Bonnet, J.-Y.; Dutuit, O.; Schmitt, B.; Quirico, E.

2011-03-01

We used two types of high-resolution FT-MS to analyze the free and labile organic matter in carbonaceous chondrites of type 1 and 2. The methanol extraction and laser desorption gave access to highly and poorly functionalized molecules respectively.

Chemical leaching methods and measurements of marine labile particulate Fe

NASA Astrophysics Data System (ADS)

Revels, B. N.; John, S.

2012-12-01

Iron (Fe) is an essential nutrient for life. Yet its low solubility and concentration in the ocean limits marine phytoplankton productivity in many regions of the world. Dissolved phase Fe (<0.4μm) has traditionally been considered the most biologically accessible form, however, the particulate phase (>0.4μm) may contain an important, labile reservoir of Fe that may also be available to phytoplankton. However, concentration data alone cannot elucidate the sources of particulate Fe to the ocean and to what extent particulate iron may support phytoplankton growth. Isotopic analysis of natural particles may help to elucidate the biogeochemical cycling of Fe, though it is important to find a leaching method which accesses bioavailable Fe. Thirty-three different chemical leaches were performed on a marine sediment reference material, MESS-3. The combinations included four different acids (25% acetic acid, 0.01M HCl, 0.5M HCl, 0.1M H2SO4 at pH2), various redox conditions (0.02M hydroxylamine hydrochloride or 0.02M H2O2), three temperatures (25°C, 60°C, 90°C), and three time points (10 minutes, 2 hours, 24 hours). Leached Fe concentrations varied from 1mg/g to 35mg/g, with longer treatment times, stronger acids, and hotter temperatures generally associated with an increase in leached Fe. δ56Fe in these leaches varied from -1.0‰ to +0.2‰. Interestingly, regardless of leaching method used, there was a very similar relationship between the amount of Fe leached from the particles and the δ56Fe of this iron. Isotopically lighter δ56Fe values were associated with smaller amounts of leached Fe whereas isotopically heavier δ56Fe values were associated with larger amounts of leached Fe. Two alternate hypotheses could explain these data. Either, the particles may contain pools of isotopically light Fe that are easily accessed early in dissolution, or isotopically light Fe may be preferentially leached from the particle due to a kinetic isotope effect during dissolution

Effects of a Dam Reservoir on the Distribution of Heavy Metals in Two Chilean Native Freshwater Fish Species.

PubMed

Copaja, S V; Muñoz, G S; Nuñez, V R; Pérez, C; Vila, I; Véliz, D

2016-07-01

In order to determine the effect of a dam on metal concentrations in riverine fish species, we studied fish inhabiting the influent (Cachapoal River) and effluent (Rapel River) of the Rapel Reservoir in central Chile. Heavy metals were quantified in gills, liver and muscle of the catfish Trichomycterus areolatus and the silverside Basilichthys microlepidotus. Also, the bioaccumulation index (BAI) was estimated by considering heavy metal concentrations obtained from water and sediment. Results showed the presence of Al, Cu, Fe, Mn, Pb and Zn in the fish organs. The analysis showed high metal concentrations in catfish inhabiting the influent compared to those collected in the effluent. These results indicate a possible filter effect of the dam for most of the metals identified in the fish organs, because metal concentrations decreased in the effluent. Finally, catfish exhibited a larger BAI for most metals analyzed.

Unveiling the chemistry behind the green synthesis of metal nanoparticles.

PubMed

Santos, Sónia A O; Pinto, Ricardo J B; Rocha, Sílvia M; Marques, Paula A A P; Pascoal Neto, Carlos; Silvestre, Armando J D; Freire, Carmen S R

2014-09-01

Nanobiotechnology has emerged as a fundamental domain in modern science, and metallic nanoparticles (NPs) are one of the largest classes of NPs studied because of their wide spectrum of possible applications in several fields. The use of plant extracts as reducing and stabilizing agents in their synthesis is an interesting and reliable alternative to conventional methodologies. However, the role of the different components of such extracts in the reduction/stabilization of metal ions has not yet been understood clearly. Here we studied the behavior of the main components of a Eucalyptus globulus Labill. bark aqueous extract during metal-ion reduction followed by advanced chromatographic techniques, which allowed us to establish their specific role in the process. The obtained results showed that phenolic compounds, particularly galloyl derivatives, are mainly responsible for the metal-ion reduction, whereas sugars are essentially involved in the stabilization of the NPs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroxytyrosol inhibits hydrogen peroxide-induced apoptotic signaling via labile iron chelation.

PubMed

Kitsati, Natalia; Mantzaris, Michalis D; Galaris, Dimitrios

2016-12-01

Although it is known that Mediterranean diet plays an important role in maintaining human health, the underlying molecular mechanisms remain largely unknown. The aim of this investigation was to elucidate the potential role of ortho-dihydroxy group containing natural compounds in H 2 O 2 -induced DNA damage and apoptosis. For this purpose, the main phenolic alcohols of olive oil, namely hydroxytyrosol and tyrosol, were examined for their ability to protect cultured cells under conditions of oxidative stress. A strong correlation was observed between the ability of hydroxytyrosol to mitigate intracellular labile iron level and the protection offered against H 2 O 2 -induced DNA damage and apoptosis. On the other hand, tyrosol, which lacks the ortho-dihydroxy group, was ineffective. Moreover, hydroxytyrosol (but not tyrosol), was able to diminish the late sustained phase of H 2 O 2 -induced JNK and p38 phosphorylation. The derangement of intracellular iron homeostasis, following exposure of cells to H 2 O 2 , played pivotal role both in the induction of DNA damage and the initiation of apoptotic signaling. The presented results suggest that the protective effects exerted by ortho-dihydroxy group containing dietary compounds against oxidative stress-induced cell damage are linked to their ability to influence changes in the intracellular labile iron homeostasis. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Deposition and solubility of airborne metals to four plant species grown at varying distances from two heavily trafficked roads in London.

PubMed

Peachey, C J; Sinnett, D; Wilkinson, M; Morgan, G W; Freer-Smith, P H; Hutchings, T R

2009-01-01

In urban areas, a highly variable mixture of pollutants is deposited as particulate matter. The concentration and bioavailability of individual pollutants within particles need to be characterised to ascertain the risks to ecological receptors. This study, carried out at two urban parks, measured the deposition and water-solubility of metals to four species common to UK urban areas. Foliar Cd, Cr, Cu, Fe, Ni, Pb and Zn concentrations were elevated in at least one species compared with those from a rural control site. Concentrations were, however, only affected by distance to road in nettle and, to a lesser extent, birch leaves. Greater concentrations of metal were observed in these species compared to cypress and maple possibly due to differences in plant morphology and leaf surfaces. Solubility appeared to be linked to the size fraction and, therefore, origin of the metal with those present predominantly in the coarse fraction exhibiting low solubility.

Experimental Investigation of Molecular Species Formation in Metal Plasmas During Laser Ablation

NASA Astrophysics Data System (ADS)

Radousky, H.; Crowhurst, J.; Rose, T.; Armstrong, M.; Stavrou, E.; Zaug, J.; Weisz, D.; Azer, M.; Finko, M.; Curreli, D.

2016-10-01

Atomic and molecular spectra on metal plasmas generated by laser ablation have been measured using single, nominally 6-7 ns pulses at 1064 nm, and with energies less than 50 mJ. The primary goal for these studies is to constrain the physical and chemical mechanisms that control the distribution of radionuclides in fallout after a nuclear detonation. In this work, laser emission spectroscopy was used to obtain in situdata for vapor phase molecular species as they form in a controlled oxygen atmosphere for a variety of metals such as Fe, Al, as well as preliminary results for U. In particular, the ablation plumes created from these metals have been imaged with a resolution of 10 ns, and it is possible to observe the expansion of the plume out to 0.5 us. These data serve as one set of inputs for a semi-empirical model to describe the chemical fractionation of uranium during fallout formation. Prepared by LLNL under Contract DE-AC52-07NA27344. This project was sponsored by the Department of the Defense, Defense Threat Reduction Agency, under Grant Number HDTRA1-16-1-0020.

Forms and Lability of Phosphorus in Humic Acid Fractions of Hord Silt Loam Soil

USDA-ARS?s Scientific Manuscript database

Phosphorus (P) has long been known to be present in soil humic fractions, but little is known about specific P forms in humic fractions, or their lability. We extracted the mobile humic acid (MHA) and recalcitrant calcium humate (CaHA) fractions from a Nebraska Hord silt loam soil under continuous c...

Ecological transfer of radionuclides and metals to free-living earthworm species in natural habitats rich in NORM.

PubMed

Mrdakovic Popic, Jelena; Salbu, Brit; Skipperud, Lindis

2012-01-01

Transfer of radionuclides ((232)Th and (238)U) and associated metals (As, Cd, Pb and Cr) from soil to free-living earthworm species was investigated in a thorium ((232)Th) rich area in Norway. Sampling took place within former mining sites representing the technologically enhanced naturally occurring radioactive materials (TENORM), at undisturbed site with unique bedrock geology representing the naturally occurring radioactive materials (NORM) and at site outside the (232)Th rich area taken as reference Background site. Soil analysis revealed the elevated levels of investigated elements at NORM and TENORM sites. Based on sequential extraction, uranium ((238)U) and cadmium (Cd) were quite mobile, while the other elements were strongly associated with mineral components of soil. Four investigated earthworm species (Aporrectodea caliginosa, Aporrectodea rosea, Dendrodrilus rubidus and Lumbricus rubellus) showed large individual variability in the accumulation of radionuclides and metals. Differences in uptake by epigeic and endogeic species, as well as differences within same species from the NORM, TENORM and Background sites were also seen. Based on total concentrations in soil, the transfer factors (TF) were in ranges 0.03-0.08 and 0.09-0.25, for (232)Th and (238)U, respectively. TFs for lead (Pb), chromium (Cr) and arsenic (As) were low (less than 0.5), while TFs for Cd were higher (about 10). Using the ERICA tool, the estimated radiation exposure dose rate of the earthworms ranged from 2.2 to 3.9 μGy/h. The radiological risk for investigated earthworms was low (0.28). The obtained results demonstrated that free-living earthworm species can survive in soil containing elevated (232)Th and (238)U, as well As, Cd, Pb and Cr levels, although certain amount of radionuclides was accumulated within their bodies. The present investigation contributes to general better understanding of complex soil-to-biota transfer processes of radionuclides and metals and to assessment

How spatial variation in areal extent and configuration of labile vegetation states affect the riparian bird community in Arctic tundra.

PubMed

Henden, John-André; Yoccoz, Nigel G; Ims, Rolf A; Langeland, Knut

2013-01-01

The Arctic tundra is currently experiencing an unprecedented combination of climate change, change in grazing pressure by large herbivores and growing human activity. Thickets of tall shrubs represent a conspicuous vegetation state in northern and temperate ecosystems, where it serves important ecological functions, including habitat for wildlife. Thickets are however labile, as tall shrubs respond rapidly to both abiotic and biotic environmental drivers. Our aim was to assess how large-scale spatial variation in willow thicket areal extent, configuration and habitat structure affected bird abundance, occupancy rates and species richness so as to provide an empirical basis for predicting the outcome of environmental change for riparian tundra bird communities. Based on a 4-year count data series, obtained through a large-scale study design in low arctic tundra in northern Norway, statistical hierarchical community models were deployed to assess relations between habitat configuration and bird species occupancy and community richness. We found that species abundance, occupancy and richness were greatly affected by willow areal extent and configuration, habitat features likely to be affected by intense ungulate browsing as well as climate warming. In sum, total species richness was maximized in large and tall willow patches of small to intermediate degree of fragmentation. These community effects were mainly driven by responses in the occupancy rates of species depending on tall willows for foraging and breeding, while species favouring other vegetation states were not affected. In light of the predicted climate driven willow shrub encroachment in riparian tundra habitats, our study predicts that many bird species would increase in abundance, and that the bird community as a whole could become enriched. Conversely, in tundra regions where overabundance of large herbivores leads to decreased areal extent, reduced height and increased fragmentation of willow thickets

How Spatial Variation in Areal Extent and Configuration of Labile Vegetation States Affect the Riparian Bird Community in Arctic Tundra

PubMed Central

Henden, John-André; Yoccoz, Nigel G.; Ims, Rolf A.; Langeland, Knut

2013-01-01

The Arctic tundra is currently experiencing an unprecedented combination of climate change, change in grazing pressure by large herbivores and growing human activity. Thickets of tall shrubs represent a conspicuous vegetation state in northern and temperate ecosystems, where it serves important ecological functions, including habitat for wildlife. Thickets are however labile, as tall shrubs respond rapidly to both abiotic and biotic environmental drivers. Our aim was to assess how large-scale spatial variation in willow thicket areal extent, configuration and habitat structure affected bird abundance, occupancy rates and species richness so as to provide an empirical basis for predicting the outcome of environmental change for riparian tundra bird communities. Based on a 4-year count data series, obtained through a large-scale study design in low arctic tundra in northern Norway, statistical hierarchical community models were deployed to assess relations between habitat configuration and bird species occupancy and community richness. We found that species abundance, occupancy and richness were greatly affected by willow areal extent and configuration, habitat features likely to be affected by intense ungulate browsing as well as climate warming. In sum, total species richness was maximized in large and tall willow patches of small to intermediate degree of fragmentation. These community effects were mainly driven by responses in the occupancy rates of species depending on tall willows for foraging and breeding, while species favouring other vegetation states were not affected. In light of the predicted climate driven willow shrub encroachment in riparian tundra habitats, our study predicts that many bird species would increase in abundance, and that the bird community as a whole could become enriched. Conversely, in tundra regions where overabundance of large herbivores leads to decreased areal extent, reduced height and increased fragmentation of willow thickets

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

PubMed

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of heavy metals and metalloids in tissues of two frog species: Rana tigrina and Euphlyctis cyanophlyctis from industrial city Sialkot, Pakistan.

PubMed

Qureshi, Irfan Zia; Kashif, Zeshan; Hashmi, Muhammad Zaffar; Su, Xiaomei; Malik, Riffat Naseem; Ullah, Kalim; Hu, Jinxing; Dawood, Muhammad

2015-09-01

In the present study, we investigated the concentrations of Ni, Fe, Pb, Cu, Co, Zn, Cd, Mn, and Cr in selected body tissues (liver, stomach, kidney, heart, lungs, and skeletal muscles) of two frog species: Rana tigrina and Euphlyctis cyanophlyctis captured from industrial wastewater of Sialkot city known worldwide for its tanning industry. The both frog species had darker appearance, distinctively different wet body weight, and snout-vent length. The results revealed that the heavy metal concentrations were high in the samples collected from industrial sites as compared to non-industrial sites. The different tissues of R. tigrina and E. cyanophlyctis exhibited little significant differences from two sites. The concentrations of heavy metals were more in tissues of R. tigrina as compared to E. cyanophlyctis. Mean concentration of Cd, Fe, Ni, Mn, Cu, and Cr was comparatively greater in R. tigrina, whereas Pb and Co were higher in E. cyanophlyctis. The concentration of Cu and Cd in the liver and kidney were relatively more in both species as compared to other organs. Further, the results indicated that frogs collected from industrial sites showed decreased body length and weight, and greater metal accumulation. The results will help the authorities for the conservation of these frog species which are under the influence of heavy metal contamination.

Acute Toxicity, Respiratory Reaction, and Sensitivity of Three Cyprinid Fish Species Caused by Exposure to Four Heavy Metals

PubMed Central

Wang, Hongjun; Liang, Youguang; Li, Sixin; Chang, Jianbo

2013-01-01

Using 3 cyprinid fish species zebra fish, rare minnow, and juvenile grass carp, we conducted assays of lethal reaction and ventilatory response to analyze sensitivity of the fish to 4 heavy metals. Our results showed that the 96 h LC50 of Hg2+ to zebra fish, juvenile grass carp, and rare minnow were 0.14 mg L−1, 0.23 mg L−1, and 0.10 mg L−1, respectively; of Cu2+0.17 mg L−1, 0.09 mg L−1, and 0.12 mg L−1 respectively; of Cd2+6.5 mg L−1, 18.47 mg L−1, 5.36 mg L−1, respectively; and of Zn2+44.48 mg L−1, 31.37 mg L−1, and 12.74 mg L−1, respectively. Under a 1-h exposure, the ventilatory response to the different heavy metals varied. Ventilatory frequency (Vf) and amplitude (Va) increased in zebra fish, juvenile grass carp, and rare minnows exposed to Hg2+ and Cu2+ (P<0.05), and the Vf and Va of the 3 species rose initially and then declined when exposed to Cd2+. Zn2+ had markedly different toxic effects than the other heavy metals, whose Vf and Va gradually decreased with increasing exposure concentration (P<0.05). The rare minnow was the most highly susceptible of the 3 fish species to the heavy metals, with threshold effect concentrations (TEC) of 0.019 mg L−1, 0.046 mg L−1, 2.142 mg L−1, and 0.633 mg L−1 for Hg2+, Cu2+, Cd2+, and Zn2+, respectively. Therefore, it is feasible to use ventilatory parameters as a biomarker for evaluating the pollution toxicity of metals and to recognize early warning signs by using rare minnows as a sensor. PMID:23755209

Determination of trace metals and analysis of arsenic species in tropical marine fishes from Spratly islands.

PubMed

Li, Jingxi; Sun, Chengjun; Zheng, Li; Jiang, Fenghua; Wang, Shuai; Zhuang, Zhixia; Wang, Xiaoru

2017-09-15

Trace metal contents in 38 species of tropical marine fishes harvested from the Spratly islands of China were determined by microwave digestion and inductively coupled plasma mass spectrometry analysis. Arsenic species were determined by high-performance liquid chromatography and inductively coupled plasma mass spectrometry analysis. The average levels of Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Pb, and U in the fish samples were 1.683, 0.350, 0.367, 2.954, 36.615, 0.087, 0.319, 1.566, 21.946, 20.845, 2.526, 3.583, 0.225, 0.140, and 0.061mg·kg -1 , respectively; Fe, Zn, and As were found at high concentrations. The trace metals exhibited significant positive correlation between each other, with r value of 0.610-0.852. Further analysis indicated that AsB (8.560-31.020mg·kg -1 ) was the dominant arsenic species in the fish samples and accounted for 31.48% to 47.24% of the total arsenic. As(III) and As(V) were detected at low concentrations, indicating minimal arsenic toxicity. Copyright © 2017. Published by Elsevier Ltd.

Comparative study of species sensitivity distributions based on non-parametric kernel density estimation for some transition metals.

PubMed

Wang, Ying; Feng, Chenglian; Liu, Yuedan; Zhao, Yujie; Li, Huixian; Zhao, Tianhui; Guo, Wenjing

2017-02-01

Transition metals in the fourth period of the periodic table of the elements are widely widespread in aquatic environments. They could often occur at certain concentrations to cause adverse effects on aquatic life and human health. Generally, parametric models are mostly used to construct species sensitivity distributions (SSDs), which result in comparison for water quality criteria (WQC) of elements in the same period or group of the periodic table might be inaccurate and the results could be biased. To address this inadequacy, the non-parametric kernel density estimation (NPKDE) with its optimal bandwidths and testing methods were developed for establishing SSDs. The NPKDE was better fit, more robustness and better predicted than conventional normal and logistic parametric density estimations for constructing SSDs and deriving acute HC5 and WQC for transition metals in the fourth period of the periodic table. The decreasing sequence of HC5 values for the transition metals in the fourth period was Ti > Mn > V > Ni > Zn > Cu > Fe > Co > Cr(VI), which were not proportional to atomic number in the periodic table, and for different metals the relatively sensitive species were also different. The results indicated that except for physical and chemical properties there are other factors affecting toxicity mechanisms of transition metals. The proposed method enriched the methodological foundation for WQC. Meanwhile, it also provided a relatively innovative, accurate approach for the WQC derivation and risk assessment of the same group and period metals in aquatic environments to support protection of aquatic organisms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dual, differential isotope labeling shows the preferential movement of labile plant constituents into mineral-bonded soil organic matter.

PubMed

Haddix, Michelle L; Paul, Eldor A; Cotrufo, M Francesca

2016-06-01

The formation and stabilization of soil organic matter (SOM) are major concerns in the context of global change for carbon sequestration and soil health. It is presently believed that lignin is not selectively preserved in soil and that chemically labile compounds bonding to minerals comprise a large fraction of the SOM. Labile plant inputs have been suggested to be the main precursor of the mineral-bonded SOM. Litter decomposition and SOM formation are expected to have temperature sensitivity varying with the lability of plant inputs. We tested this framework using dual (13) C and (15) N differentially labeled plant material to distinguish the metabolic and structural components within a single plant material. Big Bluestem (Andropogon gerardii) seedlings were grown in an enriched (13) C and (15) N environment and then prior to harvest, removed from the enriched environment and allowed to incorporate natural abundance (13) C-CO2 and (15) N fertilizer into the metabolic plant components. This enabled us to achieve a greater than one atom % difference in (13) C between the metabolic and structural components within the plant litter. This differentially labeled litter was incubated in soil at 15 and 35 °C, for 386 days with CO2 measured throughout the incubation. After 14, 28, 147, and 386 days of incubation, the soil was subsequently fractionated. There was no difference in temperature sensitivity of the metabolic and structural components with regard to how much was respired or in the amount of litter biomass stabilized. Only the metabolic litter component was found in the sand, silt, or clay fraction while the structural component was exclusively found in the light fraction. These results support the stabilization framework that labile plant components are the main precursor of mineral-associated organic matter. © 2016 John Wiley & Sons Ltd.

Constraints on Transport and Emplacement Mechanisms of Labile Fractions in Lunar Cold Traps

NASA Technical Reports Server (NTRS)

Rickman, D.; Gertsch, L.

2014-01-01

Sustaining the scientific exploration of the Solar System will require a significant proportion of the necessary fuels and propellants, as well as other bulk commodities, to be produced from local raw materials [1]. The viability of mineral production depends on the ability to locate and characterize mineable deposits of the necessary feedstocks. This requires, among other things, a workable understanding of the mechanisms by which such deposits form, which is the subject of Economic Geology. Multiple deposition scenarios are possible for labile materials on the Moon. This paper suggests labile fractions moved diffusely through space; deposits may grow richer with depth until low porosity rock; lateral transport is likely to have occurred with the regolith, at least for short distances; crystalline ice may not exist; the constituent phases could be extremely complex. At present we can constrain the sources only mildly; once on the Moon, the transport mechanisms inherently mix and therefore obscure the origins. However, the importance of expanding our understanding of ore-forming processes on the Moon behooves us to make the attempt. Thus begins a time of new inquiry for Economic Geology.

Liquid metal ion source and alloy for ion emission of multiple ionic species

DOEpatents

Clark, Jr., William M.; Utlaut, Mark W.; Wysocki, Joseph A.; Storms, Edmund K.; Szklarz, Eugene G.; Behrens, Robert G.; Swanson, Lynwood W.; Bell, Anthony E.

