Molybdenum drawdown during Cretaceous Oceanic Anoxic Event 2

NASA Astrophysics Data System (ADS)

Goldberg, Tatiana; Poulton, Simon W.; Wagner, Thomas; Kolonic, Sadat F.; Rehkämper, Mark

2016-04-01

During the Cretaceous greenhouse, episodes of widespread ocean deoxygenation were associated with globally occurring events of black shale deposition. Possibly the most pronounced of these oceanic anoxic events (OAE's) was the Cenomanian-Turonian OAE2 (∼94 Ma). However, although certain redox sensitive trace metals tend to be preferentially sequestered in sediments deposited under anoxic conditions, with Mo drawdown being specifically prone to euxinic settings, these elements are generally somewhat depleted in sediments deposited during OAE2. To understand the driving factors responsible for this depleted trace metal drawdown, we have studied a low latitude section from the proto-North Atlantic Ocean (Tarfaya S57), where existing biomarker and iron-sulphur data point to a dominantly euxinic water column, with periodic transitions to ferruginous (Fe-rich) water column conditions. We utilise a variety of redox proxies (Fe-speciation, redox sensitive trace metals and Mo isotopes), which, in combination, allows us to evaluate the detailed nature of ocean redox conditions and hence controls on trace metal drawdown. The results suggest that seawater δ98Mo values may have ranged between ∼0.6 and 1.1‰ during OAE2, likely connected to changes in the local Mo reservoir as a consequence of low and probably heterogeneous concentrations of Mo in the ocean. The very low Mo/TOC ratios at Tarfaya and elsewhere in the proto-North Atlantic may support a model in which deep-water circulation was partially restricted within and between the North Atlantic and other ocean basins. We propose that the combination of a low and possibly heterogeneous δ98Mo of seawater Mo, together with low Mo/TOC ratios, points to a large decrease in the global oceanic Mo reservoir during OAE2, reflecting a major global scale increase in Mo drawdown under persistent euxinic conditions.

Cycling of Redox-Sensitive Trace Elements in the Lower Mississippi River Delta as a Function of River Stage and Sediment Heterogeneity

NASA Astrophysics Data System (ADS)

Telfeyan, K.; Breaux, A.; Kim, J.; Johannesson, K. H.; Kolker, A.; Cable, J. E.

2015-12-01

Telfeyan, K.1, Johannesson, K.H.1, Breaux, A.M.2,1, Kim, J.3, Kolker, A.S.2,1, Cable, J.E.31 Department of Earth and Environmental Sciences, Tulane University, New Orleans, LA, USA 2 Louisiana Universities Marine Consortium, Cocoderie, LA, USA 3 Department of Marine Sciences, University of North Carolina, Chapel Hill, NC, USA The Mississippi River drains 40% of the continental United States and discharges 0.1 Pg sediment and an average of 18,400 m3 s-1 water annually to the Gulf of Mexico1. The flow of groundwater through the Mississippi River Delta (MRD) to the Gulf, however, has been largely understudied and is typically overlooked in MRD biogeochemical studies. Previous work demonstrated that sand-rich paleochannels that maintain a hydrologic connection to the Mississippi River could transport riverine water to the MRD2. We present data from biogeochemical surveys at 2 sites in the lower MRD to explore the effects of river-derived submarine groundwater discharge on the biogeochemistry of MRD wetlands. Lac des Allemands is a fresh water lake and Myrtle Grove is a brackish canal with variable salinities. Both are surrounded by extensive wetlands. Over the course of a year, surface water, shallow pore water, and deeper groundwaters were sampled to understand the cycling of redox-sensitive trace elements (Fe, Mn, V, As) and the potential supply from groundwater to surface water bodies. Major ion chemistry suggests that both Lac des Allemands and Myrtle Grove Canal receive river-derived terrestrial water at their heads, the flux of which varies as a function of river stage. However, the lateral flow through adjacent wetlands is altered as a function of sediment heterogeneity. Evidence for sulfate reduction exists in the near-surface sediment and at depth where a continuous vertical organic matter layer exists. In sand-rich layers, iron reduction buffers redox conditions, and V varies inversely with dissolved Fe. Concentrations of V and As are much greater in near-surface pore waters than in deeper groundwaters and in surface waters, suggesting that the subterranean estuary serves as a sink of these redox-sensitive trace elements. [1] Bianchi and Allison (2009) PNAS 1068085-8092. [2] Kolker et al. (2013) Journal of Hydrology 498 319-334.