1987-06-02

A liquid metal ion source and alloy for the simultaneous ion evaporation of arsenic and boron, arsenic and phosphorus, or arsenic, boron and phosphorus. The ionic species to be evaporated are contained in palladium-arsenic-boron and palladium-arsenic-boron-phosphorus alloys. The ion source, including an emitter means such as a needle emitter and a source means such as U-shaped heater element, is preferably constructed of rhenium and tungsten, both of which are readily fabricated. The ion sources emit continuous beams of ions having sufficiently high currents of the desired species to be useful in ion implantation of semiconductor wafers for preparing integrated circuit devices. The sources are stable in operation, experience little corrosion during operation, and have long operating lifetimes.

Interactions and accumulation differences of metal(loid)s in three sea cucumber species collected from the Northern Mediterranean Sea.

PubMed

Tunca, Evren; Aydın, Mehmet; Şahin, ÜlküAlver

2016-10-01

This study was conducted on Holothuria polii, Holothuria tubulosa, and Holothuria mammata collected from five stations with different depths in the Northern Mediterranean Sea. The body walls and guts of these holothurians were examined in terms of interactions of 10 metals (iron (Fe), copper (Cu), manganese (Mn), zinc (Zn), chromium (Cr), cobalt (Co), vanadium (V), nickel (Ni), cadmium (Cd), and lead (Pb)) and one metalloid (arsenic (As)) using a multivariate analysis, and interspecies differences were determined. The multivariate analysis of variance (MANOVA) revealed significant differences between the species in terms of metal(loid) accumulations. The principal component analysis (PCA) showed a more association between H. tubulosa and H. polii with regard to the accumulation. The cluster analysis (CA) located Pb concentrations of the guts to the farthest place from all elements regardless of the species. A correlation analysis displayed that the element concentrations of the guts were more closely related to each other compared with those of the walls. The most inconsistent element in terms of correlations was the gut Fe contents. Accordingly, while Fe concentrations of H. mammata and H. tubulosa were correlated with all elements (except Pb) in divalent metal transporter 1 (DMT1) (divalent cation transporter 1 (DCT1) or natural resistance-associated macrophage protein 2 (NRAMP2)) belonging to the NRAM protein family, this was not the case in H. polii. Consequently, significant relationships between accumulated metal(loid)s that changed by tissues and sea cucumber species were observed.

Glaciers as a source of ancient and labile organic matter to the marine environment.

Treesearch

Eran Hood; Jason Fellman; Robert G.M. Spencer; Peter J. Hernes; Rick Edwards; David D' Amore; Durelle Scott

2009-01-01

Riverine organic matter supports of the order of one-fifth of estuarine metabolism. Coastal ecosystems are therefore sensitive to alteration of both the quantity and lability of terrigenous dissolved organic matter (DOM) delivered by rivers. Here we characterize streamwater DOM from 11 coastal watersheds on the Gulf of Alaska that vary widely in glacier coverage. In...

Accumulation of Heavy Metals in Vegetable Species Planted in Contaminated Soils and the Health Risk Assessment

PubMed Central

Zhou, Hang; Yang, Wen-Tao; Zhou, Xin; Liu, Li; Gu, Jiao-Feng; Wang, Wen-Lei; Zou, Jia-Ling; Tian, Tao; Peng, Pei-Qin; Liao, Bo-Han

2016-01-01

The objectives of the present study were to investigate heavy metal accumulation in 22 vegetable species and to assess the human health risks of vegetable consumption. Six vegetable types were cultivated on farmland contaminated with heavy metals (Pb, Cd, Cu, Zn, and As). The target hazard quotient (THQ) method was used to assess the human health risks posed by heavy metals through vegetable consumption. Clear differences were found in the concentrations of heavy metals in edible parts of the different vegetables. The concentrations of heavy metals decreased in the sequence as leafy vegetables > stalk vegetables/root vegetables/solanaceous vegetables > legume vegetables/melon vegetables. The ability of leafy vegetables to uptake and accumulate heavy metals was the highest, and that of melon vegetables was the lowest. This indicated that the low accumulators (melon vegetables) were suitable for being planted on contaminated soil, while the high accumulators (leafy vegetables) were unsuitable. In Shizhuyuan area, China, the total THQ values of adults and children through consumption of vegetables were 4.12 and 5.41, respectively, suggesting that the residents may be facing health risks due to vegetable consumption, and that children were vulnerable to the adverse effects of heavy metal ingestion. PMID:26959043

Photoreactivity of Metal-Organic Frameworks in Aqueous Solutions: Metal Dependence of Reactive Oxygen Species Production.

PubMed

Liu, Kai; Gao, Yanxin; Liu, Jing; Wen, Yifan; Zhao, Yingcan; Zhang, Kunyang; Yu, Gang

2016-04-05

Promising applications of metal-organic frameworks (MOFs) in various fields have raised concern over their environmental fate and safety upon inevitable discharge into aqueous environments. Currently, no information regarding the transformation processes of MOFs is available. Due to the presence of repetitive π-bond structure and semiconductive property, photochemical transformations are an important fate process that affects the performance of MOFs in practical applications. In the current study, the generation of reactive oxygen species (ROS) in isoreticular MIL-53s was studied. Scavengers were employed to probe the production of (1)O2, O2(•-), and •OH, respectively. In general, MIL-53(Cr) and MIL-53(Fe) are dominated by type I and II photosensitization reactions, respectively, and MIL-53(Al) appears to be less photoreactive. The generation of ROS in MIL-53(Fe) may be underestimated due to dismutation. Further investigation of MIL-53(Fe) encapsulated diclofenac transformation revealed that diclofenac can be easily transformed by MIL-53(Fe) generated ROS. However, the cytotoxicity results implied that the ROS generated from MIL-53s have little effect on the viability of the human hepatocyte (HepG2) cell line. These results suggest that the photogeneration of ROS by MOFs may be metal-node dependent, and the application of MIL-53s as drug carriers needs to be carefully considered due to their high photoreactivity.

Unravelling the bioherbicide potential of Eucalyptus globulus Labill: Biochemistry and effects of its aqueous extract

PubMed Central

Reigosa, Manuel J.; Valentão, Patrícia; Andrade, Paula B.

2018-01-01

In the worldwide search for new strategies in sustainable weed management, the use of plant species able to produce and release phytotoxic compounds into the environment could be an effective alternative to synthetic herbicides. Eucalyptus globulus Labill. is known to be a source of biologically active compounds responsible for its phytotoxic and allelopathic properties. Our previous results demonstrated the bioherbicide potential of eucalyptus leaves incorporated into the soil as a green manure, probably through the release of phytotoxins into the soil solution. Thus, the aims of this study were to understand the phytotoxicity of the eucalyptus leaves aqueous extract applied in pre- and post-emergence, and to identify and quantify its potentially phytotoxic water-soluble compounds. The effects were tested on the germination and early growth of the model target species Lactuca sativa and Agrostis stolonifera, and on physiological parameters of L. sativa adult plants after watering or spraying application. Dose-response curves and ED50 and ED80 values for eucalyptus aqueous extracts revealed pre-emergence inhibitory effects on both target species, effects being comparable to the herbicide metolachlor. While spraying treatment reduced the aerial and root biomass and increased the dry weight/fresh weight ratio of lettuce adult plants, watering application reduced protein contents and chlorophyll concentrations with respect to control, reflecting different modes of action depending on the site of phytotoxin entry. Via HPLC analyses, a total of 8 phenolic compounds (chlorogenic, two ρ-coumaric derivatives, ellagic, hyperoside, rutin, quercitrin, and kaempferol 3-O-glucoside) and other 5 low weight organic acids (citric, malic, shikimic, succinic and fumaric acids) were obtained from aqueous extract, the latter being identified for the first time in E. globulus. Despite some phytotoxic effects were found on lettuce adult plants, the use of eucalyptus aqueous extract

Unravelling the bioherbicide potential of Eucalyptus globulus Labill: Biochemistry and effects of its aqueous extract.

PubMed

Puig, Carolina G; Reigosa, Manuel J; Valentão, Patrícia; Andrade, Paula B; Pedrol, Nuria

2018-01-01

In the worldwide search for new strategies in sustainable weed management, the use of plant species able to produce and release phytotoxic compounds into the environment could be an effective alternative to synthetic herbicides. Eucalyptus globulus Labill. is known to be a source of biologically active compounds responsible for its phytotoxic and allelopathic properties. Our previous results demonstrated the bioherbicide potential of eucalyptus leaves incorporated into the soil as a green manure, probably through the release of phytotoxins into the soil solution. Thus, the aims of this study were to understand the phytotoxicity of the eucalyptus leaves aqueous extract applied in pre- and post-emergence, and to identify and quantify its potentially phytotoxic water-soluble compounds. The effects were tested on the germination and early growth of the model target species Lactuca sativa and Agrostis stolonifera, and on physiological parameters of L. sativa adult plants after watering or spraying application. Dose-response curves and ED50 and ED80 values for eucalyptus aqueous extracts revealed pre-emergence inhibitory effects on both target species, effects being comparable to the herbicide metolachlor. While spraying treatment reduced the aerial and root biomass and increased the dry weight/fresh weight ratio of lettuce adult plants, watering application reduced protein contents and chlorophyll concentrations with respect to control, reflecting different modes of action depending on the site of phytotoxin entry. Via HPLC analyses, a total of 8 phenolic compounds (chlorogenic, two ρ-coumaric derivatives, ellagic, hyperoside, rutin, quercitrin, and kaempferol 3-O-glucoside) and other 5 low weight organic acids (citric, malic, shikimic, succinic and fumaric acids) were obtained from aqueous extract, the latter being identified for the first time in E. globulus. Despite some phytotoxic effects were found on lettuce adult plants, the use of eucalyptus aqueous extract

Experimental evidence for an effect of early-diagenetic interaction between labile and refractory marine sedimentary organic matter on nitrogen dynamics

NASA Astrophysics Data System (ADS)

Turnewitsch, Robert; Domeyer, Bettina; Graf, Gerhard

2007-05-01

In most natural sedimentary systems labile and refractory organic material (OM) occur concomitantly. Little, however, is known on how different kinds of OM interact and how such interactions affect early diagenesis in sediments. In a simple sediment experiment, we investigated how interactions of OM substrates of different degradability affect benthic nitrogen (N) dynamics. Temporal evolution of a set of selected biogeochemical parameters was monitored in sandy sediment over 116 days in three experimental set-ups spiked with labile OM (tissue of Mytilus edulis), refractory OM (mostly aged Zostera marina and macroalgae), and a 1:1 mixture of labile and refractory OM. The initial amounts of particulate organic carbon (POC) were identical in the three set-ups. To check for non-linear interactions between labile and refractory OM, the evolution of the mixture system was compared with the evolution of the simple sum of the labile and refractory systems, divided by two. The sum system is the experimental control where labile and refractory OM are virtually combined but not allowed to interact. During the first 30 days there was evidence for net dissolved-inorganic-nitrogen (DIN) production followed by net DIN consumption. (Here 'DIN' is the sum of ammonium, nitrite and nitrate.) After ˜ 30 days a quasi steady state was reached. Non-linear interactions between the two types of OM were reflected by three main differences between the early-diagenetic evolutions of nitrogen dynamics of the mixture and sum (control) systems: (1) In the mixture system the phases of net DIN production and consumption commenced more rapidly and were more intense. (2) The mixture system was shifted towards a more oxidised state of DIN products [as indicated by increased (nitrite + nitrate)/(ammonium) ratios]. (3) There was some evidence that more OM, POC and particulate nitrogen were preserved in the mixture system. That is, in the mixture system more particulate OM was preserved while a higher

Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

PubMed

Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

2014-03-01

Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances. Copyright © 2014. Published by Elsevier B.V.

Changes in labile soil organic matter fractions following land use change from monocropping to poplar-based agroforestry systems in a semiarid region of Northeast China.

PubMed

Mao, Rong; Zeng, De-Hui; Li, Lu-Jun; Hu, Ya-Lin

2012-11-01

Labile fractions of soil organic matter (SOM) respond rapidly to land management practices and can be used as a sensitive indicator of changes in SOM. However, there is little information about the effect of agroforestry practices on labile SOM fractions in semiarid regions of China. In order to test the effects of land use change from monocropping to agroforestry systems on labile SOM fractions, we investigated soil microbial biomass C (MBC) and N, particulate organic matter C (POMC) and N (POMN), as well as total organic C (TOC) and total N (TN) in the 0- to 15-cm and the 15- to 30-cm layers in 4-year-old poplar-based agroforestry systems and adjoining monocropping systems with two different soil textures (sandy loam and sandy clay loam) in a semiarid region of Northeast China. Our results showed that poplar-based agroforestry practices affected soil MBC, POMC, and POMN, albeit there was no significant difference in TOC and TN. Agroforestry practices increased MBC, POMC, and POMN in sandy clay loam soils. However, in sandy loam soils, agroforestry practices only increased MBC and even decreased POMC and POMN at the 0- to 15-cm layer. Our results suggest that labile SOM fractions respond sensitively to poplar-based agroforestry practices and can provide early information about the changes in SOM in semiarid regions of Northeast China and highlight that the effects of agroforestry practices on labile SOM fractions vary with soil texture.

Initial cloning and sequencing of hydHG, an operon homologous to ntrBC and regulating the labile hydrogenase activity in Escherichia coli K-12.

PubMed Central

Stoker, K; Reijnders, W N; Oltmann, L F; Stouthamer, A H

1989-01-01

To isolate genes from Escherichia coli which regulate the labile hydrogenase activity, a plasmid library was used to transform hydL mutants lacking the labile hydrogenase. A single type of gene, designated hydG, was isolated. This gene also partially restored the hydrogenase activity in hydF mutants (which are defective in all hydrogenase isoenzymes), although the low hydrogenase 1 and 2 levels were not induced. Therefore, hydG apparently regulates, specifically, the labile hydrogenase activity. Restoration of this latter activity in hydF mutants was accompanied by a proportional increase of the H2 uptake activity, suggesting a functional relationship. H2:fumarate oxidoreductase activity was not restored in complemented hydL mutants. These latter strains may therefore lack, in addition to the labile hydrogenase, a second component (provisionally designated component R), possibly an electron carrier coupling H2 oxidation to the anerobic respiratory chain. Sequence analysis showed an open reading frame of 1,314 base pairs for hydG. It was preceded by a ribosome-binding site but apparently lacked a promoter. Minicell experiments revealed a single polypeptide of approximately 50 kilodaltons. Comparison of the predicted amino acid sequence with a protein sequence data base revealed strong homology to NtrC from Klebsiella pneumoniae, a DNA-binding transcriptional activator. The 411 base pairs upstream from pHG40 contained a second open reading frame overlapping hydG by four bases. The deduced amino acid sequence showed considerable homology with the C-terminal part of NtrB. This sequence was therefore assumed to be part of a second gene, encoding the NtrB-like component, and was designated hydH. The labile hydrogenase activity in E. coli is apparently regulated by a multicomponent system analogous to the NtrB-NtrC system. This conclusion is in agreement with the results of Birkmann et al. (A. Birkmann, R. G. Sawers, and A. Böck, Mol. Gen. Genet. 210:535-542, 1987), who

Assessing ecotoxicity and uptake of metals and metalloids in relation to two different earthworm species (Eiseina hortensis and Lumbricus terrestris).

PubMed

Leveque, Thibaut; Capowiez, Yvan; Schreck, Eva; Mazzia, Christophe; Auffan, Mélanie; Foucault, Yann; Austruy, Annabelle; Dumat, Camille

2013-08-01

Due to diffuse atmospheric fallouts of process particles enriched by metals and metalloids, polluted soils concern large areas at the global scale. Useful tools to assess ecotoxicity induced by these polluted soils are therefore needed. Earthworms are currently used as biotest, however the influence of specie and earthworm behaviour, soil characteristics are poorly highlighted. Our aim was therefore to assess the toxicity of various polluted soils with process particles enriches by metals and metalloids (Pb, Cd, Cu, Zn, As and Sb) collected from a lead recycling facility on two earthworm species belonging to different ecological types and thus likely to have contrasted behavioural responses (Eiseina hortensis and Lumbricus terrestris). The combination of behavioural factors measurements (cast production and biomass) and physico-chemical parameters such as metal absorption, bioaccumulation by earthworms and their localization in invertebrate tissues provided a valuable indication of pollutant bioavailability and ecotoxicity. Soil characteristics influenced ecotoxicity and metal uptake by earthworms, as well as their soil bioturbation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

Type II Heat-labile Enterotoxins: Structure, Function, and Immunomofdulatory Properties

PubMed Central

Hajishengallis, George; Connell, Terry D.

2012-01-01

The heat-labile enterotoxins (HLTs) of Escherichia coli and Vibrio cholerae are classified into two major types on the basis of genetic, biochemical, and immunological properties. Type I and Type II HLT have been intensively studied for their exceptionally strong adjuvant activities. Despite general structural similarities, these molecules, in intact or derivative (non-toxic) forms, display notable differences in their mode of immunomodulatory action. The molecular basis of these differences has remained largely uncharacterized until recently. This review focuses on the Type II HLTs and their immunomodulatory properties which depend largely on interactions with unique gangliosides and Toll-like receptors that are not utilized by the Type I HLTs. PMID:23137790

Evolution of phenotypic plasticity and environmental tolerance of a labile quantitative character in a fluctuating environment.

PubMed

Lande, R

2014-05-01

Quantitative genetic models of evolution of phenotypic plasticity are used to derive environmental tolerance curves for a population in a changing environment, providing a theoretical foundation for integrating physiological and community ecology with evolutionary genetics of plasticity and norms of reaction. Plasticity is modelled for a labile quantitative character undergoing continuous reversible development and selection in a fluctuating environment. If there is no cost of plasticity, a labile character evolves expected plasticity equalling the slope of the optimal phenotype as a function of the environment. This contrasts with previous theory for plasticity influenced by the environment at a critical stage of early development determining a constant adult phenotype on which selection acts, for which the expected plasticity is reduced by the environmental predictability over the discrete time lag between development and selection. With a cost of plasticity in a labile character, the expected plasticity depends on the cost and on the environmental variance and predictability averaged over the continuous developmental time lag. Environmental tolerance curves derived from this model confirm traditional assumptions in physiological ecology and provide new insights. Tolerance curve width increases with larger environmental variance, but can only evolve within a limited range. The strength of the trade-off between tolerance curve height and width depends on the cost of plasticity. Asymmetric tolerance curves caused by male sterility at high temperature are illustrated. A simple condition is given for a large transient increase in plasticity and tolerance curve width following a sudden change in average environment. © 2014 The Author. Journal of Evolutionary Biology © 2014 European Society For Evolutionary Biology.

Distribution and origin of major and trace elements (particularly REE, U and Th) into labile and residual phases in an acid soil profile (Vosges Mountains, France)

NASA Astrophysics Data System (ADS)

Aubert, D.; Probst, A.; Stille, P.

2003-04-01

Physical and chemical weathering of rocks and minerals lead to soil formation and allow the removal of chemical elements from these systems to ground- or surface waters. But most of the time the determination of element concentrations in soils is not sufficient to estimate whether they are being accumulated or what is their ability to be released in the environment. Thus, the distribution and chemical binding for a given element is very important because it determines its mobility and potential bioavailability throughout a soil profile. Heavy metals and REE (Rare Earth Elements) are particularly of environmental concern because of their potential toxicity. For most of them, their chemical form strongly depends on the evolution of physico-chemical parameters like pH or redox conditions that will induce adsorption-desorption, complexation or co-precipitation phenomena in the material. The purpose of this study is to determine the distribution of several major and trace elements (especially REE, Th and U) in an acidic forested podzolic soil profile from the Vosges Mountains (France). To achieve this goal we use a 7 step sequential extraction procedure that allows determining precisely the origin and the behaviour of particular elements in the environment (Leleyter et al., 1999). In addition we performed leaching experiments using very dilute acetic and hydrochloric acid in order to establish the origin of REE in this soil. The results of the sequential extraction indicate that most of the metals, Th and U are mainly bound to Fe oxides. Organic matter appears also to be a great carrier of P, Ca, Fe and REE even if its content is very low in the deep horizons of the soil. Moreover, we show that in each soil horizon, middle REE (MREE) to heavy REE (HREE) are more labile than light REE (LREE). Leaching experiments using dilute acid solution further suggest that in the shallowest horizons REE largely derive from atmospheric deposition whereas at greater depth, weathering

Measurements of labile Cd, Cu, Ni, Pb, and Zn levels at a northeastern Brazilian coastal area under the influence of oil production with diffusive gradients in thin films technique (DGT).

PubMed

de Souza, João M; Menegário, Amauri A; de Araújo Júnior, Marcus A G; Francioni, Eleine

2014-12-01

In this work, the ability of the diffusive gradients in thin films technique (DGT) was evaluated for monitoring the concentrations, and estimating the availability, of metals at a northeastern Brazilian coastal area under the influence of oil production. Three sites with an average distance between 0m (EM-1), 100 m (EM-2), and 1,000 m (EM-3) of a submarine outfall-I (Guamaré-RN, Brazil) and another site (GA-1) with an average distance of 12,000 m east of Outfall I, near the city of Galinhos, were studied. DGT units were deployed at the same sites in three campaigns from July, 2010 to June, 2011. Effects on the accuracy of analytical results regarding the deployment time, gel porosity, and thickness were evaluated. There was no difference between the measurements obtained with two sets of DGT devices, those assembled with open or restrictive pore gel, respectively, showing that organic metallic species are not present near the submarine outlet. After 21 day deployments in a region (near Submarine Outfall I) that receives produced waters that have been treated, there was evidence of biofilm formation on DGT membranes. However, it was demonstrated that the biofilm interference with DGT measurements was negligible. Data found in this work show that total concentrations of Cd, Cu, Pb, Ni, and Zn in seawater samples collected at sites GA-1 and EM-1 in two campaigns were below 0.33, 1.67, 0.47, 0.70, 2.86 ng mL(-1) respectively. For the first time, labile levels of Cd, Cu, Pb, Ni, and Zn in an area under the influence of oil production were determined. DGT measurements allowed the verification of the effects of temporal variation on levels of Zn and Ni. There were no effects of spatial variations on levels of Cd, Cu, Ni, Pb, and Zn at the four studied sites, suggesting no contamination of these metals at the northeastern Brazilian coastal area investigated in this work. Copyright © 2014. Published by Elsevier B.V.

Assessing the resistance and bioremediation ability of selected bacterial and protozoan species to heavy metals in metal-rich industrial wastewater.

PubMed

Kamika, Ilunga; Momba, Maggy N B

2013-02-06

Heavy-metals exert considerable stress on the environment worldwide. This study assessed the resistance to and bioremediation of heavy-metals by selected protozoan and bacterial species in highly polluted industrial-wastewater. Specific variables (i.e. chemical oxygen demand, pH, dissolved oxygen) and the growth/die-off-rates of test organisms were measured using standard methods. Heavy-metal removals were determined in biomass and supernatant by the Inductively Couple Plasma Optical Emission Spectrometer. A parallel experiment was performed with dead microbial cells to assess the biosorption ability of test isolates. The results revealed that the industrial-wastewater samples were highly polluted with heavy-metal concentrations exceeding by far the maximum limits (in mg/l) of 0.05-Co, 0.2-Ni, 0.1-Mn, 0.1-V, 0.01-Pb, 0.01-Cu, 0.1-Zn and 0.005-Cd, prescribed by the UN-FAO. Industrial-wastewater had no major effects on Pseudomonas putida, Bacillus licheniformis and Peranema sp. (growth rates up to 1.81, 1.45 and 1.43 d-1, respectively) compared to other test isolates. This was also revealed with significant COD increases (p < 0.05) in culture media inoculated with living bacterial isolates (over 100%) compared to protozoan isolates (up to 24% increase). Living Pseudomonas putida demonstrated the highest removal rates of heavy metals (Co-71%, Ni-51%, Mn-45%, V-83%, Pb-96%, Ti-100% and Cu-49%) followed by Bacillus licheniformis (Al-23% and Zn-53%) and Peranema sp. (Cd-42%). None of the dead cells were able to remove more than 25% of the heavy metals. Bacterial isolates contained the genes copC, chrB, cnrA3 and nccA encoding the resistance to Cu, Cr, Co-Ni and Cd-Ni-Co, respectively. Protozoan isolates contained only the genes encoding Cu and Cr resistance (copC and chrB genes). Peranema sp. was the only protozoan isolate which had an additional resistant gene cnrA3 encoding Co-Ni resistance. Significant differences (p < 0.05) observed between dead and living microbial

Investigation of heavy metals release from sediment with bioturbation/bioirrigation.

PubMed

He, Yi; Men, Bin; Yang, Xiaofang; Li, Yaxuan; Xu, Hui; Wang, Dongsheng

2017-10-01

Bioturbation/bioirrigation can affect the remobilization of metals from sediments. In this study, experiments were performed to examine the effect of bioturbation/bioirrigation by different organisms on cadmium (Cd), copper (Cu), zinc (Zn) and lead (Pb) releasing from the spiked sediment. The diffusive gradient in thin films technique (DGT) revealed that at the end of exposure time, the labile heavy metals concentrations in the pore water for all metal and organisms combinations except Cu and chironomid larvae were much lower than that in the control group. However, the concentrations of heavy metals detected by the DGT were virtually indistinguishable among the treatments with tubificid, chironomid larvae and loach. The correlation analysis of heavy metals with iron (Fe) and manganese (Mn) suggested that Cd, Zn and Pb were most likely bound as Fe-Mn oxidation form in the pore water, but Cu was in other forms. After 28 d of exposure, bioturbation/bioirrigation produced a significant release of particulate heavy metals into the overlying water, especially in the treatment with loach. The bioturbation/bioirrigation impact on the Pb remobilization was less than the other three heavy metals. The effects of bioturbaiton/bioirrigation on the heavy metals remobilization in the sediment were complex that with studying the heavy metals remobilization in the sediment and water interface, the biological indicators should be recommended. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biomonitoring potential of five sympatric Tillandsia species for evaluating urban metal pollution (Cd, Hg and Pb)

NASA Astrophysics Data System (ADS)

Sánchez-Chardi, Alejandro

2016-04-01

The present study quantifies non essential heavy metals highly toxic for biological systems (Pb, Hg and Cd) in five autochthonous epiphytic plants from Tillandsia genus (T. recurvata, T. meridionalis, T. duratii, T. tricholepis, T. loliacea) according to different traffic levels (reference, low, medium and high polluted sites) in Asunción (Paraguay). The three metals increased in polluted sites following Pb (till 62.99 ppm in T. tricholepis) > Cd (till 1.35 ppm in T. recurvata) > Hg (till 0.36 ppm in T. recurvata) and Pb and Cd levels were directly related to traffic flow. Although the species showed similar bioaccumulation pattern (namely, higher levels of metals in polluted sites), enrichment factors (maximum EF values 37.00, 18.16, and 11.90 for Pb, Hg, and Cd, respectively) reported T. tricholepis as the most relevant bioindicator due to its wide distribution and abundance in study sites, low metal content in control site and high metal contents in polluted sites, and significant correlations with traffic density of Pb and Cd. This study emphasizes the necessity of biomonitoring air pollution in areas out of air monitoring control such as Asunción, where the high levels of metal pollution especially Pb, may represent an increment of risk for the human population inhabiting this urban area.

Alkali and alkaline earth metallic (AAEM) species leaching and Cu(II) sorption by biochar.

PubMed

Li, Mi; Lou, Zhenjun; Wang, Yang; Liu, Qiang; Zhang, Yaping; Zhou, Jizhi; Qian, Guangren

2015-01-01

Alkali and alkaline earth metallic (AAEM) species water leaching and Cu(II) sorption by biochar prepared from two invasive plants, Spartina alterniflora (SA) and water hyacinth (WH), were explored in this work. Significant amounts of Na and K can be released (maximum leaching for Na 59.0 mg g(-1) and K 79.9 mg g(-1)) from SA and WH biochar when they are exposed to contact with water. Cu(II) removal by biochar is highly related with pyrolysis temperature and environmental pH with 600-700 °C and pH of 6 showing best performance (29.4 and 28.2 mg g(-1) for SA and WH biochar). Cu(II) sorption exerts negligible influence on Na/K/Mg leaching but clearly promotes the release of Ca. Biochars from these two plant species provide multiple benefits, including nutrient release (K), heavy metal immobilization as well as promoting the aggregation of soil particles (Ca) for soil amelioration. AAEM and Cu(II) equilibrium concentrations in sorption were analyzed by positive matrix factorization (PMF) to examine the factors underlying the leaching and sorption behavior of biochar. The identified factors can provide insightful understanding on experimental phenomena. Copyright © 2014 Elsevier Ltd. All rights reserved.

Collagenase-labile polyurethane urea synthesis and processing into hollow fiber membranes.

PubMed

Fu, Hui-Li; Hong, Yi; Little, Steven R; Wagner, William R

2014-08-11

As a means to stimulate wound healing, a hollow fiber membrane system might be placed within a wound bed to provide local and externally regulated controlled delivery of regenerative factors. After sufficient healing, it would be desirable to triggerably degrade these fibers as opposed to pulling them out. Accordingly, a series of enzymatically degradable thermoplastic elastomers was developed as potential hollow fiber base material. Polyurethane ureas (PUUs) were synthesized based on 1, 4-diisocyanatobutane, polycaprolactone (PCL) diol and polyethylene glycol (PEG) at different molar fractions as soft segments, and collagenase-sensitive peptide GGGLGPAGGK-NH2 as a chain extender (defined as PUU-CLxEGy-peptide, where x and y are the respective molar percents). In these polymers, PEG in the polymer backbone decreased tensile strengths and initial moduli of solvent-cast films in the wet state, while increasing water absorption. Collagenase degradation was observed at 75% relative PEG content in the soft segment. Control PUUs with putrescine or nonsense peptide chain extenders did not degrade acutely in collagenase. Conduits electrospun from PUU-CL25EG75-peptide and PUU-CL50EG50-peptide exhibited appropriate mechanical strength and sustained release of a model protein from the tube lumen for 7 days. Collapse of PUU-CL25EG75-peptide tubes occurred after collagenase degradation for 3 days. In conclusion, through molecular design, synthesis and characterization, a collagenase-labile PUU-CL25EG75-peptide polymer was identified that exhibited the desired traits of triggerable lability, processability, and the capacity to act as a membrane to facilitate controlled protein release.

Simultaneous experimental determination of labile proton fraction ratio and exchange rate with irradiation radio frequency power-dependent quantitative CEST MRI analysis.

PubMed

Sun, Phillip Zhe; Wang, Yu; Xiao, Gang; Wu, Renhua

2013-01-01

Chemical exchange saturation transfer (CEST) imaging is sensitive to dilute proteins/peptides and microenvironmental properties, and has been increasingly evaluated for molecular imaging and in vivo applications. However, the experimentally measured CEST effect depends on the CEST agent concentration, exchange rate and relaxation time. In addition, there may be non-negligible direct radio-frequency (RF) saturation effects, particularly severe for diamagnetic CEST (DIACEST) agents owing to their relatively small chemical shift difference from that of the bulk water resonance. As such, the commonly used asymmetry analysis only provides CEST-weighted information. Recently, it has been shown with numerical simulation that both labile proton concentration and exchange rate can be determined by evaluating the RF power dependence of DIACEST effect. To validate the simulation results, we prepared and imaged two CEST phantoms: a pH phantom of serially titrated pH at a fixed creatine concentration and a concentration phantom of serially varied creatine concentration titrated to the same pH, and solved the labile proton fraction ratio and exchange rate per-pixel. For the concentration phantom, we showed that the labile proton fraction ratio is proportional to the CEST agent concentration with negligible change in the exchange rate. Additionally, we found the exchange rate of the pH phantom is dominantly base-catalyzed with little difference in the labile proton fraction ratio. In summary, our study demonstrated quantitative DIACEST MRI, which remains promising to augment the conventional CEST-weighted MRI analysis. Copyright © 2013 John Wiley & Sons, Ltd.

Mayolenes: Labile defensive lipids from the glandular hairs of a caterpillar (Pieris rapae)

PubMed Central

Smedley, Scott R.; Schroeder, Frank C.; Weibel, Douglas B.; Meinwald, Jerrold; Lafleur, Katie A.; Renwick, J. Alan; Rutowski, Ronald; Eisner, Thomas

2002-01-01

Larvae of the European cabbage butterfly, Pieris rapae (Pieridae), are beset with glandular hairs, bearing droplets of a clear oily secretion at their tip. The fluid consists primarily of a series of chemically labile, unsaturated lipids, the mayolenes, which are derived from 11-hydroxylinolenic acid. In bioassays with the ant Crematogaster lineolata, the secretion was shown to be potently deterrent, indicating that the fluid plays a defensive role in nature. PMID:11997469

Development of Hplc Techniques for the Analysis of Trace Metal Species in the Primary Coolant of a Pressurised Water Reactor.

NASA Astrophysics Data System (ADS)

Barron, Keiron Robert Philip

Available from UMI in association with The British Library. The need to monitor corrosion products in the primary circuit of a pressurised water reactor (PWR), at a concentration of 10pg ml^{-1} is discussed. A review of trace and ultra-trace metal analysis, relevant to the specific requirements imposed by primary coolant chemistry, indicated that high performance liquid chromatography (HPLC), coupled with preconcentration of sample was an ideal technique. A HPLC system was developed to determine trace metal species in simulated PWR primary coolant. In order to achieve the desired detection limit an on-line preconcentration system had to be developed. Separations were performed on Aminex A9 and Benson BC-X10 analytical columns. Detection was by post column reaction with Eriochrome Black T and Calmagite Linear calibrations of 2.5-100ng of cobalt (the main species of interest), were achieved using up to 200ml samples. The detection limit for a 200ml sample was 10pg ml^{-1}. In order to achieve the desired aim of on-line collection of species at 300^circ C, the use of inorganic ion-exchangers is essential. A novel application, utilising the attractive features of the inorganic ion-exchangers titanium dioxide, zirconium dioxide, zirconium arsenophosphate and pore controlled glass beads, was developed for the preconcentration of trace metal species at temperature and pressure. The performance of these exchangers, at ambient and 300^ circC was assessed by their inclusion in the developed analytical system and by the use of radioisotopes. The particular emphasis during the development has been upon accuracy, reproducibility of recovery, stability of reagents and system contamination, studied by the use of radioisotopes and response to post column reagents. This study in conjunction with work carried out at Winfrith, resulted in a monitoring system that could follow changes in coolant chemistry, on deposition and release of metal species in simulated PWR water loops. On

Heavy metal accumulation and ecosystem engineering by two common mine site-nesting ant species: implications for pollution-level assessment and bioremediation of coal mine soil.

PubMed

Khan, Shbbir R; Singh, Satish K; Rastogi, Neelkamal

2017-04-01

The present study focuses on the abundance, heavy metal content, and the impact of ecosystem engineering activities of two coal mine site-inhabiting ant species, Cataglyphis longipedem and Camponotus compressus. The abundance of Ct. longipedem increased while that of C. compressus decreased, with increasing soil pollution. Correspondence analysis reveals a close association between soil heavy metal concentrations and Ct. longipedem abundance, but this association is lacking in the case of C. compressus. Cataglyphis ants which occupy stress-characterized niches appear to be pre-adapted to tolerate heavy metal pollution. Higher concentrations of Zn and Mn in Ct. longipedem may contribute to the strengthening of the cuticular structures, necessary for nest excavation in the hard, arid soil and for single load carrying. C. compressus ants appear to be pollution sensitive. Their higher Fe content may be related to metal uptake via plant-derived liquids and species-specific regulatory mechanisms. The metal pollution index and biota-to-soil accumulation factors, calculated by using the ant body metal content of the two species, indicate an overall decrease of soil heavy metal concentrations with increase of the site age, which reflects the degree of pollution related to the mine site age. The concentrations of total and available heavy metals (Fe, Zn, Mn, Pb, and Cu) were significantly lower in the ant nest debris soil as compared to the reference soil. The results of the present study highlight the role of ants as bioindicators and in bioremediation of contaminated soil.

The Use of Enzyme Hydrolysis to Assess the Seasonal Mobility and Bioavailability of Organic Phosphorus in Lake Sediments

NASA Astrophysics Data System (ADS)

Giles, C. D.; Lee, L. G.; Cade-Menun, B. J.; Rutila, B. C.; Schroth, A. W.; Xu, Y.; Hill, J. E.; Druschel, G.

2013-12-01

Lake sediments represent a significant internal source of phosphorus (P) in eutrophic freshwater systems during periods of high biological activity and oxygen depletion in sediments. Enzyme-labile and redox-sensitive P fractions may be a major component of the mobile sediment P pool which contributes to the development of harmful algal blooms. We present a high-through-put enzyme-based method for assessing potentially bioavailable (enzyme-labile) P in lake sediments and describe the relationship between enzyme-labile P, ascorbate-extractable (reactive) P and metals (Fe, Mn, Al, Ca), and P species identified using solution 31-P NMR spectroscopy. Sediment cores (0-10 cm) were collected from Lake Champlain over multiple years (Missisquoi Bay, VT, USA; 2007-2013). A principal components analysis of sediment properties suggests that enzyme-labile and reactive P, Mn, and Fe concentrations were more effective than the 31-P NMR methodology alone for differentiating algal bloom stage associated with periods of sediment anoxia. Bloom onset (July 2008) and peak bloom (August 2008, 2012) periods corresponded to the highest enzyme-labile P and lowest reactive P and metals proportions, despite 31-P NMR profiles which did not change significantly with respect to time and depth. High levels of reduced Fe and Mn ions were also detected in pore-water during this period, confirming previous reports that organic P bioavailability is linked to the redox status of sediments. High through-put analysis of enzyme-labile P fractions will provide spatially and temporally resolved information on bioavailable P pools at lower cost than traditional methods (i.e., 31-P NMR), and provide much-needed detail on aquatic P cycles during discrete stages of algal bloom development and sediment anoxia.

The role of metals in production and scavenging of reactive oxygen species in photosystem II.

PubMed

Pospíšil, Pavel

2014-07-01

Metal ions play a crucial role in enzymatic reactions in all photosynthetic organisms such as cyanobacteria, algae and plants. It well known that metal ions maintain the binding of substrate in the active site of the metalloenzymes and control the redox activity of the metalloenzyme in the enzymatic reaction. A large pigment-protein complex, PSII, known to serve as a water-plastoquinone oxidoreductase, contains three metal centers comprising non-heme iron, heme iron of Cyt b559 and the water-splitting manganese complex. Metal ions bound to PSII proteins maintain the electron transport from water to plastoquinone and regulate the pro-oxidant and antioxidant activity in PSII. In this review, attention is focused on the role of PSII metal centers in (i) the formation of superoxide anion and hydroxyl radicals by sequential one-electron reduction of molecular oxygen and the formation of hydrogen peroxide by incomplete two-electron oxidation of water; and (ii) the elimination of superoxide anion radical by one-electron oxidation and reduction (superoxide dismutase activity) and of hydrogen peroxide by two-electron oxidation and reduction (catalase activity). The balance between the formation and elimination of reactive oxygen species by PSII metal centers is discussed as an important aspect in the prevention of photo-oxidative damage of PSII proteins and lipids. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Occurrence and abundance of carbohydrates and amino compounds in sequentially extracted labile soil organic matter fractions.

USDA-ARS?s Scientific Manuscript database

This study aimed to investigate the content of carbohydrates and amino compounds in three labile fraction of soil organic matter (SOM). Soil samples were collected from two agricultural fields in southern Italy and the light fraction (LF), the 500–53-µm particulate organic matter (POM) and the mobil...

Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

PubMed

Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

2015-06-25

Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions.

Force-induced chemical reactions on the metal centre in a single metalloprotein molecule

PubMed Central

Zheng, Peng; Arantes, Guilherme M.; Field, Martin J.; Li, Hongbin

2015-01-01

Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

Lability of High Molecular Weight Dissolved Organic Matter Polysaccharides Increases with Mild Acid or Base Treatment.

NASA Astrophysics Data System (ADS)

Pedler Sherwood, B.; Sosa, O.; Nelson, C. E.; Repeta, D.; DeLong, E.

2016-02-01

Approximately 662 Pg of dissolved organic carbon (DOC) has accumulated in the global ocean, yet the biological and chemical constraints on DOC turnover remain poorly understood. High molecular weight dissolved organic matter (HMWDOM) is largely comprised of semi-labile polysaccharides. These polysaccharides resist degradation even in the presence of nutrient amendments, suggesting unknown factors of polysaccharide composition affect microbial degradation. In a series of microcosm incubations conducted at station ALOHA in the North Pacific Subtropical Gyre, we tested the affect of mild base (KOH-DOM) and acid (HCl-DOM) treatments on polysaccharide lability. KOH-DOM, HCl-DOM, and untreated HMWDOM was added to seawater from the deep chlorophyll maximum and 200m. Microcosms amended with KOH-DOM and HCl-DOM yielded higher bacterial abundance and greater carbon drawdown relative to untreated HMWDOM and unamended controls. Microcosms amended with KOH-DOM and HCl-DOM also showed significant production of fluorescent DOM (fDOM), whereas untreated HMWDOM and unamended controls showed a net decrease in fDOM as measured by parallel factor analysis of DOM excitation-emission spectra. Metagenomic analyses revealed that microcosms amended with untreated HMWDOM and controls became dominated by Alteromonas genera ( 60% total sequence reads). In contrast, KOH-DOM and HCl-DOM amended microcosms yielded greater bacterial diversity; Alteromonas genera comprised 25% of sequence reads, with differences primarily accounted for by proportional increases in vibrio, roseobacter, rugeria and marinomonas clades. Transcriptomic analyses identified differential gene expression during growth on each DOM fraction. This study provides new insight into specific chemical moieties that may limit the bacterial degradation rate of semi-labile HMWDOM in the ocean.

Complete Characterization of trans- Co(en)2Cl2[3 Fe(ox)3[.4-1/2H2O: An Extended Undergraduate Project Involving an Unknown Metal Complex.

ERIC Educational Resources Information Center

Bull, Graham S.; Searle, Graeme H.

1986-01-01

Discusses the need for student experiments involving the complete characterization of "unknown" inorganic compounds. Describes a project employing a complex metal compound. The compound contains six different components in both inert and labile complexions. Outlines the complete procedure and the preparation of the unknown compound. (TW)

Assessing the resistance and bioremediation ability of selected bacterial and protozoan species to heavy metals in metal-rich industrial wastewater

PubMed Central

2013-01-01

Background Heavy-metals exert considerable stress on the environment worldwide. This study assessed the resistance to and bioremediation of heavy-metals by selected protozoan and bacterial species in highly polluted industrial-wastewater. Specific variables (i.e. chemical oxygen demand, pH, dissolved oxygen) and the growth/die-off-rates of test organisms were measured using standard methods. Heavy-metal removals were determined in biomass and supernatant by the Inductively Couple Plasma Optical Emission Spectrometer. A parallel experiment was performed with dead microbial cells to assess the biosorption ability of test isolates. Results The results revealed that the industrial-wastewater samples were highly polluted with heavy-metal concentrations exceeding by far the maximum limits (in mg/l) of 0.05-Co, 0.2-Ni, 0.1-Mn, 0.1-V, 0.01-Pb, 0.01-Cu, 0.1-Zn and 0.005-Cd, prescribed by the UN-FAO. Industrial-wastewater had no major effects on Pseudomonas putida, Bacillus licheniformis and Peranema sp. (growth rates up to 1.81, 1.45 and 1.43 d-1, respectively) compared to other test isolates. This was also revealed with significant COD increases (p < 0.05) in culture media inoculated with living bacterial isolates (over 100%) compared to protozoan isolates (up to 24% increase). Living Pseudomonas putida demonstrated the highest removal rates of heavy metals (Co-71%, Ni-51%, Mn-45%, V-83%, Pb-96%, Ti-100% and Cu-49%) followed by Bacillus licheniformis (Al-23% and Zn-53%) and Peranema sp. (Cd-42%). None of the dead cells were able to remove more than 25% of the heavy metals. Bacterial isolates contained the genes copC, chrB, cnrA3 and nccA encoding the resistance to Cu, Cr, Co-Ni and Cd-Ni-Co, respectively. Protozoan isolates contained only the genes encoding Cu and Cr resistance (copC and chrB genes). Peranema sp. was the only protozoan isolate which had an additional resistant gene cnrA3 encoding Co-Ni resistance. Conclusion Significant differences (p < 0

Methods of recovering alkali metals

DOEpatents

Krumhansl, James L; Rigali, Mark J

2014-03-04

Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

Effect of warming on the degradation and production of low-molecular-weight labile organic carbon in an Arctic tundra soil

DOE PAGES

Yang, Ziming; Wullschleger, Stan D.; Liang, Liyuan; ...