Biogeochemical redox processes and their impact on contaminant dynamics

USGS Publications Warehouse

Borch, Thomas; Kretzschmar, Ruben; Kappler, Andreas; Van Cappellen, Philippe; Ginder-Vogel, Matthew; Campbell, Kate M.

2010-01-01

Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

Simulated Patterns of Unforced Centennial-Scale Climate Variability in the Tropical Pacific

NASA Astrophysics Data System (ADS)

Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

2011-12-01

Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

NASA Astrophysics Data System (ADS)

Huck, Claire E.; van de Flierdt, Tina; Jiménez-Espejo, Francisco J.; Bohaty, Steven M.; Röhl, Ursula; Hammond, Samantha J.

2016-03-01

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources.

Trace Element Geochemistry as a Tool for the Reconstruction of Upwelling Patterns at 12oS off Peru since the Last Glacial Maximum (LGM)

NASA Astrophysics Data System (ADS)

Boening, P.; Brumsack, H.; Wolf, A.

2002-05-01

Laminated sediments (core 106KL), recovered during R/V Sonne cruise 147 from the Peruvian upper slope mud lens at 12oS, were analyzed for bulk parameters (TOC, TIC, TS) and opal as well as major and trace element composition by XRF and ICP-MS in 5 cm intervals. The composition of the terrigenous-detrital sediment fraction is comparable to average shale. The sediments exhibit slight increases in biogenic silica (diatoms) and carbonate contents (foraminifera) in varying layers. The experimentally determined opal contents correlate well with Si/Al ratios. High TOC and P contents are due to enhanced primary productivity, high sedimentation rates and corresponding organic matter preservation under a strong OMZ. We distinguish between three different groups of elements: 1.) trace elements involved in bio-cycling (e.g. Cd, Ag, Ni, Cu) are highly enriched in the sediments due to their association with plankton, high sedimentation rates (preventing remobilization from the sediments) and fixation as sulfides. 2.) redox-sensitive elements (e.g. Re, Mo) are significantly enriched probably due to reduction and precipitation under suboxic/anoxic conditions. Diffusion of these elements from the water column into sub/anoxic sediments seems to be the controlling factor, besides sulfide precipitation. An average Re/Mo ratio of 1.3 indicates anoxic sedimentary conditions. Most trace elements correlate well with the TOC content presumably documenting productivity events. 3.) Al, Zr and Y are well correlated, presumably representing sporadic high-energy fluvial input from the continent or enhanced current velocities. The three element groups were used to reconstruct the upwelling patterns off Lima since the LGM: TOC content and Al-normalized trace element patterns from the bio/redox-sensitive fractions represent the signal from the water column, whereas Al, Y and Zr reflect the terrigenous input. During the LGM (about 17 ky BP) the site was hardly affected by upwelling as the upwelling cell was located more basinward. As the sea level rose during the Late Glacial (17-10 ky BP) the upwelling cell shifted towards the coast. The Early Holocene (10-5 ky BP) is not documented likely because strong currents (presumably the Peru counter current) eroded the slope. In the Late Holocene the upwelling cell was established at the site. However, a higher terrrigenous proportion and lower input from the water column suggest a basinward shifting of the upwelling cell during the Second Neoglacial (2000-2700 BP). Stronger Element/Al and TOC variabilities indicate the influence of El Nino during the Late Holocene.

Trace elements in coal ash

USGS Publications Warehouse

Deonarine, Amrika; Kolker, Allan; Doughten, Michael W.

2015-01-01

In this fact sheet, the form, distribution, and behavior of trace elements of environmental interest in samples of coal fly ash were investigated in response to concerns about element mobility in the event of an ash spill. The study includes laboratory-based leaching experiments to examine the behavior of trace elements, such as arsenic (As) and chromium (Cr), in response to key environmental factors including redox conditions (degree of oxygenation), which are known to vary with depth within coal ash impoundments and in natural ecosystems. The experiments show that As dissolves from samples of coal fly ash into simulated freshwater under both oxic (highly oxygenated) and anoxic (poorly oxygenated) conditions, whereas dissolved Cr concentrations are very redox dependent. This U.S. Geological Survey research helps define the distribution of elements such as As in coal ash and shows that element mobility can vary considerably under different conditions expected in the environment.