2016-01-16

The fate of soil organic carbon (SOC) stored in the Arctic permafrost is a key concern as temperatures continue to rise in the northern hemisphere. Studies and conceptual models suggest that SOC degradation is affected by the composition of SOC, but it is unclear exactly what portions of SOC are vulnerable to rapid breakdown and what mechanisms may be controlling SOC degradation upon permafrost thaw. Here, we examine the dynamic consumption and production of labile SOC in an anoxic incubation experiment using soil samples from the active layer at the Barrow Environmental Observatory, Barrow, Alaska, USA. Free-reducing sugars, alcohols, andmore » low-molecular-weight (LMW) organic acids were analyzed during incubation at either –2 or 8 °C for up to 240 days. Results show that simple sugar and alcohol SOC largely account for the initial rapid release of CO 2 and CH 4 through anaerobic fermentation, whereas the fermentation products, acetate and formate, are subsequently utilized as primary substrates for methanogenesis. Iron(III) reduction is correlated to acetate production and methanogenesis, suggesting its important role as an electron acceptor in tundra SOC respiration. These observations are further supported in a glucose addition experiment, in which rapid CO 2 and CH 4 production occurred concurrently with rapid production and consumption of labile organics such as acetate. However, addition of tannic acid, as a more complex organic substrate, showed little influence on the overall production of CO 2 and CH 4 and organic acids. Together our study shows that LMW labile organics in SOC control the initial rapid release of green-house gases upon warming. We thus present a conceptual framework for the labile SOC transformations and their relations to fermentation, iron reduction and methanogenesis, thereby providing the basis for improved model prediction of climate feedbacks in the Arctic.« less

A Multivariate Analysis of Metal Concentrations in Two Fish Species of the Nyl River System, Limpopo Province, South Africa.

PubMed

Musa, R; Gerber, R; Greenfield, R

2017-06-01

Increased toxicity due to high metal concentrations may hinder the ecological integrity of aquatic ecosystems in sustaining life. The non-biodegradable nature of metals may result in bioaccumulation in aquatic organisms. Due to ecological and social aspects it is imperative for monitoring schemes to identify possible impacts to the systems integrity. This paper discusses accumulation patterns of seven metals (Al, Cr, Cu, Fe, Mn, Sr and Zn) in tissues of two fish species, namely Clarias gariepinus and Oreochromis mossambicus at two selected sites, the first located upstream of Modimolle (NRS1), and the second located downstream of the town (NRS2). Gills, liver, muscle and skin tissues were analysed for metal concentrations using standard microwave digestion and inductively coupled plasma mass spectrometry techniques. Statistical results indicated higher concentrations of metals at NRS2 in comparison to NRS1, indicating that Modimolle plays a potential role in introducing metals into the aquatic system.

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes.

PubMed

Abdelhamid, Hani Nasser

2018-03-01

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks. Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

Process for the enhanced capture of heavy metal emissions

DOEpatents

Biswas, Pratim; Wu, Chang-Yu

2001-01-01

This invention is directed to a process for forming a sorbent-metal complex. The process includes oxidizing a sorbent precursor and contacting the sorbent precursor with a metallic species. The process further includes chemically reacting the sorbent precursor and the metallic species, thereby forming a sorbent-metal complex. In one particular aspect of the invention, at least a portion of the sorbent precursor is transformed into sorbent particles during the oxidation step. These sorbent particles then are contacted with the metallic species and chemically reacted with the metallic species, thereby forming a sorbent-metal complex. Another aspect of the invention is directed to a process for forming a sorbent metal complex in a combustion system. The process includes introducing a sorbent precursor into a combustion system and subjecting the sorbent precursor to an elevated temperature sufficient to oxidize the sorbent precursor and transform the sorbent precursor into sorbent particles. The process further includes contacting the sorbent particles with a metallic species and exposing the sorbent particles and the metallic species to a complex-forming temperature whereby the metallic species reacts with the sorbent particles thereby forming a sorbent-metal complex under UV irradiation.

Production of metal particles and clusters

NASA Technical Reports Server (NTRS)

Mcmanus, S. P.

1982-01-01

The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

Purification and characterization of an oxygen-labile, NAD-dependent alcohol dehydrogenase from Desulfovibrio gigas.

PubMed Central

Hensgens, C M; Vonck, J; Van Beeumen, J; van Bruggen, E F; Hansen, T A

1993-01-01

A NAD-dependent, oxygen-labile alcohol dehydrogenase was purified from Desulfovibrio gigas. It was decameric, with subunits of M(r) 43,000. The best substrates were ethanol (Km, 0.15 mM) and 1-propanol (Km, 0.28 mM). N-terminal amino acid sequence analysis showed that the enzyme belongs to the same family of alcohol dehydrogenases as Zymomonas mobilis ADH2 and Bacillus methanolicus MDH. Images PMID:8491707

Metal concentrations, sperm motility, and RNA/DNA ratio in two echinoderm species from a highly contaminated fjord (the Sørfjord, Norway).

PubMed

Catarino, Ana I; Cabral, Henrique N; Peeters, Kris; Pernet, Philippe; Punjabi, Usha; Dubois, Philippe

2008-07-01

The present study evaluated the effects of field metal contamination on sperm motility and the RNA/DNA ratio in echinoderms. Populations of Asterias rubens and Echinus acutus that occur naturally along a contamination gradient of sediments by cadmium, copper, lead, and zinc in a Norwegian fjord (the Sørfjord) were studied. Sperm motility, a measure of sperm quality, was quantified using a computer-assisted sperm analysis system. The RNA/DNA ratio, a measure of protein synthesis, was assessed by a one-dye (ethidium bromide)/one-enzyme (RNase), 96-well microplate fluorometric assay. Although both species accumulate metals at high concentrations, neither sperm motility parameters in A. rubens nor the RNA/DNA ratio in both species were affected. The Sørfjord is still one of the most metal-contaminated marine sites in Europe, but even so, populations of A. rubens and E. acutus are able to endure under these conditions.

Microwave-assisted extraction performed in low temperature and in vacuo for the extraction of labile compounds in food samples.

PubMed

Xiao, Xiaohua; Song, Wei; Wang, Jiayue; Li, Gongke

2012-01-27

In this study, low temperature vacuum microwave-assisted extraction, which simultaneous performed microwave-assisted extraction (MAE) in low temperature and in vacuo environment, was proposed. The influencing parameters including solid/liquid ratio, extraction temperature, extraction time, degree of vacuum and microwave power were discussed. The predominance of low temperature vacuum microwave-assisted extraction was investigated by comparing the extraction yields of vitamin C, β-carotene, aloin A and astaxanthin in different foods with that in MAE and solvent extraction, and 5.2-243% increments were obtained. On the other hand, the chemical kinetics of vitamin C and aloin A, which composed two different steps including the extraction step of analyte transferred from matrix into solvent and the decomposition step of analyte degraded in the extraction solvent, were proposed. All of the decomposition rates (K(2)) for the selected analyte in low temperature, in vacuo and in nitrogen atmosphere decreased significantly comparing with that in conventional MAE, which are in agreement with that obtained from experiments. Consequently, the present method was successfully applied to extract labile compound from different food samples. These results showed that low temperature and/or in vacuo environment in microwave-assisted extraction system was especially important to prevent the degradation of labile components and have good potential on the extraction of labile compound in foods, pharmaceutical and natural products. Copyright © 2011 Elsevier B.V. All rights reserved.

Phylogeny and species traits predict bird detectability

USGS Publications Warehouse

Solymos, Peter; Matsuoka, Steven M.; Stralberg, Diana; Barker, Nicole K. S.; Bayne, Erin M.

2018-01-01

Avian acoustic communication has resulted from evolutionary pressures and ecological constraints. We therefore expect that auditory detectability in birds might be predictable by species traits and phylogenetic relatedness. We evaluated the relationship between phylogeny, species traits, and field‐based estimates of the two processes that determine species detectability (singing rate and detection distance) for 141 bird species breeding in boreal North America. We used phylogenetic mixed models and cross‐validation to compare the relative merits of using trait data only, phylogeny only, or the combination of both to predict detectability. We found a strong phylogenetic signal in both singing rates and detection distances; however the strength of phylogenetic effects was less than expected under Brownian motion evolution. The evolution of behavioural traits that determine singing rates was found to be more labile, leaving more room for species to evolve independently, whereas detection distance was mostly determined by anatomy (i.e. body size) and thus the laws of physics. Our findings can help in disentangling how complex ecological and evolutionary mechanisms have shaped different aspects of detectability in boreal birds. Such information can greatly inform single‐ and multi‐species models but more work is required to better understand how to best correct possible biases in phylogenetic diversity and other community metrics.

Acid-Labile Acyclic Cucurbit[n]uril Molecular Containers for Controlled Release.

PubMed

Mao, Dake; Liang, Yajun; Liu, Yamin; Zhou, Xianhao; Ma, Jiaqi; Jiang, Biao; Liu, Jia; Ma, Da

2017-10-02

Stimuli-responsive molecular containers are of great importance for controlled drug delivery and other biomedical applications. A new type of acid labile acyclic cucurbit[n]uril (CB[n]) molecular containers is presented that can degrade and release the encapsulated cargo at accelerated rates under mildly acidic conditions (pH 5.5-6.5). These containers retain the excellent recognition properties of CB[n]-type hosts. A cell culture study demonstrated that the cellular uptake of cargos could be fine-tuned by complexation with different containers. The release and cell uptake of cargo dye was promoted by acidic pH. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method and apparatus for back-extracting metal chelates

DOEpatents

Wai, Chien M.; Smart, Neil G.; Lin, Yuehe

1998-01-01

A method of extracting metal and metalloid species from a solid or liquid substrate using a supercritical fluid solvent containing one or more chelating agents followed by back-extracting the metal and metalloid species from the metal and metalloid chelates formed thereby. The back-extraction acidic solution is performed utilizing an acidic solution. Upon sufficient exposure of the metal and metalloid chelates to the acidic solution, the metal and metalloid species are released from the chelates into the acid solution, while the chelating agent remains in the supercritical fluid solvent. The chelating agent is thereby regenerated and the metal and metalloid species recovered.

Transfert de nickel, de cuivre et de zinc lors de la manipulation de pièces de monnaie : le cas du dirham marocain

NASA Astrophysics Data System (ADS)

Fournier, Paul-Guy; Nourtier, Alain; Monkade, Mohammed; Berrada, Khalid; Boughaleb, Hichame; Outzourhit, Abdelkader; Pichon, Rémy; Haut, Christian; Govers, Thomas

2006-03-01

When the euro was introduced, the fact that some coins contain nickel, which is known to be an allergen, gave rise to controversy. More generally, this raises the question of metal transfer from coins to skin. Morocco has used for decades one-dirham coins made of pure or alloyed nickel. Studying their wear, the labile metal on their surface and the transfer to fingers in handling may therefore be especially instructive. Weighing statistics for a sample of 401 coins confirm that cupronickel coins wear out more quickly than pure nickel coins and reveal that the dirham suffers a much stronger wear than other currencies for which wear statistics are available. SEM studies supplemented by ICP quantitative analyses show that the labile metal is mainly made up of chips, even after many handlings. These chips are often cupronickel, even on pure nickel coins, which shows that they are produced by the friction of coins against one another. Secondly, the surface of coins presents sweat residue with an important proportion of copper and a little nickel, which confirms that sweat dissolves surface copper. Depending on the alloy and date, coins have between 20 and 140 μg of labile copper and nickel, with a content of one quarter of nickel on cupronickel coins and about one half on pure nickel coins. The most worn cupronickel coins are the coins that present the largest amount of labile metal, and even labile nickel. In our experiments, the metal transfer to fingers when a cupronickel coin is handled for the first time represents between 4 and 9% of the labile metal and 0.05% of the annual wear. A simple and reliable test of nickel contamination consists in measuring the labile nickel. To cite this article: P.-G. Fournier et al., C. R. Physique 7 (2006).

Field-assisted nanopatterning of metals, metal oxides and metal salts

NASA Astrophysics Data System (ADS)

Liu, Jun-Fu; Miller, Glen P.

2009-02-01

The tip-based nanofabrication method called field-assisted nanopatterning or FAN has now been extended to the transfer of metals, metal oxides and metal salts onto various receiving substrates including highly ordered pyrolytic graphite, passivated gold and indium-tin oxide. Standard atomic force microscope tips were first dip-coated using suspensions of inorganic compounds in solvent. The films prepared in this manner were non-uniform and contained inorganic nanoparticles. Tip-based nanopatterning on chosen substrates was conducted under high electric field conditions. The same tip was used for both nanofabrication and imaging. Arbitrary patterns were formed with dimensions that ranged from tens of microns to sub-20 nm and were controlled by tuning the tip bias during fabrication. Most tip-based nanopatterning techniques are limited in terms of the type of species that can be deposited and the type of substrates onto which the deposition occurs. With the successful deposition of inorganic species reported here, FAN is demonstrated to be a truly versatile tip-based nanofabrication technique that is useful for the deposition of a wide variety of both organic and inorganic species including small molecules, large molecules and polymers.

Reduction of aqueous transition metal species on the surfaces of Fe(II) -containing oxides

NASA Astrophysics Data System (ADS)

White, Art F.; Peterson, Maria L.

1996-10-01

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25°C. For an aqueous transition metal m, such reactions are 3[FeFe23+]O+2/nm→4[Fe23+]O+Fe+2/nm and 3[FeTi]O+→Fe23+TiO+Fe+2/nm, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] → [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe 2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 × 10 -10 mol m -2 s -1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe 2+ is oxidized homogeneously in solution to Fe 3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show

A Longitudinal Study of Emotion Regulation, Emotion Lability-Negativity, and Internalizing Symptomatology in Maltreated and Nonmaltreated Children

ERIC Educational Resources Information Center

Kim-Spoon, Jungmeen; Cicchetti, Dante; Rogosch, Fred A.

2013-01-01

The longitudinal contributions of emotion regulation and emotion lability-negativity to internalizing symptomatology were examined in a low-income sample (171 maltreated and 151 nonmaltreated children, from age 7 to 10 years). Latent difference score models indicated that for both maltreated and nonmaltreated children, emotion regulation was a…

Differences in dissolved organic matter lability between alpine glaciers and alpine rock glaciers of the American West

NASA Astrophysics Data System (ADS)

Hall, E.; Fegel, T. S., II; Baron, J.; Boot, C. M.

2015-12-01

While alpine glaciers in montane regions represent the largest flux of dissolved organic matter (DOM) from global ice melt no research has examined the bioavailability of DOM melted out of glacial ice in the western continental United States. Furthermore, rock glaciers are an order of magnitude more abundant than ice glaciers in U.S., yet are not included in budgets for perennial ice carbon stores. Our research aims to understand differences in the bioavailability of carbon from ice glaciers and rock glaciers along the Central Rocky Mountains of Colorado. Identical microbial communities were fed standardized amounts of DOM from four different ice glacier-rock glaciers pairs. Using laboratory incubations, paired with mass spectrometry based metabolomics and 16S gene sequencing; we were able to examine functional definitions of DOM lability in glacial ice. We hypothesized that even though DOM quantities are similar in the outputs of both glacial types in our study area, ice glacial DOM would be more bioavailable than DOM from rock glaciers due to higher proportions of byproducts from microbial metabolism than rock glacier DOM, which has higher amounts of "recalcitrant" plant material. Our results show that DOM from ice glaciers is more labile than DOM from geologically and geographically similar paired rock glaciers. Ice glacier DOM represents an important pool of labile carbon to headwater ecosystems of the Rocky Mountains. Metabolomic analysis shows numerous compounds from varying metabolite pathways, including byproducts of nitrification before and after incubation, meaning that, similar to large maritime glaciers in Alaska and Europe, subglacial environments in the mountain ranges of the United States are hotspots for biological activity and processing of organic carbon.

Efficient catalysis of Nazarov cyclization using a cationic iridium complex possessing adjacent labile coordination sites.

PubMed

Janka, Mesfin; He, Wei; Frontier, Alison J; Eisenberg, Richard

2004-06-09

The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BARF)2 having adjacent labile sites has been found to be a very effective catalyst for promoting the Nazarov cyclization of aryl vinyl and divinyl ketones. Spectroscopic evidence for a substate-catalyst complex before cyclization is presented. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via chelation.

Experimental considerations in metal mobilization from soil by chelating ligands: The influence of soil-solution ratio and pre-equilibration - A case study on Fe acquisition by phytosiderophores.

PubMed

Schenkeveld, W D C; Kimber, R L; Walter, M; Oburger, E; Puschenreiter, M; Kraemer, S M

2017-02-01

The efficiency of chelating ligands in mobilizing metals from soils and sediments is generally examined under conditions remote from those under which they are exuded or applied in the field. This may lead to incorrect estimations of the mobilizing efficiency. The aim of this study was to establish the influence of the soil solution ratio (SSR) and pre-equilibration with electrolyte solution on metal mobilization and metal displacement. For this purpose a series of interaction experiments with a calcareous clay soil and a biogenic chelating agent, the phytosiderophore 2'-deoxymugineic acid (DMA) were carried out. For a fixed ligand concentration, the SSR had a strong influence on metal mobilization and displacement. Metal complexation was faster at higher SSR. Reactive pools of metals that were predominantly mobilized at SSR 6 (in this case Cu), became depleted at SSR 0.1, whereas metals that were marginally mobilized at SSR 6, were dominantly mobilized at SSR 0.1 (in this case Fe), because of large soil reactive pools. For a fixed "amount of ligand"-to-"amount of soil"-ratio, metal complexation scaled linearly with the SSR. The efficiency of ligands in mobilizing metals under field conditions can be predicted with batch experiments, as long as the ligand-to-soil-ratio is matched. In most previously reported studies this criterion was not met. Equivalent metal-complex concentrations under field conditions can be back-calculated using adsorption isotherms for the respective metal-complexes. Drying and dry storage created labile pools of Fe, Cu and Zn, which were rapidly mobilized upon addition of DMA solution to dry soil. Pre-equilibration decreased these labile pools, leading to smaller concentrations of these metals during initial mobilization, but did not reduce the lag time between ligand addition and onset of microbial degradation of the metal-complexes. Hence SSR and pre-equilibration should be carefully considered when testing the metal mobilizing efficiency

Method and apparatus for back-extracting metal chelates

DOEpatents

Wai, C.M.; Smart, N.G.; Lin, Y.

1998-08-11

A method is described for extracting metal and metalloid species from a solid or liquid substrate using a supercritical fluid solvent containing one or more chelating agents followed by back-extracting the metal and metalloid species from the metal and metalloid chelates formed thereby. The back-extraction acidic solution is performed utilizing an acidic solution. Upon sufficient exposure of the metal and metalloid chelates to the acidic solution, the metal and metalloid species are released from the chelates into the acid solution, while the chelating agent remains in the supercritical fluid solvent. The chelating agent is thereby regenerated and the metal and metalloid species recovered. 3 figs.

Trace metals in liver, skin and muscle of Lethrinus lentjan fish species in relation to body length and sex.

PubMed

Al-Yousuf, M H; El-Shahawi; Al-Ghais, S M

2000-07-10

A post-Gulf sea water pollution assessment program was carried out in the liver, skin and muscle tissues of the localized Lethrinus lentjan fish species [Family: Lethrinidae (Teleost)]. Monitoring the concentration of the major heavy metals at different sites along the western coast of the United Arab Emirates (UAE) on the Arabian Gulf was studied. The concentrations of Zn, Cu and Mn were found to follow the order: liver > skin > muscle while the cadmium level follows the sequence: liver > muscle > skin. The influence of fish sex and body length on the metal accumulation of those metals in the tested fish organs was critically investigated. The average metal concentrations in liver, skin and muscle of female fish were found to be higher than those found in the male fish. The detected metal levels were generally similar to previous pre-war, 1991 levels. The study concludes that the marine fish from the Arabian Gulf are comparatively clean and do not constitute a risk for human health.

Toxic metal tolerance in native plant species grown in a vanadium mining area.

PubMed

Aihemaiti, Aikelaimu; Jiang, Jianguo; Li, De'an; Li, Tianran; Zhang, Wenjie; Ding, Xutong

2017-12-01

Vanadium (V) has been extensively mined in China and caused soil pollution in mining area. It has toxic effects on plants, animals and humans, posing potential health risks to communities that farm and graze cattle adjacent to the mining area. To evaluate in situ phytoremediation potentials of native plants, V, chromium, copper and zinc concentrations in roots and shoots were measured and the bioaccumulation (BAF) and translocation (TF) efficiencies were calculated. The results showed that Setaria viridis accumulated greater than 1000 mg kg -1 V in its shoots and exhibited TF > 1 for V, Cr, Zn and BAF > 1 for Cu. The V accumulation amount in the roots of Kochia scoparia also surpassed 1000 mg kg -1 and showed TF > 1 for Zn. Chenopodium album had BAF > 1 for V and Zn and Daucus carota showed TF > 1 for Cu. Eleusine indica presented strong tolerance and high metal accumulations. S. viridis is practical for in situ phytoextractions of V, Cr and Zn and phytostabilisation of Cu in V mining area. Other species had low potential use as phytoremediation plant at multi-metal polluted sites, but showed relatively strong resistance to V, Cr, Cu and Zn toxicity, can be used to vegetate the contaminated soils and stabilise toxic metals in V mining area.

Formation of Reactive Br Species by Freezing in Solutions of NaBr-Metal-Hydrogen Peroxide

NASA Astrophysics Data System (ADS)

Kinjo, M.; Arakaki, T.

2005-12-01

The role of reactive halogen species (e.g. BrOH) in the destruction of stratospheric ozone is well known and largely understood. In recent years, it became clear that reactive Br species can also play a significant role in tropospheric ozone destruction, but sources of reactive Br species in the troposphere are not well understood. When an aqueous solution is frozen, solutes in the solution are excluded from the ice phase and the solutes are concentrated in the solution phase. Freezing processes cause red-ox reactions in the solution. We tried to understand the effects of freezing processes of solutions on formation of reactive Br species. Hydrogen peroxide (HOOH) and metallic ions were added to a mixing solution of NaBr and allyl alcohol (AA). If reactive Br species are formed, they react with AA, and free Br ion concentration decreases in the solution. When HOOH and Fe(III) or Cu(II) were added to the NaBr and AA solution and frozen, free Br ion concentration decreased. It is possible that OH radical formation from reaction between HOOH and Fe(II) or Cu(I) was induced by freezing processes and the OH radical probably oxidized Br ion to reactive Br species. Study of the effects of pH showed that decrease of Br ion concentration was the highest at pH = 4.0. Freezing processes could be an important source of reactive Br species in high altitude clouds and Polar Regions.

Analysis of certain fatty acids and toxic metal bioaccumulation in various tissues of three fish species that are consumed by Turkish people.

PubMed

Kaya, Gökçe; Türkoğlu, Semra

2017-04-01

Concentrations of toxic metals (Mn, Ni, Hg, Cd, Pb, Cr) in the muscle, skin, and liver of Mugil cephalus, Mullus barbatus, and Pagellus erythrinus which were purchased in large supermarkets of Elazig, and Mullus barbatus, which were caught on the sea of İskenderun Bay, Turkey, were analyzed. Fundamental analyses were carried out by inductively coupled plasma-mass spectrometry (ICP-MS) after samples were prepared by microwave digestion. Mean metal concentrations in different tissues were varied in the ranges of Cd 4-426, Cr 116-4458, Mn 141-24774, Hg 9-471, Pb 96-695, and Ni 68-6581 μg kg -1 , for wet weight. The investigated metal bioaccumulation in the muscles of fish species, in general, was lower than those in the liver and skin. This method was verified by NCS ZC73016 chicken trace element-certified reference material analysis. In addition, fatty acids in the muscles of three fish species were analyzed. According to the gas chromatography (GC) results of fatty acids, the monounsaturated fatty acids (MUFA) were found to be between 23.76 and 31.97%. The fatty acids' polyunsaturated fatty acids (PUFA) ratio was found to be between 13.67 and 30.71% and saturated fatty acids ratios were determined in the range of 24.06-32.30%. In all fish species, eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) ratio, which increase the value of these fish species, were high. These results show that these three fish species are good sources of fatty acids.