How Reducing was the Late Devonian Ocean? The Role of Extensive Expansion of Anoxia in Marine Biogeochemical Cycles of Redox Sensitive Metals.

NASA Astrophysics Data System (ADS)

Sahoo, S. K.; Jin, H.

2017-12-01

The evolution of Earth's biogeochemical cycles is intimately linked to the oxygenation of the oceans and atmosphere. The Late Devonian is no exception as its characterized with mass extinction and severe euxinia. Here we use concentrations of Molybdenum (Mo), Vanadium (V), Uranium (U) and Chromium (Cr) in organic rich black shales from the Lower Bakken Formation of the Williston Basin, to explore the relationship between extensive anoxia vs. euxinia and it's relation with massive release of oxygen in the ocean atmosphere system. XRF data from 4 core across the basin shows that modern ocean style Mo, U and Cr enrichments are observed throughout the Lower Bakken Formation, yet V is not enriched until later part of the formation. Given the coupling between redox-sensitive-trace element cycles and ocean redox, various models for Late Devonian ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients. Here, we examine the differing redox behavior of molybdenum and vanadium under an extreme anoxia and relatively low extent of euxinia. The model suggests that Late Devonian was perhaps extensively anoxic- 40-50% compared to modern seafloor area, and a very little euxinia. Mo enrichments extend up to 500 p.p.m. throughout the section, representative of a modern reducing ocean. However, coeval low V enrichments only support towards anoxia, where anoxia is a source of V, and a sink for Mo. Our model suggests that the oceanic V reservoir is extremely sensitive to perturbations in the extent of anoxic condition, particularly during post glacial times.

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

NASA Technical Reports Server (NTRS)

Szumila, Ian; Danielson, Lisa; Trail, Dustin

2017-01-01

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Understanding Biogeochemical Transformations Of Trace Elements In Multi Metal-Rich Geomaterials Under Stimulated Redox Conditions

EPA Science Inventory

Natural and anthropogenic influences on hydrological conditions can induce periodic or long-term reduced conditions in geologic materials. Such conditions can cause significant impacts on biogeochemical processes of trace elements in subsurface or near surface environments. The...

Kinetics of steel slag leaching: Batch tests and modeling

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

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr; Chaurand, Perrine; Rose, Jerome

2011-02-15

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can bemore » used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.« less

Bottom-Water Conditions in a Marine Basin after the Cretaceous–Paleogene Impact Event: Timing the Recovery of Oxygen Levels and Productivity

PubMed Central

Sosa-Montes De Oca, Claudia; Martínez-Ruiz, Francisca; Rodríguez-Tovar, Francisco Javier

2013-01-01

An ultra-high-resolution analysis of major and trace element contents from the Cretaceous–Paleogene boundary interval in the Caravaca section, southeast Spain, reveals a quick recovery of depositional conditions after the impact event. Enrichment/depletion profiles of redox sensitive elements indicate significant geochemical anomalies just within the boundary ejecta layer, supporting an instantaneous recovery –some 102 years– of pre-impact conditions in terms of oxygenation. Geochemical redox proxies point to oxygen levels comparable to those at the end of the Cretaceous shortly after impact, which is further evidenced by the contemporary macrobenthic colonization of opportunistic tracemakers. Recovery of the oxygen conditions was therefore several orders shorter than traditional proposals (104–105 years), suggesting a probable rapid recovery of deep-sea ecosystems at bottom and in intermediate waters. PMID:24349232

Paleo-environmental conditions of the Early Cambrian Niutitang Formation in the Fenggang area, the southwestern margin of the Yangtze Platform, southern China: Evidence from major elements, trace elements and other proxies

NASA Astrophysics Data System (ADS)

Li, Jin; Tang, Shuheng; Zhang, Songhang; Xi, Zhaodong; Yang, Ning; Yang, Guoqiao; Li, Lei; Li, Yanpeng

2018-06-01

The Precambrian/Cambrian transition was a key time in Earth history, especially for marine biological evolution and oceanic chemistry. The redox-stratification with oxic shallow water and anoxic (even euxinic) deeper water in the Early Cambrian Yangtze Sea, which gradually became completely oxygenated, has been suggested as a possible trigger for the "Cambrian explosion" of biological diversity. However, for some areas in northern Guizhou where the exploration and research are lacking, identifying this pattern of redox-stratification by paleo-environmental analysis from borehole data is still in need. Here, we report a remarkable variation range in trace elements (Mo, V, U, Ni, Th, Co, Sc, Zn and Cu), molar Corg:P ratios and pyrite morphology from 27 core samples from one new drill hole (XY1, located in the Fenggang area, northern Guizhou) on the Yangtze Platform, South China. High levels of Ba (from 3242 ppm to 33,800 ppm) and total organic carbon (TOC; from 4% to 9.36%) in 15 core samples in the Lower Member (LM) of the Niutitang Formation indicated elevated primary productivity in the study area. Redox change was recorded based on enrichment factors (EFs) for RSTEs (Mo, U, and V), redox proxies (V/(V + Ni), Ni/Co, V/Sc and Th/U), Corg:P ratios and particle size of framboidal pyrite. These signatures demonstrate that the LM was deposited under anoxic conditions with sulfidic episodes, whereas the Upper Member (UM) of the Niutitang Formation was deposited under suboxic/oxic conditions with intermittently anoxic episodes. Mo/TOC ratios (from 3.72 to 39.86, mean 18.76) suggest weak-moderate water mass restriction. Mo-U covariation patterns (strong but variable enrichment of Mo and U; MoEF ranging from 31.45 to 257.97; UEF ranging from 4.68 to 39.07) in the LM show alternation of particulate shuttling and redox conditions occurred in the Early Cambrian Yangtze Sea, whereas Mo-U covariation patterns (moderate Mo enrichment but depletion or non-enrichment of U; mean MoEF: 7.29; mean UEF: 0.95) in the UM may indicate the combined influence of particulate shuttling and diagenetic diffusion of U via bioactivities, which result in low U values and an anoxic signature from frambiodal pyrite particle size (mean: 4.556 μm; median: 4.41 μm). Additionally, excess Ba (Baxs) concentration (33,800 ppm and 32,500 ppm) and association patterns of trace-metal enrichment in the LM indicate the existence of submarine hydrothermal events. In addition, during deposition of the UM, bioactivities indicated by Mo-U systematics and oxic conditions indicated by redox sensitive trace elements (RSTEs) and multiple-proxies, may be a cause of biological diversification recorded in the Early Cambrian. Finally, data in this record a progressive transition from anoxic bottom waters with euxinic episodes to overwhelming oxic conditions during Early Cambrian.

Biogeochemical Cycling of Fe, S, C, N, and Mo in the 3.2 Ga ocean: Constraints from DXCL-DP Black Shales from Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Naraoka, H.; Ikehara, M.; Ito, T.; Kiyokawa, S.

2014-12-01

Records of geochemical cycling of bio-essential, redox-sensitive elements have keys to decipher mysteries of the co-evolution of Earth and life. To obtain insight into biogeochemical cycling of those elements and early evolution of microbial biosphere from high-quality samples, we drilled through Mesoarchean strata in coastal Pilbara (Dixon Island-Cleaverville Drilling Project, see Yamaguchi et al., 2009; Kiyokawa et al., 2012), and obtained 3.2 Ga old drillcores (CL1, CL2, and DX) of sulfide-rich black shales in the Cleaverville Group, Pilbara Supergroup. We conducted a systematic geochemical study involving sequential extractions of Fe, S, C, and N for phase-dependent contents (e.g., pyrite-Fe, reactive-Fe, highly reactive-Fe, unreactive-Fe, pyrite-S, sulfate-S, organic-S, elemental-S, Corg, Ccarb, Norg, and Nclay) and their stable isotope compositions, micro FT-IR and laser Raman spectroscopy for extracted kerogen, in addition to major and trace (redox-sensitive; e.g., Mo) element analysis, for >100 samples. Here we integrate our recent multidisciplinary investigations into the redox state of ocean and nature of microbial biosphere in the ocean 3.2 Ga ago. All of the obtained data are very difficult to explain only by geochemical processes in strictly anoxic environments, where both atmosphere and oceans were completely anoxic, like an environment before the inferred "Great Oxidation Event" when pO2 was lower than 0.00001 PAL (e.g., Holland, 1994). Our extensive data set consistently suggests that oxygenic photosynthesis, bacterial sulfate reduction, and microbially mediated redox-cycling of nitrogen, possibly involving denitrification and N2-fixation, are very likely to have been operating, and may be used as a strong evidence for at least local and temporal existence of oxidized environment as far back as 3.2 Ga ago. Modern-style biogeochemical cycling of Fe, S, C, N, and Mo has been operating since then. The atmosphere-hydrosphere system 3.2 Ga ago would have been sufficiently oxidized to allow redox-cycling of elements during deposition of the sediments, ~800 Ma earlier than commonly thought. Our suggestions have far-reaching and astrobiological implications for earlier evolution of the surface environment, especially redox state, and marine microbial biosphere.