Studies of Metal-Metal Bonded Compounds in Catalysis

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

Berry, John F.

The overall goals of this research are (1) to define the fundamental coordination chemistry underlying successful catalytic transformations promoted by metal-metal bonded compounds, and (2) to explore new chemical transformations that occur at metal-metal bonded sites that could lead to the discovery of new catalytic processes. Transformations of interest include metal-promoted reactions of carbene, nitrene, or nitrido species to yield products with new C–C and C–N bonds, respectively. The most promising suite of transition metal catalysts for these transformations is the set of metal-metal bonded coordination compounds of Ru and Rh of the general formula M 2(ligand) 4, where Mmore » = Ru or Rh and ligand = a monoanionic, bridging ligand such as acetate. Development of new catalysts and improvement of catalytic conditions have been stymied by a general lack of knowledge about the nature of highly reactive intermediates in these reactions, the knowledge that is to be supplied by this work. Our three specific objectives for this year have been (A) to trap, isolate, and characterize new reactive intermediates of general relevance to catalysis, (B) to explore the electronic structure and reactivity of these unusual species, and how these two properties are interrelated, and (C) to use our obtained mechanistic knowledge to design new catalysts with a focus on Earth-abundant first-row transition metal compounds.« less

Contribution of transition metals in the reactive oxygen species activity of PM emissions from retrofitted heavy-duty vehicles

NASA Astrophysics Data System (ADS)

Verma, Vishal; Shafer, Martin M.; Schauer, James J.; Sioutas, Constantinos

2010-12-01

We assessed the contribution of water-soluble transition metals to the reactive oxygen species (ROS) activity of diesel exhaust particles (DEPs) from four heavy-duty vehicles in five retrofitted configurations (V-SCRT, Z-SCRT, DPX, hybrid, and school bus). A heavy-duty truck without any control device served as the baseline vehicle. Particles were collected from all vehicle-configurations on a chassis dynamometer under three driving conditions: cruise (80 km h -1), transient UDDS, and idle. A sensitive macrophage-based in vitro assay was used to determine the ROS activity of collected particles. The contribution of water-soluble transition metals in the measured activity was quantified by their removal using a Chelex ® complexation method. The study demonstrates that despite an increase in the intrinsic ROS activity (per mass basis) of exhaust PM with use of most control technologies, the overall ROS activity (expressed per km or per h) was substantially reduced for retrofitted configurations compared to the baseline vehicle. Chelex treatment of DEPs water extracts removed a substantial (≥70%) and fairly consistent fraction of the ROS activity, which ascertains the dominant role of water-soluble metals in PM-induced cellular oxidative stress. However, relatively lower removal of the activity in few vehicle-configurations (V-SCRT, DPX and school bus idle), despite a large aggregate metals removal, indicated that not all species were associated with the measured activity. A univariate regression analysis identified several transition metals (Fe, Cr, Co and Mn) as significantly correlated ( R > 0.60; p < 0.05) with the ROS activity. Multivariate linear regression model incorporating Fe, Cr and Co explained 90% of variability in ROS levels, with Fe accounting for the highest (84%) fraction of the variance.

Determination of antimicrobial and heavy metal resistance profiles of some bacteria isolated from aquatic amphibian and reptile species.

PubMed

Hacioglu, Nurcihan; Tosunoglu, Murat

2014-01-01

The aim of the present study was to determine the level of antibiotic resistance patterns and distribution of heavy metal resistance of bacterial isolates from aquatic animals (Lissotriton vulgaris, Pelophylax ridibundus, Emys orbicularis, Mauremys rivulata, and Natrix natrix) in Turkey (Kavak Delta). A total of 153 bacteria have been successfully isolated from cloaca and oral samples of the aquatic amphibians and reptilians which were found, namely, Aeromonas sp. (n = 29), Plesiomonas sp. (n = 7), Vibrio sp. (n = 12), Citrobacter sp. (n = 12), Enterobacter sp. (n = 11), Escherichia sp. (n = 22), Klebsiella sp. (n = 22), Edwardsiella sp. (n = 6), Hafnia sp. (n = 1), Proteus sp. (n = 19), Providencia sp. (n = 8), and Pseudomonas sp. (n = 4). In terms of antibiotic and heavy metal susceptibility testing, each isolate was tested against 12 antibiotics and 4 metals. There was a high incidence of resistance to cefoxitin (46.40 %), ampicillin (44.44 %), erythromycin (35.29 %), and a low incidence of resistance to gentamicin (6.53 %), kanamycin (8.49 %), chloramphenicol (9.15 %), and cefotaxime (10.45 %). The multiple antibiotic resistance index of each bacterial species indicated that bacteria from raised amphibians and reptiles have been exposed to tested antibiotics, with results ranging from 0 to 0.58. Most isolates showed tolerance to different concentrations of heavy metals, and minimal inhibition concentrations ranged from100 to >3,200 μg/mL. According to these results, a significant occurrence of bacteria in the internal organs of reptiles and amphibians, with a high incidence of resistance against antibiotics and heavy metals, may risk aquatic animals and the public health. These data appoint the importance of epidemiological surveillance and microbiological monitoring and reinforce the need to implement environment protection programs for amphibian and reptile species.

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

EPA Science Inventory

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

Red mud (RM)-Induced enhancement of iron plaque formation reduces arsenic and metal accumulation in two wetland plant species.

PubMed

Yang, J X; Guo, Q J; Yang, J; Zhou, X Y; Ren, H Y; Zhang, H Z; Xu, R X; Wang, X D; Peters, M; Zhu, G X; Wei, R F; Tian, L Y; Han, X K

2016-01-01

Human activities have resulted in arsenic (As) and heavy metals accumulation in paddy soils in China. Phytoremediation has been suggested as an effective and low-cost method to clean up contaminated soils. A combined soil-sand pot experiment was conducted to investigate the influence of red mud (RM) supply on iron plaque formation and As and heavy metal accumulation in two wetland plant species (Cyperus alternifolius Rottb., Echinodorus amazonicus Rataj), using As and heavy metals polluted paddy soil combined with three rates of RM application (0, 2%, 5%). The results showed that RM supply significantly decreased As and heavy metals accumulation in shoots of the two plants due to the decrease of As and heavy metal availability and the enhancement of the formation of iron plaque on the root surface and in the rhizosphere. Both wetland plants supplied with RM tended to have more Fe plaque, higher As and heavy metals on roots and in their rhizospheres, and were more tolerant of As and heavy metal toxicity. The results suggest that RM-induced enhancement of the formation of iron plaque on the root surface and in the rhizosphere of wetland plants may be significant for remediation of soils contaminated with As and heavy metals.

Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

DOEpatents

Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

2017-02-07

A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

Expression of the B subunit of E. coli heat-labile enterotoxin in the chloroplasts of plants and its characterization.

PubMed

Kang, Tae-Jin; Loc, Nguyen-Hoang; Jang, Mi-Ok; Jang, Yong-Suk; Kim, Young-Sook; Seo, Jo-Eun; Yang, Moon-Sik

2003-12-01

Transgenic chloroplasts have become attractive systems for heterologous gene expressions because of unique advantages. Here, we report a feasibility study for producing the nontoxic B subunit of Escherichia coli heat-labile enterotoxin (LTB) via chloroplast transformation of tobacco. Stable site-specific integration of the LTB gene into chloroplast genome was confirmed by PCR and genomic Southern blot analysis in transformed plants. Immunoblot analysis indicated that plant-derived LTB protein was oligomeric, and dissociated after boiling. Pentameric LTB molecules were the dominant molecular species in LTB isolated from transgenic tobacco leaf tissues. The amount of LTB protein detected in transplastomic tobacco leaf was approximately 2.5% of the total soluble plant protein, approximately 250-fold higher than in plants generated via nuclear transformation. The GM1-ELISA binding assay indicated that chloroplast-synthesized LTB protein bound to GM1-ganglioside receptors. LTB protein with biochemical properties identical to native LTB protein in the chloroplast of edible plants opens the way for inexpensive, safe, and effective plant-based edible vaccines for humans and animals.

Emotional Lability in Children and Adolescents with Attention Deficit/Hyperactivity Disorder (ADHD): Clinical Correlates and Familial Prevalence

ERIC Educational Resources Information Center

Sobanski, Esther; Banaschewski, Tobias; Asherson, Philip; Buitelaar, Jan; Chen, Wai; Franke, Barbara; Holtmann, Martin; Krumm, Bertram; Sergeant, Joseph; Sonuga-Barke, Edmund; Stringaris, Argyris; Taylor, Eric; Anney, Richard; Ebstein, Richard P.; Gill, Michael; Miranda, Ana; Mulas, Fernando; Oades, Robert D.; Roeyers, Herbert; Rothenberger, Aribert; Steinhausen, Hans-Christoph; Faraone, Stephen V.

2010-01-01

Background: The goal of this study was to investigate the occurrence, severity and clinical correlates of emotional lability (EL) in children with attention deficit/hyperactivity disorder (ADHD), and to examine factors contributing to EL and familiality of EL in youth with ADHD. Methods: One thousand, one hundred and eighty-six children with ADHD…

Maximum sustainable xylem sap tensions in Rhododendron and other species.

PubMed

Crombie, D S; Milburn, J A; Hipkins, M F

1985-01-01

The acoustic technique was used in conjunction with the pressure chamber to determine the tensions causing cavitation of xylem sap in leaves of five woody angiosperms (Acer pseudoplatanus L., Alnus glutinosa L. Gaertn., Eucalyptus globulus Labill., Fraxinus excelsior L. and Rhododendron ponticum L.) and three species of herbs (Lycopersicum esculentum Mill., Plantago major L. and Ricinus communis L.). The results showed leaves of most species to suffer considerably from cavitation at sap tensions of 1.6-3 MPa. Two of the herbs, Lycopersicum and Ricinus, cavitated extensively at sap tensions below 1 MPa. Additional evidence is presented that clicks, detected by acoustic amplification, are caused by cavitation of sap in the xylem conduits. A rapid method is suggested for the determination of sap tensions in cavitating leaves and which is suitable for surveys of the critical sap tension in a large number of species.

Influence of Different Plant Species on Methane Emissions from Soil in a Restored Swiss Wetland

PubMed Central

Bhullar, Gurbir S.; Edwards, Peter J.; Olde Venterink, Harry

2014-01-01

Plants are a major factor influencing methane emissions from wetlands, along with environmental parameters such as water table, temperature, pH, nutrients and soil carbon substrate. We conducted a field experiment to study how different plant species influence methane emissions from a wetland in Switzerland. The top 0.5 m of soil at this site had been removed five years earlier, leaving a substrate with very low methanogenic activity. We found a sixfold difference among plant species in their effect on methane emission rates: Molinia caerulea and Lysimachia vulgaris caused low emission rates, whereas Senecio paludosus, Carex flava, Juncus effusus and Typha latifolia caused relatively high rates. Centaurea jacea, Iris sibirica, and Carex davalliana caused intermediate rates. However, we found no effect of either plant biomass or plant functional groups – based on life form or productivity of the habitat – upon methane emission. Emissions were much lower than those usually reported in temperate wetlands, which we attribute to reduced concentrations of labile carbon following topsoil removal. Thus, unlike most wetland sites, methane production in this site was probably fuelled chiefly by root exudation from living plants and from root decay. We conclude that in most wetlands, where concentrations of labile carbon are much higher, these sources account for only a small proportion of the methane emitted. Our study confirms that plant species composition does influence methane emission from wetlands, and should be considered when developing measures to mitigate the greenhouse gas emissions. PMID:24586894

N2-dependent growth and nitrogenase activity in the metal-metabolizing bacteria, Geobacter and Magnetospirillum species

USGS Publications Warehouse

Bazylinski, D.A.; Dean, A.J.; Schuler, D.; Phillips, E.J.P.; Lovley, D.R.

2000-01-01

Cells of Geobacter metallireducens, Magnetospirillum strain AMB-1, Magnetospirillum magnetotacticum and Magnetospirillum gryphiswaldense showed N2-dependent growth, the first anaerobically with Fe(lll) as the electron acceptor, and the latter three species micro-aerobically in semi-solid oxygen gradient cultures. Cells of the Magnetospirillum species grown with N2 under microaerobic conditions were magnetotactic and therefore produced magnetosomes. Cells of Geobacter metallireducens reduced acetylene to ethylene (11.5 ?? 5.9nmol C2H4 produced min-1 mg-1 cell protein) while growing with Fe(lll) as the electron acceptor in anaerobic growth medium lacking a fixed nitrogen source. Cells of the Magnetospirillum species, grown in a semi-solid oxygen gradient medium, also reduced acetylene at comparable rates. Uncut chromosomal and fragments from endonuclease-digested chromosomal DNA from these species, as well as Geobacter sulphurreducens organisms, hybridized with a nifHDK probe from Rhodospirillum rubrum, indicating the presence of these nitrogenase structural genes in these organisms. The evidence presented here shows that members of the metal-metabolizing genera, Geobacter and Magnetospirillum, fix atmospheric dinitrogen.

Measuring free metal ion concentrations in situ in natural waters using the Donnan Membrane Technique.

PubMed

Kalis, Erwin J J; Weng, Liping; Dousma, Freerk; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2006-02-01

Metal toxicity is not related to the total but rather to the free or labile metal ion concentration. One of the techniques that can be used to measure several free metal ion concentrations simultaneously is the Donnan Membrane Technique (DMT) in combination with the inductively coupled plasma-mass spectrometer (ICP-MS). However, free metal ion concentrations in natural waters are commonly below the detection limit of ICP-MS. We decreased the detection limit by making use of a ligand, and we developed a field DMT cell that can be applied in situ in natural waters. A kinetic approach can be used to calculate free metal ion concentrations when the equilibrium time becomes too large. The field DMT measured in situ in natural waters a free metal ion concentration ranging from 0.015% (Cu) to 13% (Zn) of a total metal concentration ranging from 0.06 nM (Cd) to 237 nM (Zn). The free metal ion concentrations were difficult to predict using an equilibrium speciation model, probably due to the uncertainty in the nature of the dissolved organic matter or the presence of other reactive colloids. It is shown that DMT can follow changes in the free metal ion concentration on times scales less than a day under certain conditions.

Heavy metals in fish tissues/stomach contents in four marine wild commercially valuable fish species from the western continental shelf of South China Sea.

PubMed

Gu, Yang-Guang; Lin, Qin; Huang, Hong-Hui; Wang, Liang-Gen; Ning, Jia-Jia; Du, Fei-Yan

2017-01-30

The concentrations of heavy metals (Cd, Pb, Cr, Ni, Cu and Zn) were determined in four commercially valuable fish species (Thunnus obesus, Decapterus lajang, Cubiceps squamiceps and Priacanthus macracanthus), collected in the western continental shelf of the South China Sea. Concentrations of Cd, Pb, Cr, Ni, Cu, and Zn in fish muscles were 0.006-0.050, 0.13-0.68, 0.18-0.85, 0.11-0.25, 0.12-0.77, and 2.41-4.73μg/g, wet weight, respectively. Concentrations of heavy metals in all species were below their acceptable daily upper limit, suggesting human consumption of these wild fish species may be safe, with health risk assessment based on the target hazard quotients (THQ) and total THQ, indicating no significant adverse health effects with consumption. The average concentrations of Zn were higher in gills than in stomach contents, backbones or muscle, while conversely, the other heavy metals had higher concentrations in stomach contents than in other tissues. Copyright © 2016 Elsevier Ltd. All rights reserved.

Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils.

PubMed

Ahumada, Inés; Escudero, Paula; Carrasco, M Adriana; Castillo, Gabriela; Ascar, Loreto; Fuentes, Edwar

2004-04-01

In Chile, the increasing number of plants for the treatment of wastewater has brought about an increase in the generation of sludge. One way of sludge disposal is its application on land; this, however involves some problems, some of them being heavy metal accumulation and the increase in organic matter and other components from sewage sludge which may change the distribution and mobility of heavy metals. The purpose of the present study was to determine the effect of sewage sludge application on the distribution of Cr, Ni, Cu, Zn and Pb in agricultural soils in Chile. Three different soils, two Mollisols and one Alfisol, were sampled from an agricultural area in Central Chile. The soils were treated with sewage sludge at the rates of 0 and 30 ton ha(-1), and were incubated at 25 degrees C for 45 days. Before and after incubation, the soils were sequentially extracted to obtain labile (exchangeable and sodium acetate-soluble), potentially labile (soluble in moderately reducing conditions, K4P2O7-soluble and soluble in reducing conditions) and inert (soluble in strong acid oxidizing conditions) fractions. A two-level factored design was used to assess the effect of sludge application rate, incubation time and their interaction on the mobility of the elements under study. Among the metals determined in the sludge, zinc has the highest concentration. However, with the exception of Ni, the total content of metals was lower than the recommended limit values in sewage sludge as stated by Chilean regulations. Although 23% of zinc in sludge was in more mobile forms, the residual fraction of all metals was the predominant form in soils and sludge. The content of zinc only was significantly increased in two of the soils by sewage sludge application. On the other hand, with the exception of copper, the metals were redistributed in the first four fractions of amended soils. The effect of sludge application rate, incubation time and their interaction depended on the metal or

Processing thermally labile drugs by hot-melt extrusion: The lesson with gliclazide.

PubMed

Huang, Siyuan; O'Donnell, Kevin P; Delpon de Vaux, Sophie M; O'Brien, John; Stutzman, John; Williams, Robert O

2017-10-01

The formation of molecularly dispersed amorphous solid dispersions by the hot-melt extrusion technique relies on the thermal and mechanical energy inputs, which can cause chemical degradation of drugs and polymeric carriers. Additionally, drug degradation may be exacerbated as drugs convert from a more stable crystalline form to a higher energy amorphous form. Therefore, it is imperative to study how drug degrades and evaluate methods to minimize drug degradation during the extrusion process. In this work, gliclazide was used as a model thermally labile drug for the degradation kinetics and process optimization studies. Preformulation studies were conducted using thermal analyses, and liquid chromatography-mass spectroscopy to identify drug degradation pathways and to determine initial extrusion conditions. Formulations containing 10% drug and 90% AFFINISOL™ HPMC HME 100LV were then extruded using a twin screw extruder, and the extrudates were characterized using X-ray powder diffraction, modulated dynamic scanning calorimetry, and potency testing to evaluate physicochemical properties. The energies of activation for both amorphous gliclazide, crystalline gliclazide, and gliclazide solution were calculated using the Arrhenius equation to further guide the extrusion optimization process. Preformulation studies identify two hydrolysis degradation pathways of gliclazide at elevated temperatures. The activation energy study indicates a significantly higher degradation rate for the amorphous gliclazide compared to the crystalline form. After optimization of the hot-melt extrusion process, including improved screw designs, machine setup, and processing conditions, gliclazide amorphous solid dispersion with ∼95% drug recovery was achieved. The ability to process thermally labile drugs and polymers using hot-melt extrusion will significantly expand the possible applications of this manufacturing process. Copyright © 2017 Elsevier B.V. All rights reserved.

Quantitative chemical exchange saturation transfer (qCEST) MRI--RF spillover effect-corrected omega plot for simultaneous determination of labile proton fraction ratio and exchange rate.

PubMed

Sun, Phillip Zhe; Wang, Yu; Dai, ZhuoZhi; Xiao, Gang; Wu, Renhua

2014-01-01

Chemical exchange saturation transfer (CEST) MRI is sensitive to dilute proteins and peptides as well as microenvironmental properties. However, the complexity of the CEST MRI effect, which varies with the labile proton content, exchange rate and experimental conditions, underscores the need for developing quantitative CEST (qCEST) analysis. Towards this goal, it has been shown that omega plot is capable of quantifying paramagnetic CEST MRI. However, the use of the omega plot is somewhat limited for diamagnetic CEST (DIACEST) MRI because it is more susceptible to direct radio frequency (RF) saturation (spillover) owing to the relatively small chemical shift. Recently, it has been found that, for dilute DIACEST agents that undergo slow to intermediate chemical exchange, the spillover effect varies little with the labile proton ratio and exchange rate. Therefore, we postulated that the omega plot analysis can be improved if RF spillover effect could be estimated and taken into account. Specifically, simulation showed that both labile proton ratio and exchange rate derived using the spillover effect-corrected omega plot were in good agreement with simulated values. In addition, the modified omega plot was confirmed experimentally, and we showed that the derived labile proton ratio increased linearly with creatine concentration (p < 0.01), with little difference in their exchange rate (p = 0.32). In summary, our study extends the conventional omega plot for quantitative analysis of DIACEST MRI. Copyright © 2014 John Wiley & Sons, Ltd.

Phytoremediation of soil co-contaminated with heavy metals and TNT using four plant species.

PubMed

Lee, Insook; Baek, Kyunghwa; Kim, Hyunhee; Kim, Sunghyun; Kim, Jaisoo; Kwon, Youngseok; Chang, Yoontoung; Bae, Bumhan

2007-11-01

We investigated the germination, growth rates and uptake of contaminants of four plant species, barnyard grass (Echinochloa crusgalli), sunflower (Helianthus annuus), Indian mallow (Abutilon avicennae) and Indian jointvetch (Aeschynomene indica), grown in soil contaminated with cadmium (Cd), lead (Pb) and 2,4,6-trinitrotoluene (TNT). These contaminants are typically found at shooting ranges. Experiments were carried out over 180 days using both single plant cultures and cultures containing an equal mix of the 4 plant species. Germination rates differed among the species in single culture (92% for H. annuus, 84% for E. crusgalli, 48% for A. avicennae and 38% Ae. indica). In the 4-plant mix culture, < 20% of seeds germinated for all 4 species. E. crusgalli and H. annuus grew slightly faster in the four-plant mix culture than in single culture, whereas A. avicennae and Ae. indica grew much slower in the 4-plant mix culture. In both single and 4-plant mix cultures, Cd concentrations in the roots of A. avicennae and E. crusgalliwere high, and Pb concentrations were high in A. avicennae and H. annuus. Cd and Pb concentrations in shoots were low to negligible in both treatment cultures for all species, except E. crusgalli in the 4-plant mix culture. The concentrations of TNT and its metabolites, 2-amino-4,6-dinitrotoluene (2ADNT) and 4-amino-2,6-dinitrotoluene (4ADNT) were high in H. annuus, Ae. indica and A. avicennae. Total Cd removal from soil differed among species, with E. crusgalliremoving the most (50.1%) followed by H. annuus(41.3%), Ae. indica(41.1%) and A. avicennae(33.3%). The four-plant mix removed more Cd (25.8%) than a no-plant control (12.9%). Pb removal was negligible for all plant species. All plant species rapidly removed TNT and its metabolites, regardless of whether the culture was single or mixed. From in these results, we conclude that a phytoremediation for the removal of heavy metals and TNT from contaminated soils should use a single plant species

Heat-labile Enterotoxins as Adjuvants or Anti-Inflammatory Agents

PubMed Central

Liang, Shuang; Hajishengallis, George

2010-01-01

Escherichia coli and Vibrio cholerae produce structurally related AB5-type heat-labile enterotoxins which are classified into two major types. The Type I subfamily includes cholera toxin and E. coli LT-I, whereas the Type II subfamily comprises LT-IIa and LT-IIb. In addition to their roles in microbial pathogenesis, the enterotoxins are widely and intensively studied for their exceptionally strong adjuvant and immunomodulatory activities, which are not necessarily dependent upon their abilities to elevate intracellular cAMP levels. Despite general structural similarities, these molecules, in intact or derivative form, display notable differences in their interactions with gangliosides or Toll-like receptors. This divergence results in differential immune response outcomes, the underlying mechanisms of which remain largely uncharacterized. Whereas the study of these molecules has been pivotal in understanding basic mechanisms of immune regulation, a formidable challenge is to dissociate toxicity from useful properties that can be exploited in vaccine development or for the treatment of autoimmune inflammatory diseases. PMID:20461887

Heat-labile enterotoxins as adjuvants or anti-inflammatory agents.

PubMed

Liang, Shuang; Hajishengallis, George

2010-01-01

Escherichia coli and Vibrio cholerae produce structurally related AB5-type heat-labile enterotoxins, which are classified into two major types. The Type I subfamily includes cholera toxin and E. coli LT-I, whereas the Type II subfamily comprises LT-IIa and LT-IIb. In addition to their roles in microbial pathogenesis, the enterotoxins are widely and intensively studied for their exceptionally strong adjuvant and immunomodulatory activities, which are not necessarily dependent upon their abilities to elevate intracellular cAMP levels. Despite general structural similarities, these molecules, in intact or derivative form, display notable differences in their interactions with gangliosides or Toll-like receptors. This divergence results in differential immune response outcomes, the underlying mechanisms of which remain largely uncharacterized. Whereas the study of these molecules has been pivotal in understanding basic mechanisms of immune regulation, a formidable challenge is to dissociate toxicity from useful properties that can be exploited in vaccine development or for the treatment of autoimmune inflammatory diseases.

Removal of heavy metal species from industrial sludge with the aid of biodegradable iminodisuccinic acid as the chelating ligand.

PubMed

Wu, Qing; Duan, Gaoqi; Cui, Yanrui; Sun, Jianhui

2015-01-01

High level of heavy metals in industrial sludge was the obstacle of sludge disposal and resource recycling. In this study, iminodisuccinic acid (IDS), a biodegradable chelating ligand, was used to remove heavy metals from industrial sludge generated from battery industry. The extraction of cadmium, copper, nickel, and zinc from battery sludge with aqueous solution of IDS was studied under various conditions. It was found that removal efficiency greatly depends on pH, chelating agent's concentration, as well as species distribution of metals. The results showed that mildly acidic and neutral systems were not beneficial to remove cadmium. About 68 % of cadmium in the sample was extracted at the molar ratio of IDS to heavy metals 7:1 without pH adjustment (pH 11.5). Copper of 91.3 % and nickel of 90.7 % could be removed by IDS (molar ratio, IDS: metals = 1:1) with 1.2 % phosphoric acid effectively. Removal efficiency of zinc was very low throughout the experiment. Based on the experimental results, IDS could be a potentially useful chelant for heavy metal removal from battery industry sludge.

Enantiomeric Excesses of Acid Labile Amino Acid Precursors of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Pizzarello, Sandra

1998-10-01

Amino acids present in carbonaceous chondrite are extracted in water in part as free compounds and in approximately equal part as acid labile precursors. On the assumption that they would be free of contamination, the precursors of two Murchison amino acids that have terrestrial occurrence, alanine and glutamic acid, have been targeted for analysis of their enantiomeric ratios. Pyroglutamic acid, the precursor of glutamic acid, was found with an L-enantiomeric excess comparable to that of the free acid, while alanine's precursor, N-acetyl alanine, appears approximately racemic. Also alpha-imino propioacetic acid, a proposed end product of alanine synthesis in the meteorite, was analyzed and found racemic.

Enantiomeric Excesses of Acid Labile Amino Acid Precursors of the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Pizzarello, Sandra

1998-01-01

Amino acids present in carbonaceous chondrite are extracted in water in part as free compounds and in approximately equal part as acid labile precursors. On the assumption that they would be free of contamination, the precursors of two Murchison amino acids that have terrestrial occurrence, alanine and glutamic acid, have been targeted for analysis of their enantiomeric ratios. Pyroglutamic acid, the precursor of glutamic acid, was found with an L-enantiomeric excess comparable to that of the free acid, while alanine's precursor, N-acetyl alanine, appears approximately racemic. Also alpha-imino propioacetic acid, a proposed end product of alanine synthesis in the meteorite, was analyzed and found racemic.

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

USGS Publications Warehouse

White, A.F.; Peterson, M.L.

1996-01-01

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

Assessment of heavy metal accumulation in two species of Tillandsia in relation to atmospheric emission sources in Argentina.

PubMed

Wannaz, Eduardo D; Carreras, Hebe A; Pérez, Carlos A; Pignata, María L

2006-05-15

The ability of Tillandsia capillaris Ruiz and Pav. f. capillaris and Tillandsia permutata A. Cast. to accumulate heavy metals was evaluated in relation to potential atmospheric emission sources in Argentina. The sampling areas (n=38) were chosen in the province of Córdoba, located in the center of Argentina, and categorized according to land use, anthropogenic activities and/or distance to potential heavy metal emission sources. In each sampling site, pools of 40-50 individuals of each species were made from plants collected along the four cardinal directions. The concentrations of V, Mn, Fe, Co, Ni, Cu, Zn, Pb and Br of these samples were measured by Total Reflection X-Ray Fluorescence (TXRF) analysis with Synchrotron Radiation. Each species was submitted to a cluster analysis in order to discriminate different groups of heavy metals as tracers of natural or anthropogenic sources. A Contamination Factor (CF) was calculated using the concentrations of the elements in each sample compared to their concentrations in the control samples. Finally, the rank coefficients of correlation between the CFs and the categorical variables characteristic of each site (land use and anthropogenic load) were analyzed. A positive correlation was found for T. capillaris between the CFs of V, Mn, Co, Ni, Cu and Zn and the urban-industrial category, whereas the CF values for Zn and Pb were positively correlated with the road category. In T. permutata there was a positive correlation between the CF of Zn and the urban-industrial category and the CF of Pb with the road category. We therefore conclude that T. capillaris is a more efficient metal accumulator in passive biomonitoring studies.

Lability landscape and protease resistance of human insulin amyloid: a new insight into its molecular properties.

PubMed

Malisauskas, Mantas; Weise, Christoph; Yanamandra, Kiran; Wolf-Watz, Magnus; Morozova-Roche, Ludmilla

2010-02-12

Amyloid formation is a universal behavior of proteins central to many important human pathologies and industrial processes. The extreme stability of amyloids towards chemical and proteolytic degradation is an acquired property compared to the precursor proteins and is a major prerequisite for their accumulation. Here, we report a study on the lability of human insulin amyloid as a function of pH and amyloid ageing. Using a range of methods such as atomic force microscopy, thioflavin T fluorescence, circular dichroism, and gas-phase electrophoretic mobility macromolecule analysis, we probed the propensity of human insulin amyloid to propagate or dissociate in a wide span of pH values and ageing in a low concentration regime. We generated a three-dimensional amyloid lability landscape in coordinates of pH and amyloid ageing, which displays three distinctive features: (i) a maximum propensity to grow near pH 3.8 and an age corresponding to the inflection point of the growth phase, (ii) an abrupt cutoff between growth and disaggregation at pH 8-10, and (iii) isoclines shifted towards older age during the amyloid growth phase at pH 4-9, reflecting the greater stability of aged amyloid. Thus, lability of amyloid strongly depends on the ionization state of insulin and on the structure and maturity of amyloid fibrils. The stability of insulin amyloid towards protease K was assessed by using real-time atomic force microscopy and thioflavin T fluorescence. We estimated that amyloid fibrils can be digested both from the free ends and within the length of the fibril with a rate of ca 4 nm/min. Our results highlight that amyloid structures, depending on solution conditions, can be less stable than commonly perceived. These results have wide implications for understanding the propagation of amyloids via a seeding mechanism as well as for understanding their natural clearance and dissociation under solution conditions unfavorable for amyloid formation in biological systems and

Hemodynamic changes in systolic and diastolic function during isoproterenol challenge predicts symptomatic response to myectomy in hypertrophic cardiomyopathy with labile obstruction.

PubMed

Prasad, Megha; Geske, Jeffrey B; Sorajja, Paul; Ommen, Steve R; Schaff, Hartzell V; Gersh, Bernard J; Nishimura, Rick A

2016-11-15

We aimed to assess the utility of changes in systolic and diastolic function by isoproterenol challenge in predicting symptom resolution post-myectomy in selected patients with hypertrophic cardiomyopathy (HCM) and labile obstruction. In a subset of symptomatic HCM patients without resting/provocable obstruction on noninvasive assessment, isoproterenol challenge during hemodynamic catheterization may elicit labile left ventricular outflow tract (LVOT) obstruction, and demonstrate the effect of obstruction on diastolic function. These changes may determine whether patients achieve complete symptom resolution post-myectomy. Between February 2003 and April 2009, 18 symptomatic HCM patients without LVOT obstruction on noninvasive testing underwent isoproterenol provocation and septal myectomy due to presence of provocable gradient and were followed for 4 (IQR 3-7) years. Thirteen (72.2%) had complete symptom resolution, while 5 (27.8%) had improved, but persistent symptoms. Those with provoked gradient >100 mm Hg or increase in left atrial pressure (LAP) with isoproterenol had symptom resolution. Symptomatic HCM patients without LVOT gradient on noninvasive testing may demonstrate labile obstruction with isoproterenol. With isoproterenol, patients with high LVOT gradient or increase in LAP concomitant with an increase in gradient achieved complete symptom resolution post-myectomy. Thus, improved diastolic filling as well as outflow gradient production in patients with HCM may predict symptom response to myectomy. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Relation between different metal pollution criteria in sediments and its contribution on assessing toxicity.

PubMed

Alves, Cristina M; Ferreira, Carlos M H; Soares, Helena M V M

2018-05-14

Several tools have been developed and applied to evaluate the metal pollution status of sediments and predict their potential ecological risk assessment. To date, a comprehensive relationship between the information given by these sediment tools for predicting metal bioavailability and the effective toxicity observed is lacking. In this work, the possible inter-correlations between the data outcoming from using several qualitative evaluation tools of the sediment contamination (contamination factor, CF, the enrichment factor, EF, or the geoaccumulation index, Igeo), metal speciation on sediments (evaluated by the modified BCR sequential extraction procedure) and free metal concentrations in pore waters were studied. It was also our aim to evaluate if these assessment tools could be used for predicting the pore waters toxicity data as toxicity proxy. Principal component analysis and cluster analysis revealed that two quality indices used (CF and EF) were highly correlatable with the more labile fractions from BCR sediment speciation. However, neither of these parameters did correlate with the toxicity of pore waters measured by the chronic toxicity (72 h) in Pseudokirchneriella subcapitata. In contrast, the toxic effects of the given total metal load in sediments were better evaluated by using an additive metal approach using pore water free metal concentrations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Integrated multi-biomarker responses in two dreissenid species following metal and thermal cross-stress.

PubMed

Potet, Marine; Devin, Simon; Pain-Devin, Sandrine; Rousselle, Philippe; Giambérini, Laure

2016-11-01

With current global changes, the combination of several stressors such as temperature and contaminants may impact species distribution and ecosystem functioning. In this study, we evaluated the combined impact of two metals (Ni and Cr) with a thermal stress (from 12 to 17 °C) on biomarker responses in two bivalves, Dreissena rostriformis bugensis and Dreissena polymorpha. Biomarkers are informative tools to evaluate exposure and effects of stressors on organisms. The set of 14 biomarkers measured here was representative of both physiologic (filtration activity) and cellular antioxidant and detoxification mechanisms. Our aim was to study the response pattern of both species, and its meaning in terms of invasive potential. The implications for the use of these mussels in environmental monitoring are also discussed. Results evidenced that the two species do not respond to multiple stressors in the same way. Indeed, the effects of contamination on biomarker responses were more marked for D. polymorpha, especially under nickel exposure. While we cannot conclude as to the effect of temperature, invasiveness could be influenced by species sensitivity to contaminants. The physiological and cellular differences between D. polymorpha and D. r. bugensis might also be of concern for environmental risk assessment. The two species present differential bioaccumulation patterns, filtration activity and cellular biomarker responses. If D. polymorpha populations decline, their substitution by D. r. bugensis for biomonitoring or laboratory studies will not be possible without a deeper understanding of biomarker responses of the new invasive. Copyright © 2016 Elsevier Ltd. All rights reserved.

Seasonal Dynamics of Soil Labile Organic Carbon and Enzyme Activities in Relation to Vegetation Types in Hangzhou Bay Tidal Flat Wetland

PubMed Central

Shao, Xuexin; Yang, Wenying; Wu, Ming

2015-01-01

Soil labile organic carbon and soil enzymes play important roles in the carbon cycle of coastal wetlands that have high organic carbon accumulation rates. Soils under three vegetations (Phragmites australis, Spartina alterniflora, and Scirpusm mariqueter) as well as bare mudflat in Hangzhou Bay wetland of China were collected seasonally. Seasonal dynamics and correlations of soil labile organic carbon fractions and soil enzyme activities were analyzed. The results showed that there were significant differences among vegetation types in the contents of soil organic carbon (SOC) and dissolved organic carbon (DOC), excepting for that of microbial biomass carbon (MBC). The P. australis soil was with the highest content of both SOC (7.86 g kg-1) and DOC (306 mg kg-1), while the S. mariqueter soil was with the lowest content of SOC (6.83 g kg-1), and the bare mudflat was with the lowest content of DOC (270 mg kg-1). Soil enzyme activities were significantly different among vegetation types except for urease. The P. australis had the highest annual average activity of alkaline phosphomonoesterase (21.4 mg kg-1 h-1), and the S. alterniflora had the highest annual average activities of β-glycosidase (4.10 mg kg-1 h-1) and invertase (9.81mg g-1 24h-1); however, the bare mudflat had the lowest activities of alkaline phosphomonoesterase (16.2 mg kg-1 h-1), β-glycosidase (2.87 mg kg-1 h-1), and invertase (8.02 mg g-1 24h-1). Analysis also showed that the soil labile organic carbon fractions and soil enzyme activities had distinct seasonal dynamics. In addition, the soil MBC content was significantly correlated with the activities of urease and β-glucosidase. The DOC content was significantly correlated with the activities of urease, alkaline phosphomonoesterase, and invertase. The results indicated that vegetation type is an important factor influencing the spatial-temporal variation of soil enzyme activities and labile organic carbon in coastal wetlands. PMID:26560310

The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

USGS Publications Warehouse

White, A.F.; Peterson, M.L.

1998-01-01

The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

A Double Blind Trial of Divalproex Sodium for Affective Lability and Alcohol Use Following Traumatic Brain Injury

DTIC Science & Technology

2009-10-01

SUBJECT TERMS Traumatic Brain Injury, Alcohol Use , Mood , Mood Stabilization 16. SECURITY CLASSIFICATION OF: U 17. LIMITATION OF ABSTRACT 18...1995 for this indication. Also, it is used in conjunction with lithium or carbamazepine to prevent recurrent manic or depressive episodes during long...0652 TITLE: A Double Blind Trial of Divalproex Sodium for Affective Lability and Alcohol Use Following Traumatic Brain Injury PRINCIPAL

Comparison of hamstring and quadriceps femoris electromyographic activity between men and women during a single-limb squat on both a stable and labile surface.

PubMed

Youdas, James W; Hollman, John H; Hitchcock, James R; Hoyme, Gregory J; Johnsen, Jeremiah J

2007-02-01

The purpose of this study was to determine if women are quadriceps dominant and men are hamstring dominant during the performance of a partial single-leg squat (SLS) on both a stable and labile ground surface against body weight resistance. Thirty healthy participants (15 men and 15 women) performed an SLS on both a stable surface and a 6.4-cm-thick vinyl pad. Surface electromyographic (EMG) recordings were obtained from the quadriceps femoris and hamstring muscles during the extension phase of the SLS. Statistical analysis revealed that women produced 14% more EMG activity (p = 0.04) in their quadriceps than the men during the SLS on a stable surface, whereas the men generated 18% more EMG activity (p = 0.04) in their hamstrings than the women during the SLS on a labile surface. Additionally, we found a statistically significant sex effect (p = 0.048) for the hamstring/quadriceps (H/Q) EMG ratio, which was 2.25 and 0.62, respectively, for men and women on the stable surface and 2.52 and 0.71, respectively, on the labile surface. We concluded that women are quadriceps dominant and men are hamstring dominant during the performance of SLS against body weight resistance on either a stable or labile surface condition. During an SLS, men showed an H/Q ratio approximately 3.5 times larger than their female counterparts, suggesting that men activate their hamstrings more effectively than women during an SLS. According to our data, the SLS may not be an ideal exercise for activating the hamstring muscles in women without additional neuromuscular training techniques, because women are quadriceps dominant during the SLS.

Amino Acid Enantiomeric Ratios in Semi-Labile vs. Refractory Dissolved Organic Matter: Implications for a Microbial N Pump

NASA Astrophysics Data System (ADS)

Bour, A. L.; Broek, T.; Gier, E. J.; Mccarthy, M. D.

2016-02-01

Microbes are key moderators in the cycling of marine dissolved organic matter (DOM), most of which remains unidentifiable at the molecular level. A major current question, however, is to what degree heterotrophic bacteria directly mediate C and N sequestration in the deep sea. Amino acids (AA) represent almost all organic N that can be identified at the molecular level, while D-AA enantiomers represent unique source-specific biomarkers for prokaryotes, known to be highly enriched in ocean DOM. If increasing bacterial-sourced material ultimately leads to millennial scale sequestration of refractory DOM (RDOM), then one would expect a clear correlation between bacterial biomarkers and DOM radiocarbon (Δ14C) ages, in particular in the deep sea. Here we directly test this idea for the first time, by measuring D-AA abundance and distribution in isolated Δ14C young vs. old DOM from the central north pacific gyre. We used a coupled ultrafiltration/solid phase extraction approach to isolate semi-labile vs. RDOM, based on known molecular weight and Δ14C age correlations. The Δ14C ages of isolated material ranged from 205-275 ybp for surface semi-labile DOM, to 6680-6740 ybp for deep ocean RDOM. We measured enantiomeric (D/L) AA ratios, as well as AA molar percentages to estimate traditional degradation parameters (DI and RI), in semi-labile vs. RDOM fractions from the surface to deep ocean at HOT, Station ALOHA. We interpret our results in terms of the hypothesis of a microbial N pump, examining the similarity of microbial source signatures (D/L distributions) and calculated organic N contributions from heterotrophic bacteria, in the context of the Δ14C age of each fraction. Finally, we also evaluate these data vs. common AA molar percentage based indices of degradation.

Quantitative chemical exchange saturation transfer (qCEST) MRI - omega plot analysis of RF-spillover-corrected inverse CEST ratio asymmetry for simultaneous determination of labile proton ratio and exchange rate.

PubMed

Wu, Renhua; Xiao, Gang; Zhou, Iris Yuwen; Ran, Chongzhao; Sun, Phillip Zhe

2015-03-01

Chemical exchange saturation transfer (CEST) MRI is sensitive to labile proton concentration and exchange rate, thus allowing measurement of dilute CEST agent and microenvironmental properties. However, CEST measurement depends not only on the CEST agent properties but also on the experimental conditions. Quantitative CEST (qCEST) analysis has been proposed to address the limitation of the commonly used simplistic CEST-weighted calculation. Recent research has shown that the concomitant direct RF saturation (spillover) effect can be corrected using an inverse CEST ratio calculation. We postulated that a simplified qCEST analysis is feasible with omega plot analysis of the inverse CEST asymmetry calculation. Specifically, simulations showed that the numerically derived labile proton ratio and exchange rate were in good agreement with input values. In addition, the qCEST analysis was confirmed experimentally in a phantom with concurrent variation in CEST agent concentration and pH. Also, we demonstrated that the derived labile proton ratio increased linearly with creatine concentration (P < 0.01) while the pH-dependent exchange rate followed a dominantly base-catalyzed exchange relationship (P < 0.01). In summary, our study verified that a simplified qCEST analysis can simultaneously determine labile proton ratio and exchange rate in a relatively complex in vitro CEST system. Copyright © 2015 John Wiley & Sons, Ltd.

Lability of secondary organic particulate matter

PubMed Central

Liu, Pengfei; Li, Yong Jie; Wang, Yan; Gilles, Mary K.; Zaveri, Rahul A.; Bertram, Allan K.

2016-01-01

The energy flows in Earth’s natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic compared with biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate Dorg for the biogenic case is at least 103 times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth’s atmosphere. PMID:27791063

Lability of secondary organic particulate matter

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

Liu, Pengfei; Li, Yong Jie; Wang, Yan

2016-10-24

We report the energy flows in Earth’s natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representativemore » of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic compared with biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate D org for the biogenic case is at least 10 3 times greater than that of the anthropogenic case. In conclusion, these differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth’s atmosphere.« less

The temperature sensitivity of soil organic carbon decomposition is not related to labile and recalcitrant carbon.

PubMed

Tang, Jie; Cheng, Hao; Fang, Changming

2017-01-01

The response of resistant soil organic matter to temperature change is crucial for predicting climate change impacts on C cycling in terrestrial ecosystems. However, the response of the decomposition of different soil organic carbon (SOC) fractions to temperature is still under debate. To investigate whether the labile and resistant SOC components have different temperature sensitivities, soil samples were collected from three forest and two grass land sites, along with a gradient of latitude from 18°40'to 43°17'N and elevation from 600 to 3510 m across China, and were incubated under changing temperature (from 12 to 32 oC) for at least 260 days. Soil respiration rates were positively related to the content of soil organic carbon and soil microbial carbon. The temperature sensitivity of soil respiration, presented as Q10 value, varies from 1.93 ± 0.15 to 2.60 ± 0.21. During the incubation, there were no significant differences between the Q10 values of soil samples from different layers of the same site, nor a clear pattern of Q10 values along with the gradient of latitude. The result of this study does not support current opinion that resistant soil carbon decomposition is more sensitive to temperature change than labile soil carbon.