TRANSPORT AND FATE OF AMMONIUM AND ITS IMPACT ON URANIUM AND OTHER TRACE ELEMENTS AT A FORMER URANIUM MILL TAILING SITE

PubMed Central

Miao, Ziheng; Nihat, Hakan; McMillan, Andrew Lee; Brusseau, Mark L.

2013-01-01

The remediation of ammonium-containing groundwater discharged from uranium mill tailing sites is a difficult problem facing the mining industry. The Monument Valley site is a former uranium mining site in the southwest US with both ammonium and nitrate contamination of groundwater. In this study, samples collected from 14 selected wells were analyzed for major cations and anions, trace elements, and isotopic composition of ammonium and nitrate. In addition, geochemical data from the U.S. Department of Energy (DOE) database were analyzed. Results showing oxic redox conditions and correspondence of isotopic compositions of ammonium and nitrate confirmed the natural attenuation of ammonium via nitrification. Moreover, it was observed that ammonium concentration within the plume area is closely related to concentrations of uranium and a series of other trace elements including chromium, selenium, vanadium, iron, and manganese. It is hypothesized that ammonium-nitrate transformation processes influence the disposition of the trace elements through mediation of redox potential, pH, and possibly aqueous complexation and solid-phase sorption. Despite the generally relatively low concentrations of trace elements present in groundwater, their transport and fate may be influenced by remediation of ammonium or nitrate at the site. PMID:24357895

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Combined organic and inorganic geochemical reconstruction of paleodepositional conditions of a Pliocene sapropel from the eastern Mediterranean Sea

NASA Astrophysics Data System (ADS)

Rinna, J.; Warning, B.; Meyers, P. A.; Brumsack, H.-J.; Rullkötter, J.

2002-06-01

Layers of organic-carbon-rich sapropels in the sediment record of the Mediterranean Sea give evidence of repetitive changes in regional Plio-Pleistocene climate. Results from biomarker molecule and major and trace element analyses of closely spaced samples are used to reconstruct the conditions leading to deposition of a Pliocene sapropel at Ocean Drilling Program (ODP) Site 969 on the Mediterranean Ridge. Organic carbon concentrations increase from 0.2% outside the sapropel and peak to more than 30% within it. Major and trace elemental composition and biomarker-derived parameters indicate elevated productivity, depletion of water-column dissolved-oxygen content, and changes in sediment provenance in response to climatic changes. Budgets of rhenium, thallium, and other trace metals indicate that deep-water exchange between the Mediterranean subbasins and the Atlantic Ocean was not completely interrupted during sapropel formation. Enrichment factors of redox-sensitive and sulfide-forming trace metals as well as the presence of isorenieratene derivatives and high stanol/sterol ratios point to an extended zone of anoxic water masses. Depth profiles of biomarker compositions (sterols, long-chain alkenones, alkandiols and -ketols, fatty acids) indicate great floral diversity during deposition of a single sapropel and highlight the sensitive response of the marine community to variable environmental conditions. Changes in water mass circulation and eolian transport can be reconstructed by use of both lithogenic elements and average chain lengths of n-alkanes (ACL index).

Regulation of trace elements and redox status in striatum of adult rats by long-term aerobic exercise depends on iron uptakes.

PubMed

Wu, Hua-Bo; Xiao, De-Sheng

2017-03-06

We investigated the effects of aerobic exercise (AE) on trace element contents and redox status in the striatum of rats with different diet iron. Weaned female rats were randomly fed with iron-adequate diet (IAD), iron-deficient diet (IDD), and iron-overloaded diet (IOD). After feeding their respective diet for 1 month, the rats fed with same diet were divided into swimming and maintaining sedentary (S) group. After 3 months, the non-heme iron (NHI), Mn, Cu, and Zn in the striatum were measured. Meanwhile, malonaldehyde acid (MDA), total superoxide dismutase activity, hydroxyl radical scavenging activity, and total antioxidant capacity were also analyzed. As compared with respective S rats, Mn, Cu, and Zn contents were significantly decreased in IDDE, but no significantly changes could be seen in IADE or IODE. A negative correlation of NHI with Cu contents in IDDE and positive correlations of NHI with Cu, or Zn contents in IADE, or with Mn or Cu contents in IODE were observed. In addition, striatum MDA was significantly decreased and anti-oxidative variables were increased in IODE compared to IODS. Our results suggest that the modification of trace elements and redox status in the striatum of rats caused by AE depends on dietary iron contents and that AE may also regulate the metabolic relationship of iron storage with other trace elements. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