Chemical Glucosylation of Labile Natural Products Using a (2-Nitrophenyl)acetyl-Protected Glucosyl Acetimidate Donor.

PubMed

Weber, Julia; Schwarz, Markus; Schiefer, Andrea; Hametner, Christian; Häubl, Georg; Fröhlich, Johannes; Mikula, Hannes

2018-06-07

The synthesis of (2-nitrophenyl)acetyl (NPAc)-protected glucosyl donors is described that were designed for the neighboring-group assisted glucosylation of base-labile natural products also being sensitive to hydrogenolysis. Glycosylation conditions were optimized using a trichloroacetimidate glucosyl donor, and cyclohexylmethanol and (+)-menthol as model acceptors. The approach was then extended to a one-pot procedure for the synthesis of 1,2- trans -glycosides. This method was finally applied for improved synthesis of the masked mycotoxin T2- O -β,d-glucoside.

Tunable electrical conductivity in metal-organic framework thin film devices

DOEpatents

Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

2016-08-30

A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

Tunable electrical conductivity in metal-organic framework thin film devices

DOEpatents

Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

2016-05-24

A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

Partitioning of Dissolved Metals (Fe, Mn, Cu, Cd, Zn, Ni, and Pb) into Soluble and Colloidal Fractions in Continental Shelf and Offshore Waters, Northern California

NASA Astrophysics Data System (ADS)

Fitzsimmons, J. N.; Parker, C.; Sherrell, R. M.

2016-02-01

The physicochemical speciation of trace metals in seawater influences their cycling as essential micronutrients for microorganisms or as tracers of anthropogenic influences on the marine environment. While chemical speciation affects lability, the size of metal complexes influences their ability to be accessed biologically and also influences their fate in the aggregation pathway to marine particles. In this study, we show that multiple trace metals in shelf and open ocean waters off northern California (IRN-BRU cruise, July 2014) have colloidal-sized components. Colloidal fractions were operationally defined using two ultrafiltration methods: a 0.02 µm Anopore membrane and a 10 kDa ( 0.003 µm) cross flow filtration (CFF) system. Together these two methods distinguished small (0.003 - 0.02 µm) and large (0.02 µm - 0.2 µm) colloids. As has been found previously for seawater in other ocean regimes, dissolved Fe had a broad size distribution with 50% soluble (<10 kDa) complexes and both small and large colloidal species. Dissolved Mn had no measurable colloidal component, consistent with its predicted chemical speciation as free Mn(II). Dissolved Cu, which like Fe is thought to be nearly fully organically bound in seawater, was only 25% colloidal, and these colloids were all small. Surprisingly Cd, Ni, and Pb also showed colloidal components (8-20%, 25-40%, and 10-50%) despite their hypothesized low organic speciation. Zn and Pb were nearly completely sorbed onto the Anopore membrane, making CFF the only viable ultrafiltration method for those elements. Zn suffered incomplete recovery ( 50-75%) through the CFF system but showed 30-85% colloidal contribution; thus, verifying a Zn colloidal phase with these methods is challenging. Conclusions will reveal links between the physical and chemical speciation for these metals and what role these metal colloids might have on trace metal exchange between the ocean margin and offshore waters.

Forms and lability of phosphorus in algae and aquatic macrophytes characterized by solution 31P NMR coupled with enzymatic hydrolysis

USDA-ARS?s Scientific Manuscript database

Increased information on forms and lability of phosphorus (P) in aquatic macrophytes and algae is crucial for better understanding of P biogeochemical cycling in eutrophic lakes. In this work, solution 31P nuclear magnetic resonance (NMR) spectroscopy coupled with enzymatic hydrolysis (EH) was used ...

Labile and recalcitrant organic matter utilization by river biofilm under increasing water temperature.

PubMed

Ylla, Irene; Romaní, Anna M; Sabater, Sergi

2012-10-01

Microbial biofilms in rivers contribute to the decomposition of the available organic matter which typically shows changes in composition and bioavailability due to their origin, seasonality, and watershed characteristics. In the context of global warming, enhanced biofilm organic matter decomposition would be expected but this effect could be specific when either a labile or a recalcitrant organic matter source would be available. A laboratory experiment was performed to mimic the effect of the predicted increase in river water temperature (+4 °C above an ambient temperature) on the microbial biofilm under differential organic matter sources. The biofilm microbial community responded to higher water temperature by increasing bacterial cell number, respiratory activity (electron transport system) and microbial extracellular enzymes (extracellular enzyme activity). At higher temperature, the phenol oxidase enzyme explained a large fraction of respiratory activity variation suggesting an enhanced microbial use of degradation products from humic substances. The decomposition of hemicellulose (β-xylosidase activity) seemed to be also favored by warmer conditions. However, at ambient temperature, the enzymes highly responsible for respiration activity variation were β-glucosidase and leu-aminopeptidase, suggesting an enhanced microbial use of polysaccharides and peptides degradation products. The addition of labile dissolved organic carbon (DOC; dipeptide plus cellobiose) caused a further augmentation of heterotrophic biomass and respiratory activity. The changes in the fluorescence index and the ratio Abs(250)/total DOC indicated that higher temperature accelerated the rates of DOC degradation. The experiment showed that the more bioavailable organic matter was rapidly cycled irrespective of higher temperature while degradation of recalcitrant substances was enhanced by warming. Thus, pulses of carbon at higher water temperature might have consequences for DOC

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

NASA Astrophysics Data System (ADS)

Vystavna, Yuliya

2014-05-01

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water in poorly gauged transboundary Ukraine/Russia region. This study includes analysis of tracers use for the indication of water pollution events, including controlled and emerging discharges, and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal) and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e. DGT and POCIS) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac and ketoprofen). Samples were analysed using ICP - MS (trace metals) and LC-MS/MS ESI +/- (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: 'stable' (Cd and Cr) and 'time-varying' (Cu, Zn, Ni and Pb). The relationship Cd >> Cu > Ag > Cr ≥ Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb - Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (run-off, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g. accidents on sewage

Metallic Species, Oxygen and Silicon in the Lunar Exosphere: Upper Limits and Prospects for LADEE Measurements

NASA Technical Reports Server (NTRS)

Sarantos, Menelaos; Killen, Rosemary Margaret; Glenar, David A.; Benna, Mehdi; Stubbs, Timothy J.

2012-01-01

The only species that have been so far detected in the lunar exosphere are Na, K, Ar,and He. However, models for the production and loss of species derived from the lunarregolith through micrometeoroid impact vaporization, sputtering, and photon-stimulateddesorption, predict that a host of other species should exist in the lunar exosphere.Assuming that loss processes are limited to ballistic escape, photoionization, and recyclingto the surface, we have computed column abundances and compared them to publishedupper limits for the Moon. Only for Ca do modeled abundances clearly exceed theavailable measurements. This result suggests the relevance of some loss processes thatwere not included in the model, such as the possibility of gas-to-solid phasecondensation during micrometeoroid impacts or the formation of stable metallic oxides.Our simulations and the recalculation of efficiencies for resonant light scattering showthat models for other species studied are not well constrained by existingmeasurements. This fact underlines the need for improved remote and in situmeasurements of the lunar exosphere such as those planned by the Lunar Atmosphereand Dust Environment Explorer (LADEE) spacecraft. Our simulations of the LADEEneutral mass spectrometer and visibleultraviolet spectrometer indicate that LADEE measurements promise to provide definitive observations or set stringent upper limitsfor all regolith-driven exospheric species. We predict that observations by LADEE willconstrain assumed model parameters for the exosphere of the Moon.

Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

PubMed

Toyao, Takashi; Fujiwaki, Mika; Miyahara, Kenta; Kim, Tae-Ho; Horiuchi, Yu; Matsuoka, Masaya

2015-11-01

Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid-Labile Poly(glycidyl methacrylate)-Based Star Gene Vectors.

PubMed

Yang, Yan-Yu; Hu, Hao; Wang, Xing; Yang, Fei; Shen, Hong; Xu, Fu-Jian; Wu, De-Cheng

2015-06-10

It was recently reported that ethanolamine-functionalized poly(glycidyl methacrylate) (PGEA) possesses great potential applications in gene therapy due to its good biocompatibility and high transfection efficiency. Importing responsivity into PGEA vectors would further improve their performances. Herein, a series of responsive star-shaped vectors, acetaled β-cyclodextrin-PGEAs (A-CD-PGEAs) consisting of a β-CD core and five PGEA arms linked by acid-labile acetal groups, were proposed and characterized as therapeutic pDNA vectors. The A-CD-PGEAs owned abundant hydroxyl groups to shield extra positive charges of A-CD-PGEAs/pDNA complexes, and the star structure could decrease charge density. The incorporation of acetal linkers endowed A-CD-PGEAs with pH responsivity and degradation. In weakly acidic endosome, the broken acetal linkers resulted in decomposition of A-CD-PGEAs and morphological transformation of A-CD-PGEAs/pDNA complexes, lowering cytotoxicity and accelerating release of pDNA. In comparison with control CD-PGEAs without acetal linkers, A-CD-PGEAs exhibited significantly better transfection performances.

Control of thermal conductivity with species mass in transition-metal dichalcogenides

NASA Astrophysics Data System (ADS)

Thomas, Iorwerth O.; Srivastava, G. P.

2018-04-01

In this paper, we examine how the behaviour of the thermal conductivity of bulk and monolayer transition-metal dichalcogenides XY2 in their 2-H form can be controlled with different choices of cation and anion masses. We employ a semi-ab-initio approach, which combines first-principles phonon eigensolutions, the elastic anharmonic Hamiltonian for phonon-phonon interactions, a quasi-harmonic scheme for the temperature-dependent Grüneisen's constant, and a relaxation-time solution of the Boltzmann transport equation. Our results confirm an earlier finding [Gu and Yang, Appl. Phys. Lett. 105, 131903 (2014)] that the thermal conductivity of 2-H MoS2 is lower than that of 2-H WS2 contrary to what would be expected from the relative masses of Mo and W and the relative stiffnesses of both compounds. In addition to confirming this anomaly as a result of the larger acoustic optical gap of WS2 relative to that of MoS2, it is found that where one constituent species is fixed, more profound changes on the thermal conductivity occur for different anion masses than for different cation masses. We explain how these behaviours arise from the dispersion relations of each compound and the anharmonic interactions of phonon modes, and its connection with the relative masses of the constituent species. This finding provides useful insight into which 2-H dichalcogenides might be suitable for which thermal applications.

Heteroatom-free arene-cobalt and arene-iron catalysts for hydrogenations.

PubMed

Gärtner, Dominik; Welther, Alice; Rad, Babak Rezaei; Wolf, Robert; Jacobi von Wangelin, Axel

2014-04-01

75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is--conceptually different from heteroatom-based ligands--stabilized by π coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-"naked" anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various π acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

The DIRT on Q10: In situ depletion of labile-inputs does not increase temperature sensitivity in a laboratory incubation (Invited)

NASA Astrophysics Data System (ADS)

Reynolds, L. L.; Lajtha, K.; Bowden, R.; Johnson, B. R.; Bridgham, S. D.

2013-12-01

The decomposition of soil organic matter is expected to increase with global warming and has been commonly described by kinetic models with at least two pools with differing turnover times. Pools characterized by rapid turnover are thought to consist of labile substrates. Meanwhile, slower turnover is attributed, in part, to greater chemical complexity and a necessarily higher activation energy which should in turn lead to a higher sensitivity (Q10) to temperature and a proportionally larger response to warming. Experimental tests of the relative Q10 of these pools have been inconclusive and contradictory in part due the fact that all pools are decomposing simultaneously and soils kept under differing conditions over long periods of time diverge in more than the Q10 response making them less comparable over time. We present here a test of the temperature response on soils from a 20 yr litter manipulation experiment incubated under an experimental regime that minimizes divergence among the soils. We hypothesize that 1) if exclusion of inputs has depleted labile substrates and 2) the remaining carbon is more chemically complex, then the input exclusion treatments should show a higher Q10 compared to the ambient or increased input treatments. The soils are taken from the Detritus Input and Removal Treatment (DIRT) plots in the Bousson Forest, Pennsylvania, US. The DIRT treatments consist of litter and root exclusion (no inputs = NI), no roots (NR), no litter (NL), double litter (DL), and ambient conditions (C). Soils were incubated at 25oC for 525 days. Periodically, replicate sets were rotated into 15oC, 35oC or remained at 25oC for 24 hr. The headspace CO2 concentration was measured before and after the 24 hr temperature treatments, and then all replicate sets were returned to 25oC. Twenty years of input exclusion decreased respiration rate, with NI < NR = NL < C = DL, and total carbon content, and thus, we conclude, labile substrates. The respiration rate at 25o

Observational and experimental astrochemistry: A high resolution gas phase study of metal containing species in the laboratory and circumstellar envelopes of stars

NASA Astrophysics Data System (ADS)

Pulliam, Robin Leigh

It was once thought that molecules in the interstellar medium (ISM) would be destroyed in the harsh surroundings and conditions of space, and therefore unobservable by radio techniques. However, it is now understood that the chemistry of the ISM is vast and complex. The question still remains as to just how complex is this chemistry? Much is clearly still not understood. This dissertation presents work on the study of metal compounds and cations in the circumstellar envelopes of oxygen- and carbon-rich asymptotic giant branch (AGB) and supergiant stars. Laboratory studies were also conducted on several transition metal compounds of interstellar interest, some of high spin and orbital angular momentum states. Work has been completed to confirm the detection of the debated metal cyanide KCN in the carbon-rich AGB star IRC+10216. KCN joins the list as the fifth interstellar metal cyanide/isocyanide detected in this source. In addition, preliminary results on the search for TiO are presented towards the oxygen-rich supergiant star, VY CMa. To further understand the evolutionary processes of carbon- and oxygen-rich stars, a survey of HCO+ was taken towards the carbon star IRC+10216, the oxygen-rich AGBs TX Cam, IK Tau, and W Hya and the oxygen-rich supergiant NML Cyg. While HCO+ was detected towards all of these sources, the results are vastly different. The outflow of NML Cyg proves to be asymmetric and further study is necessary. Interestingly, while TX Cam and IK Tau are thought to be virtually similar stars, the emission of HCO+ might state otherwise. Finally, the emission from W Hya is significantly narrower than the other sources. To understand species in space with more confidence, a laboratory search for several 3d transition metal species of astrochemical interest was conducted in the laboratory: HZnCl, ZnO, ZnCl, TiS and CrS. All of the molecules have been observed for the first time through high resolution gas phase rotational spectroscopy and the work on Zn

Heavy metals concentration and availability of different soils in Sabzevar area, NE of Iran

NASA Astrophysics Data System (ADS)

Mazhari, Seyed Ali; Sharifiyan Attar, Reza; Haghighi, Faezeh

2017-10-01

Soils developed in the Sabzevar ophiolitic area originate from different bedrocks. All samples display similar physico-chemical properties, but heavy metal concentrations vary extremely in different soil samples. Serpentine soils have the highest total concentration of Cr, Ni and Co; while soils derived from mafic rocks (olivine basalts and hornblende gabbros) show the highest Cu (85.29-109.11 ppm) and Zn (46.88-86.60 ppm). The DTPA-extraction of soil samples indicates that the order of metal bioavailability was Crmetal availabilities of studied soils are not quite similar to total concentrations. The bedrock properties and minerals involved during soil formations have a significant effect on the metals availability. The soils derived from volcanic rocks have, in general, higher metal bioavailability than those derived from plutonic rocks. Serpentine soils with high concentration of Co and Cr, exhibit low availability of these elements (<1% of total Cr and <10% of total Co), whereas olivine basalt samples release high values (>3% of total Cr; >12% of total Co and >17% of total Zn). Oxide minerals (such as chromite and magnetite) in Sabzevar soils play as resistant minerals and impede the heavy metal availability; while forsterite, pyroxene, serpentine and talc are more labile and show higher DTPA-extractable of heavy metals.

Prevalence and associated demographic characteristics of exposure to multiple metals and their species in human populations: The United States NHANES, 2007-2012.

PubMed

Shim, Youn K; Lewin, Michael D; Ruiz, Patricia; Eichner, June E; Mumtaz, Moiz M

2017-01-01

Lead (Pb), cadmium (Cd), mercury (Hg), and arsenic (As) are among the top 10 pollutants of global health concern. Studies have shown that exposures to these metals produce severe adverse effects. However, the mechanisms underlying these effects, particularly joint toxicities, are poorly understood in humans. The objective of this investigation was to identify and characterize prevalent combinations of these metals and their species in the U.S. NHANES population to provide background data for future studies of potential metal interactions. Exposure was defined as urine or blood levels ≥ medians of the NHANES 2007-2012 participants ≥6 years (n = 7408). Adjusted-odds ratios (adj-OR) and 95% confidence intervals were determined for covariates (age, gender, and race/ethnicity, cotinine and body mass index). Species-specific analysis was also conducted for As and Hg including iAs (urinary arsenous acid and/or arsenic acid), met-iAs (urinary monomethylarsonic acid and/or dimethylarsinic acid), and oHg (blood methyl-mercury and/or ethyl-mercury). For combinations of As and Hg species, age- and gender-specific prevalence was determined among NHANES 2011-2012 participants (n = 2342). Data showed that approximately 49.3% of the population contained a combination of three or more metals. The most prevalent unique specific combinations were Pb/Cd/Hg/As, Pb/Cd/Hg, and Pb/Cd. Age was consistently associated with these combinations: adj-ORs ranged from 10.9 (Pb/Cd) to 11.2 (Pb/Cd/Hg/As). Race/ethnicity was significant for Pb/Cd/Hg/As. Among women of reproductive age, frequency of oHg/iAs/met-iAS and oHg/met-iAs was 22.9 and 40.3%, respectively. These findings may help prioritize efforts to assess joint toxicities and their impact on public health.

Heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in seven fish species in relation to fish size and location along the Yangtze River.

PubMed

Yi, Yu-Jun; Zhang, Shang-Hong

2012-11-01

The objective of this paper is to assess the regulation of the accumulation of heavy metals in the aquatic environment and different fish species. Water and fish samples were collected from upper to lower reaches of the Yangtze River. The heavy metal (Cd, Cr, Cu, Hg, Pb, Zn) concentrations in the muscle tissue of seven fishes were measured. Additionally, the relationships between heavy metal concentrations in fish tissue and fish size (length and weight), condition factor, water layer distribution, and trophic level were investigated. Metal concentrations (milligrams per kilogram wet weight) were found to be distributed differently among different fish species. The highest concentrations of Cu (1.22 mg/kg) and Zn (7.55 mg/kg) were measured in Pelteobagrus fulvidraco, the highest concentrations of Cd (0.115 mg/kg) and Hg (0.0304 mg/kg) were measured in Silurus asotus, and the highest concentrations of Pb (0.811 mg/kg) and Cr (0.239 mg/kg) were measured in Carassius auratus and Cyprinus carpio. A positive relationship was found between fish size and metal level in most cases. The variance of the relationships may be the result of differences in habitat, swimming behavior, and metabolic activity. In this study, fishes living in the lower water layer and river bottom had higher metals concentrations than in upper and middle layers. Benthic carnivorous and euryphagous fish had higher metals concentrations than phytoplankton and herbivorous fish. Generally, fish caught from the lower reach had higher metals concentrations than those from the upper reach. Cadmium and lead concentrations in several fishes exceeded the permissible food consumption limits, this should be considered to be an important warning signal.

Impact of electrostatics on the chemodynamics of highly charged metal-polymer nanoparticle complexes.

PubMed

Duval, Jérôme F L; Farinha, José Paulo S; Pinheiro, José P

2013-11-12

In this work, the impact of electrostatics on the stability constant, the rate of association/dissociation, and the lability of complexes formed between Cd(II), Pb(II), and carboxyl-modified polymer nanoparticles (also known as latex particles) of radius ∼ 50 nm is systematically investigated via electroanalytical measurements over a wide range of pHs and NaNO3 electrolyte concentrations. The corresponding interfacial structure and key electrostatic properties of the particles are independently derived from their electrokinetic response, successfully interpreted using soft particle electrohydrodynamic formalism, and complemented by Förster resonance energy transfer (FRET) analysis. The results underpin the presence of an ∼0.7-1 nm thick permeable and highly charged shell layer at the surface of the polymer nanoparticles. Their electrophoretic mobility further exhibits a minimum versus NaNO3 concentration due to strong polarization of the electric double layer. Integrating these structural and electrostatic particle features with recent theory on chemodynamics of particulate metal complexes yields a remarkable recovery of the measured increase in complex stability with increasing pH and/or decreasing solution salinity. In the case of the strongly binding Pb(II), the discrepancy at pH > 5.5 is unambiguously assigned to the formation of multidendate complexes with carboxylate groups located in the particle shell. With increasing pH and/or decreasing electrolyte concentration, the theory further predicts a kinetically controlled formation of metal complexes and a dramatic loss of their lability (especially for lead) on the time-scale of diffusion toward a macroscopic reactive electrode surface. These theoretical findings are again shown to be in agreement with experimental evidence.

Effects of composition of labile organic matter on biogenic production of methane in the coastal sediments of the Arabian Sea.

PubMed

Gonsalves, Maria-Judith; Fernandes, Christabelle E G; Fernandes, Sheryl Oliveira; Kirchman, David L; Bharathi, P A Loka

2011-11-01

Coastal regions are potential zones for production of methane which could be governed by ecological/environmental differences or even sediment properties of a niche. In order to test the hypothesis that methanogenesis in most marine sediments could be driven more by proteins than by carbohydrates and lipid content of labile organic matter (LOM), incubation experiments were carried out with sediments from different environmental niches to measure methane production. The methane production rates were examined in relationship to the sediment biochemistry, i.e., carbohydrates, proteins, and lipids. The gas production measured by head space method ranged from 216 ng g( -1) day( -1) in the mangrove sediments to 3.1 μg g( -1) day( -1) in the shallow Arabian Sea. LOM ranged from 1.56 to 2.85 mg g( -1) in the shallow Arabian Sea, from 3.35 to 5.43 mg g( -1) in the mangrove estuary, and from 0.66 to 0.70 mg g( -1) in the sandy sediments with proteins contributing maximum to the LOM pool. Proteins influenced methane production in the clayey sediments of shallow depths of the Arabian Sea (r = 0.933, p < 0.001) and mangrove estuary (r = 0.981, p < 0.001) but in the sandy beach sediments, carbohydrates (r = 0.924, p < 0.001) governed the net methane production. The gas production was more pronounced in shallow and surface sediments and it decreased with depth apparently governed by the decrease in lability index. Thus, the lability index and protein content are important factors that determine methane production rates in these coastal ecosystems.

Large-area experiment on uptake of metals by twelve plants growing in soils contaminated with multiple metals.