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

Mobility of radionuclides and trace elements in soil from legacy NORM and undisturbed naturally 232Th-rich sites.

PubMed

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

2014-05-01

Investigation of radionuclides (232Th and 238U) and trace elements (Cr, As and Pb) in soil from two legacy NORM (former mining sites) and one undisturbed naturally 232Th-rich site was conducted as a part of the ongoing environmental impact assessment in the Fen Complex area (Norway). The major objectives were to determine the radionuclide and trace element distribution and mobility in soils as well as to analyze possible differences between legacy NORM and surrounding undisturbed naturally 232Th-rich soils. Inhomogeneous soil distribution of radionuclides and trace elements was observed for each of the investigated sites. The concentration of 232Th was high (up to 1685 mg kg(-1), i.e., ∼7000 Bq kg(-1)) and exceeded the screening value for the radioactive waste material in Norway (1 Bq g(-1)). Based on the sequential extraction results, the majority of 232Th and trace elements were rather inert, irreversibly bound to soil. Uranium was found to be potentially more mobile, as it was associated with pH-sensitive soil phases, redox-sensitive amorphous soil phases and soil organic compounds. Comparison of the sequential extraction datasets from the three investigated sites revealed increased mobility of all analyzed elements at the legacy NORM sites in comparison with the undisturbed 232Th-rich site. Similarly, the distribution coefficients Kd (232Th) and Kd (238U) suggested elevated dissolution, mobility and transportation at the legacy NORM sites, especially at the decommissioned Nb-mining site (346 and 100 L kg(-1) for 232Th and 238U, respectively), while the higher sorption of radionuclides was demonstrated at the undisturbed 232Th-rich site (10,672 and 506 L kg(-1) for 232Th and 238U, respectively). In general, although the concentration ranges of radionuclides and trace elements were similarly wide both at the legacy NORM and at the undisturbed 232Th-rich sites, the results of soil sequential extractions together with Kd values supported the expected differences between sites as the consequences of previous mining operations. Hence, mobility and possible elevated bioavailability at the legacy NORM site could be expected and further risk assessment should take this into account when decisions about the possible intervention measures are made.

Geochemistry of organic carbon and trace elements in boreal stratified lakes during different seasons

NASA Astrophysics Data System (ADS)

Moreva, O. Y.; Pokrovsky, O. S.; Shirokova, L. S.; Viers, J.

2008-12-01

Our knowledge of chemical fluxes in the system rock-soils-rivers-ocean of boreal and glacial landscapes is limited by the least studied part, i.e., the river water transformation between the lake and the river systems. Dissolved organic carbon (DOC), nutrients, major and trace elements are being leached from soil profile to the river but subjected to chemical transformation in the lakes due to phytoplankton and bacterial activity. As a result, many lakes in boreal regions are quite different in chemical composition compared to surrounding rivers and demonstrate important chemical stratification. The main processes responsible for chemical stratification in lakes are considered to be i) diffusion fluxes from the sediment to the bottom water accompanied by sulfate reduction and methanogenesis in the sediments and ii) dissolution/mineralization of precipitating organic matter (mineral fraction, detritus, plankton pellets) in the bottom layer horizons under anoxic conditions. Up to present time, distinguishing between two processes remains difficult. This paper is aimed at filling this gap via detailed geochemical analysis of DOC and trace elements in the water column profiles of three typical stratified lakes of Arkhangelsk region in Kenozersky National Parc (64° N) in winter (glacial) and in summer period. Concentration of most trace elements (Li, B, Al, Ti, V, Cr, Ni, Co, Zn, As, Rb, Sr, Y, Zr, Mo, Sb, Ba, REEs, Th, U) are not subjected to strong variations along the water column, despite the presence of strong or partial redox stratification. Apparently, these elements are not significantly controlled by production/mineralization processes and redox phenomena in the water column, or the influence of these processes is not pronounced under the control by the allochtonous river water input. In particularly, the stability of titanium and aluminum concentration along the depth profile and their independence of iron behavior suggest the important control by dissolved organic matter. Therefore, organo-ferric colloids controlling petrogenic elements speciation in soil and river waters are being replaced by autochthonous organic colloids in the lake system. The same observation is true for some heavy metals such as nickel, copper and zinc, whereas cobalt, as limiting component, is being strongly removed from the photic zone or it is coprecipitating with manganese hydroxide. Results of the present work allow quantitative evaluation of the role of redox processes in the bottom horizons and organic detritus degradation in the creation of chemical stratification of small lakes with high DOC concentration. Further insights on geochemical migration of trace elements in lakes require : i) study of colloidal speciation using in-situ dialysis; ii) monitoring the annual and seasonal dynamics of redox processes and TE concentration variation along the profile; iii) quantitative assessment of bacterial degradation of suspended OM and Mn and Fe redox reactions along the depth profile; iv) setting the sedimentary traps for evaluation of suspended material fluxes, and, v) thorough study of chemical composition of interstitial pore waters.