PubMed

Lai, Hung-Yu; Juang, Kai-Wei; Chen, Zueng-Sang

2010-01-01

A site in central Taiwan with an area of 1.3 ha and contaminated with Cr, Cu, Ni, and Zn was selected to examine the feasibility of phytoextraction. Based on the results of a preexperiment at this site, a total of approximately 20,000 plants of 12 species were selected from plants of 33 tested species to be used in a large-area phytoextraction experiment at this site. A comparison with the initial metal concentration of 12 plant species before planting demonstrated that most species accumulated significant amounts of Cr, Cu, Ni, and Zn in their shoots after growing in this contaminated site for 31 d. Among the 12 plant species, the following accumulated higher concentrations of metals in their shoots; Garden canna and Garden verbena (45-60 mg Cr kg(-1)), Chinese ixora and Kalanchoe (30 mg Cu kg(-1)), Rainbow pink and Sunflower (30 mg Ni kg(-1)), French marigold and Sunflower (300-470 mg Zn kg(-1)). The roots of the plants of most of the 12 plant species can accumulate higher concentrations of metals than the shoots and extending the growth period promotes accumulation in the shoots. Large-area experiments demonstrated that phytoextraction is a feasible method to enable metal-contaminated soil in central Taiwan to be reused.

An electromyographic analysis of shoulder muscle activation during push-up variations on stable and labile surfaces.

PubMed

Sandhu, Jaspal S; Mahajan, Shruti; Shenoy, Shweta

2008-04-01

Numerous exercises are used to strengthen muscles around the shoulder joint including the push-up and the push-up plus. An important consideration is the addition of surface instability in the form of swiss ball for rehabilitation and strength. The justification for the use of the swiss ball is based on its potential for increasing muscular demand required to maintain postural stability and for improving joint proprioception. Evidence for this is lacking in literature. To compare the myoelectric amplitude of shoulder muscles during push-ups on labile and stable surface. Same subject experimental study. Thirty healthy male subjects in the age group 20-30 years with a mean height of 173.65 cm (+/- SD 2.56) and a mean weight of 69.9 kg (+/-SD 0.2) were taken. Surface electromyogram was recorded from triceps, pectoralis major, serratus anterior and upper trapezius while performing push-up and push-up plus exercises, both on labile and stable surface. Significant increase in muscle activity was observed in pectoralis major and triceps muscle (only during eccentric phase of elbow pushups), while serratus anterior and upper trapezius showed no change in activation level on swiss ball. The addition of a swiss ball is capable of influencing shoulder muscle activity during push-up variations, although the effect is task and muscle dependent.

Micellar electrokinetic chromatography with acid labile surfactant.

PubMed

Stanley, Bob; Lucy, Charles A

2012-02-24

We present a study of a degradable surfactant, sodium 4-[(2-methyl-2-undecyl-1,3-dioxolan-4-yl)methoxy]-1-propane sulfonate that is also known as an acid-labile surfactant (ALS). The performance of ALS as a pseudostationary phase is assessed and compared with established pseudostationary phases such as sodium dodecyl sulphate (SDS), volatile surfactants and polymeric micelles. ALS achieves separation efficiency of 100,000-145,000 theoretical plates and relative standard deviation (RSD) of electrophoretic mobility (n=5) of less than 3%. Retention factors with ALS are strongly correlated with those with SDS. This is shown by the R2=0.79 for all eleven analytes and an R2=0.992 for specifically the non-hydrogen bonding (NHB) analytes. However, ALS displays different selectivity than SDS for hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) solutes (R2 of 0.74 and 0.88, respectively). ALS is degraded to less surface active compounds in acidic solution. These less surface-active compounds are more compatible with the electrospray ionization mass spectrometry (ESI-MS). ALS has a half-life of 48 min at pH 4. ALS has the potential to couple micellar electrokinetic chromatography (MEKC) with the ESI-MS. ALS can be used as a pseudostationary phase for a high efficiency separation and later acid hydrolyzed to enable an ESI-MS analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

General aspects of metal toxicity.

PubMed

Kozlowski, H; Kolkowska, P; Watly, J; Krzywoszynska, K; Potocki, S

2014-01-01

This review is focused on the general mechanisms of metal toxicity in humans. The possible and mainly confirmed mechanisms of their action are discussed. The metals are divided into four groups due to their toxic effects. First group comprises of metal ions acting as Fenton reaction catalyst mainly iron and copper. These types of metal ions participate in generation of the reactive oxygen species. Metals such as nickel, cadmium and chromium are considered as carcinogenic agents. Aluminum, lead and tin are involved in neurotoxicity. The representative of the last group is mercury, which may be considered as a generally toxic metal. Fenton reaction is a naturally occurring process producing most active oxygen species, hydroxyl radical: Fe(2+) + He2O2 ↔ Fe(3+) + OH(-) + OH(•) It is able to oxidize most of the biomolecules including DNA, proteins, lipids etc. The effect of toxicity depends on the damage of molecules i.e. production site of the hydroxyl radical. Chromium toxicity depends critically on its oxidation state. The most hazardous seems to be Cr(6+) (chromates) which are one of the strongest inorganic carcinogenic agents. Cr(6+) species act also as oxidative agents damaging among other nucleic acids. Redox inactive Al(3+), Cd(2+) or Hg(2+) may interfere with biology of other metal ions e.g. by occupying metal binding sites in biomolecules. All these aspects will be discussed in the review.

Welding fumes from stainless steel gas metal arc processes contain multiple manganese chemical species.

PubMed

Keane, Michael; Stone, Samuel; Chen, Bean

2010-05-01

Fumes from a group of gas metal arc welding (GMAW) processes used on stainless steel were generated using three different metal transfer modes and four different shield gases. The objective was to identify and measure manganese (Mn) species in the fumes, and identify processes that are minimal generators of Mn species. The robotic welding system was operated in short-circuit (SC) mode (Ar/CO2 and He/Ar), axial spray (AXS) mode (Ar/O2 and Ar/CO2), and pulsed axial-spray (PAXS) mode (Ar/O2). The fumes were analyzed for Mn by a sequential extraction process followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis, and by X-ray diffraction (XRD). Total elemental Mn, iron (Fe), chromium (Cr) and nickel (Ni) were separately measured after aqua regia digestion and ICP-AES analysis. Soluble Mn2+, Fe2+, Fe3+, and Ni2+ in a simple biological buffer (phosphate-buffered saline) were determined at pH 7.2 and 5.0 after 2 h incubation at 37 C by ion chromatography. Results indicate that Mn was present in soluble form, acid-soluble form, and acid-soluble form after reduction by hydroxylamine, which represents soluble Mn0 and Mn2+ compounds, other Mn2+ compounds, and (Mn3+ and Mn4+) compounds, respectively. The dominant fraction was the acid-soluble Mn2+ fraction, but results varied with the process and shield gas. Soluble Mn mass percent in the fume ranged from 0.2 to 0.9%, acid-soluble Mn2+ compounds ranged from 2.6 to 9.3%, and acid plus reducing agent-soluble (Mn3+ and Mn4+) compounds ranged from 0.6 to 5.1%. Total Mn composition ranged from 7 to 15%. XRD results showed fumes had a crystalline content of 90-99% Fe3O4, and showed evidence of multiple Mn oxides, but overlaps and weak signals limited identification. Small amounts of the Mn2+ in the fume (<0.01 to ≈ 1% or <0.1 to ≈ 10 microg ml(-1)) and Ni2+ (<0.01 to ≈ 0.2% or <0.1 to ≈ 2 mg ml(-1)) ions were found in biological buffer media, but amounts were highly dependent on pH and the

Supercritical Fluid Extraction of Metal Chelate: A Review.

PubMed

Ding, Xin; Liu, Qinli; Hou, Xiongpo; Fang, Tao

2017-03-04

Supercritical fluid extraction (SFE), as a new green extraction technology, has been used in extracting various metal species. The solubilities of chelating agents and corresponding metal chelates are the key factors which influence the efficiency of SFE. Other main properties of them such as stability and selectivity are also reviewed. The extraction mechanisms of mainly used chelating agents are explained by typical examples in this paper. This is the important aspect of SFE of metal ions. Moreover, the extraction efficiencies of metal species also depend on other factors such as temperature, pressure, extraction time and matrix effect. The two main complexation methods namely in-situ and on-line chelating SFE are described in detail. As an efficient chelating agent, tributyl phosphate-nitric acid (TBP-HNO 3 ) complex attracts much attention. The SFE of metal ions, lanthanides and actinides as well as organometallic compounds are also summarized. With the proper selection of ligands, high efficient extraction of metal species can be obtained. As an efficient sample analysis method, supercritical fluid chromatography (SFC) is introduced in this paper. Recently, the extraction method combining ionic liquids (ILs) with supercritical fluid has been becoming a novel technology for treating metal ions. The kinetics related to SFE of metal species is discussed with some specific examples.

Metals in the Scheldt estuary: From environmental concentrations to bioaccumulation.

PubMed

Van Ael, Evy; Blust, Ronny; Bervoets, Lieven

2017-09-01

To investigate the relationship between metal concentrations in abiotic compartments and in aquatic species, sediment, suspended matter and several aquatic species (Polychaeta, Oligochaeta, four crustacean species, three mollusc species and eight fish species) were collected during three seasons at six locations along the Scheldt estuary (the Netherlands-Belgium) and analysed on their metal content (Ag, Cd, Co, Cr, Cu, Ni, Pb, Zn and the metalloid As). Sediment and biota tissue concentrations were significantly influenced by sampling location, but not by season. Measurements of Acid Volatile Sulphides (AVS) concentrations in relation to Simultaneously Extracted Metals (SEM) in the sediment suggested that not all metals in the sediment will be bound to sulphides and some metals might be bioavailable. For all metals but zinc, highest concentrations were measured in invertebrate species; Ag and Ni in periwinkle, Cr, Co and Pb in Oligochaete worms and As, Cd and Cu in crabs and shrimp. Highest concentrations of Zn were measured in the kidney of European smelt. In fish, for most of the metals, the concentrations were highest in liver or kidney and lowest in muscle. For Zn however, highest concentrations were measured in the kidney of European smelt. For less than half of the metals significant correlations between sediment metal concentrations and bioaccumulated concentrations were found (liver/hepatopancreas or whole organism). To calculate the possible human health risk by consumption, average and maximum metal concentrations in the muscle tissues were compared to the minimum risk levels (MRLs). Concentrations of As led to the highest risk potential for all consumable species. Cadmium and Cu posed only a risk when consuming the highest contaminated shrimp and shore crabs. Consuming blue mussel could result in a risk for the metals As, Cd and Cr. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

NASA Astrophysics Data System (ADS)

Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David

2014-03-01

true partition coefficient (Kd actual) is significantly higher. Importantly, the Kd of NOM-metal complexes [organic carbon-metal ratio) approaches 1 for the most stable aqueous complexes, as is shown here for Co, but has values of 24-150 for V, Ni and Cu. This implies that ternary surface complexation (metal-ligand co-adsorption) can occur (as for NOM-Co), but is the exception rather than the rule. We also demonstrate the potential for trace metals to record information on NOM composition as expressed through changing NOM-metal complexation patterns in dripwaters. Therefore, a suite of trace metals in stalagmites show variations clearly attributable to changes in organic ligand concentration and composition, and which potentially reflect the state of overlying surface ecosystems. The heterogeneous speciation and size distribution of aqueous NOM and metals (Lead and Wilkinson, 2006; Aiken et al., 2011). The variability in NOM-metal transport in caves that arises from the interaction between infiltration, flow routing, and the hydrodynamic properties of the fine colloids and particulates (Hartland et al., 2012). Variable dissociation kinetics through time as a function of (a) (Hartland et al., 2011). The surface charge of calcite and the availability of CaCO3 lattice sites as well as increased incidence of crystallographic defects with implications for incorporation of a range of trace species (Fairchild and Treble, 2009; Fairchild and Hartland, 2010). Thus, incorporation in speleothem calcite with consistent surface site properties will be determined by: The size and composition (i.e. hydrophilicity/hydrophobicity) of the NOM ligand, affecting adsorption and stability at the calcite surface. The lability (i.e. exchangeability) of the complexed metal and its binding affinity for the calcite surface. The concentration of aqueous complexes. Given the complexities, a partitioning approach to the problem is appropriate as a first approximation rather than a precise

A Double Blind Trial of Divalproex Sodium for Affective Lability and Alcohol Use Following Traumatic Brain Injury

DTIC Science & Technology

2013-10-01

acutely manic bipolar patients, and the FDA approved it in 1995 for this indication. Also, it is used in conjunction with lithium or carbamazepine to...0652 TITLE: A Double Blind Trial of Divalproex Sodium for Affective Lability and Alcohol Use Following Traumatic Brain Injury...and Alcohol Use Following Traumatic Brain Injury 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-08-2-0652 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR

Implications of metal accumulation mechanisms to phytoremediation.

PubMed

Memon, Abdul R; Schröder, Peter

2009-03-01

Trace elements (heavy metals and metalloids) are important environmental pollutants, and many of them are toxic even at very low concentrations. Pollution of the biosphere with trace elements has accelerated dramatically since the Industrial Revolution. Primary sources are the burning of fossil fuels, mining and smelting of metalliferous ores, municipal wastes, agrochemicals, and sewage. In addition, natural mineral deposits containing particularly large quantities of heavy metals are found in many regions. These areas often support characteristic plant species thriving in metal-enriched environments. Whereas many species avoid the uptake of heavy metals from these soils, some of them can accumulate significantly high concentrations of toxic metals, to levels which by far exceed the soil levels. The natural phenomenon of heavy metal tolerance has enhanced the interest of plant ecologists, plant physiologists, and plant biologists to investigate the physiology and genetics of metal tolerance in specialized hyperaccumulator plants such as Arabidopsis halleri and Thlaspi caerulescens. In this review, we describe recent advances in understanding the genetic and molecular basis of metal tolerance in plants with special reference to transcriptomics of heavy metal accumulator plants and the identification of functional genes implied in tolerance and detoxification. Plants are susceptible to heavy metal toxicity and respond to avoid detrimental effects in a variety of different ways. The toxic dose depends on the type of ion, ion concentration, plant species, and stage of plant growth. Tolerance to metals is based on multiple mechanisms such as cell wall binding, active transport of ions into the vacuole, and formation of complexes with organic acids or peptides. One of the most important mechanisms for metal detoxification in plants appears to be chelation of metals by low-molecular-weight proteins such as metallothioneins and peptide ligands, the phytochelatins. For

The effect of flood events on the partitioning of labile and refractory carbon in the Missouri-Mississippi River system

NASA Astrophysics Data System (ADS)

Roe, K. M.; Rosenheim, B. E.; Kolker, A.; Allison, M. A.; Nittrouer, J. A.; Duncan, D. D.; Nyman, J. A.; Butcher, K. A.; Adamic, J. F.

2009-12-01

The Missouri-Mississippi River system (MMRS) transports over 40% (4.0 x 109 kg) of the United States's annual input of total organic carbon (OC) from land to the marine environment, yet it is challenging to assess the MMRS’s exact role in the global carbon cycle because of the system’s complexity and temporal variability (i.e. high discharge events and low flow regimes). Determining the relative proportion of labile OC to refractory OC entrained in the MMRS during high and mean flow conditions would lend to the understanding of the MMRS’s role in the flux of carbon between the biospheric and atmospheric reservoirs, which is central to determining the role of anthropogenic CO2 in the global carbon cycle and in climate change. In this study, we investigate the relative proportion of labile OC to refractory OC in the lower MMRS during high and near-mean flow conditions in the springs of 2008 and 2009, respectively. The 2008 spring flood discharged 105 km3 of water, the maximum amount of water ever allowed out of the main channel, at a maximum rate of 4.3 x 104 m3s-1. Events of this scale have occurred only nine times in the past 80 years. Additionally, during the spring 2008 flood, bedload sand and large particulate OC transport rates were observed to increase exponentially. The following spring, high discharge rates returned to near-mean values with a peak discharge of 3.6 x 103 m3s-1. Using radiocarbon age and the thermal stability of organic matter (OM) as a proxy for lability, we evaluate the spectra of ages of particulate OM transported in the lower MMRS during these two flow regimes using a programmed-temperature pyrolysis/combustion system (PTP/CS) coupled with 14C determination. The PTP/CS utilizes the differences in thermal stability of acid insoluble particulate organic matter (AIPOM) to separate different components from the bulk. Employing PTP/CS on bulk AIPOM can complement experiments measuring small proportions of total OM such as compound

Incorporation of noble metals into aerogels

DOEpatents

Hair, Lucy M.; Sanner, Robert D.; Coronado, Paul R.

1998-01-01

Aerogels or xerogels containing atomically dispersed noble metals for applications such environmental remediation. New noble metal precursors, such as Pt--Si or Pd(Si--P).sub.2, have been created to bridge the incompatibility between noble metals and oxygen, followed by their incorporation into the aerogel or xerogel through sol-gel chemistry and processing. Applications include oxidation of hydrocarbons and reduction of nitrogen oxide species, complete oxidation of volatile organic carbon species, oxidative membranes for photocatalysis and partial oxidation for synthetic applications.

Speciation studies of nickel and chromium in wastewater from an electroplating plant.

PubMed

Kiptoo, Jackson K; Ngila, J Catherine; Sawula, Gerald M

2004-09-08

A speciation scheme involving the use of flame atomic absorption spectrometry (FAAS) and differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV) techniques was applied to studies of nickel and chromium in wastewater from a nickel-chrome electroplating plant. Dimethylglyoxime (DMG) and diethylenetriaminepentaacetic acid (DTPA) were employed as complexing agents for adsorptive voltammetric determination of Ni and Cr, respectively. Cr(III) and Cr(VI) were determined by exploiting differences in their reactivity towards DTPA at HMDE. Total dissolved metal content was in the range 2906-3141 and 30.7-31.2mgl(-1) for Ni and Cr, respectively. A higher percentage of the metal was present as labile species (mean value of 67.9% for Ni and 79.8% for Cr) suggesting that strongly binding ligands are not ubiquitous in the sample. About 77.8% of Cr was found to exist in the higher oxidization state, Cr(IV). Results on effect of dilution on lability of the metal forms in the sample using DPAdCSV showed slight peak shifts to a more negative (cathodic) value by -0.036V for Ni and -0.180V for Cr with a dilution factor of 100, while peak intensity (cathodic current) remained fairly constant.

Risk assessment and toxic effects of metal pollution in two cultured and wild fish species from highly degraded aquatic habitats.

PubMed

Omar, Wael A; Zaghloul, Khalid H; Abdel-Khalek, Amr A; Abo-Hegab, S

2013-11-01

Lake Qaroun is an inland lake at the lowest part of El-Fayoum depression, Egypt. It receives agricultural and domestic non-treated drainage waters, which are also used for aquaculture in Qaroun area. The results of the present study aimed to provide comparable data between wild (collected from Lake Qaroun) and cultured (collected from Qaroun fish farms and the reference site) Nile tilapia Oreochromis niloticus and mullet Mugil cephalus, as indicators of natural and anthropogenic impacts on aquatic ecosystem as well as to evaluate the human hazard index associated with fish consumption. Metal concentrations in fish tissues showed a species-specific bioaccumulation pattern. Statistically significant differences were observed in the mean metal concentrations with lower bioavailability in M. cephalus compared with O. niloticus in internal vital organs (liver, kidney, and muscle) but much higher in external organs (gill and skin). Histopathological alterations and evident damages were observed in gill, liver, and kidney of both species collected from Lake Qaroun and Qaroun fish farms compared with those from the reference site. The results showed significant increase of plasma aspartate aminotransferase and alanine aminotransferase activity as well as creatinine and uric acid concentration in both fish species from polluted locations. The human health hazard index showed that the cumulative risk greatly increases with increasing fish consumption rate, thus yielding an alarming concern for consumer health.

FTIR-PAS: a powerful tool for characterising the chemical composition and predicting the labile C fraction of various organic waste products.

PubMed

Bekiaris, Georgios; Bruun, Sander; Peltre, Clément; Houot, Sabine; Jensen, Lars S

2015-05-01

Fourier transform infrared (FT-IR) spectroscopy has been used for several years as a fast, low-cost, reliable technique for characterising a large variety of materials. However, the strong influence of sample particle size and the inability to measure the absorption of very dark and opaque samples have made FTIR unsuitable for many waste materials. FTIR-photoacoustic spectroscopy (FTIR-PAS) can eliminate some of the shortcomings of traditional FTIR caused by scattering effects and reflection issues, and recent advances in PAS technology have made commercial instruments available. In this study, FTIR-PAS was used to characterise a wide range of organic waste products and predict their labile carbon fraction, which is normally determined from time-consuming assays. FTIR-PAS was found to be capable of predicting the labile fraction of carbon as efficiently as near infrared spectroscopy (NIR) and furthermore of identifying the compounds that are correlated with the predicted parameter, thus facilitating a more mechanistic interpretation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Metallic Species, Oxygen and Silicon in the Lunar Exosphere: Upper Limits and Prospects for LADEE Measurements

NASA Technical Reports Server (NTRS)

Sarantos, Menelaos; Killen, Rosemary M.; Glenar, David A.; Benna, Mehdi; Stubbs, Timothy J.

2011-01-01

The only species that have been continued in the lunar exosphere are Na, K, Ar, and He. Models for the production and loss of lunar regolith-derived exospheric species from source processes including micrometeoroid impact vaporization, sputtering. and, for Na and K, photon-stimulated desorption, predict a host of other species should exist in the lunar exosphere. Assuming that loss processes are limited to ballistic escape and recycling to the surface, we have computed column abundances and compared them to published upper limits from the Moon and to detected abundances from Mercury. Only for Ca do the available measurements show a clear deficiency compared to the model estimates. This result suggests the importance of loss processes not included in the model, such as the possibility of gas-to-solid phase condensation during micrometeoroid impacts or the formation of stable metallic oxides, and underlines the need for improved spectroscopic measurements of the lunar exosphere. Simulations of the neutral mass (NMS) and visible/ultraviolet spectrometry (UVS) investigations planned by the Lunar Atmosphere and Dust Environment Explorer (LADEE) spacecraft are presented. Our calculations indicate that LADEE measurements promise to make definitive observations or set stringent upper limits for all regolith-driven exospheric species. Our models, along with LADEE observations, will constrain assumed model parameters for the Moon, such as sticking coefficients, source processes. and velocity distributions.

Anaerobic microbial remobilization of coprecipitated metals

DOEpatents

Francis, Arokiasamy J.; Dodge, Cleveland J.

1994-10-11

A process is provided for solubilizing coprecipitated metals. Metals in wastestreams are concentrated by treatment with an iron oxide coprecipitating agent. The coprecipitated metals are solubilized by contacting the coprecipitate with a bacterial culture of a Clostridium species ATCC 53464. The remobilized metals can then be recovered and recycled.

Incorporation of noble metals into aerogels

DOEpatents