Role of antioxidants in redox regulation of diabetic cardiovascular complications.

PubMed

Turan, Belma

2010-12-01

Cardiovascular dysfunction is leading cause for the mortality of diabetic individuals, in part due to a specific cardiomyopathy, and due to altered endothelial dependent/independent vascular reactivity. Cardiovascular complications result from multiple parameters including glucotoxicity, lipotoxicity, fibrosis and mitochondrial uncoupling. Oxidative stress arises from an imbalance between the production of reactive oxygen and nitrogen species (ROS and RNS) and the capability of biological system to readily detoxify reactive intermediates. Several studies have reported beneficial effects of a therapy with antioxidant agents, including trace elements and other antioxidants, against the cardiovascular system dysfunction due to the diabetes. Antioxidants act through different mechanisms to prevent oxidant-induced cell damages acting either directly or indirectly. They can reduce the generation of ROS, scavenge ROS, or interfere with ROS-induced alterations. Modulating mitochondrial activity is an important possibility to control ROS production. Hence, the use of PPARα agonist to reduce fatty acid oxidation and of trace elements such as selenium as antioxidant and other antioxidants such as vitamins E and C, contribute to the prevention of diabetes-induced cardiovascular dysfunction. The paradigm that, inhibiting the overproduction of superoxides and peroxides would prevent cardiac dysfunction in diabetes has been difficult to verify using conventional antioxidants like vitamins E and C. That led to use of catalytic antioxidants such as SOD/CAT mimetics. Hence, well-tuned, balanced and responsive antioxidant defence systems are vital for proper prevention against diabetic damage. Myocardial cell death is observed in the hearts of diabetic patients and animal models; however, its importance in the development of diabetic cardiomyopathy is not completely understood. This review aims to summarize our present knowledge on various strategies to control oxidative stress and antagonize cardiovascular dysfunction during diabetes. In here, we consider aspects of redox signaling in the cardiovascular system, focusing on the molecular basis of redox sensing by proteins and the array of post-translational oxidative modifications that can occur. In addition, we discuss studies identify redox-sensitive cardiac proteins, as well as those assessing redox signalling in cardiovascular disease.

Regional patterns of labile organic carbon flux in North American Arctic Margin (NAAM) as reflected by redox sensitive-elements distributions in sediments

NASA Astrophysics Data System (ADS)

Gobeil, C.; Kuzyk, Z. Z. A.; Goni, M. A.; Macdonald, R. W.

2016-02-01

Concentrations of elements (S, Mn, Mo, U, Cd, Re) providing insights on organic C metabolized through oxidative processes at the sea floor were measured in 27 sediment cores collected along a section extending from the North Bering Sea to Davis Strait via the Canadian Archipelago. Sedimentary distributions and accumulation rates of these elements were used to i) document the relative importance of aerobic versus anaerobic degradation of organic C in NAAM sediments, ii) infer variations in water column carbon flux and iii) estimate the importance of this margin as a sink for key elements in the Arctic and global ocean. Distributions of Mn, total S and reduced inorganic S demonstrated that most sediments along the NAAM had relatively thick (>1 cm) surface oxic layers, underlain by sediments with weakly reducing conditions and limited sulphate reduction. Strongly reducing conditions accompanied by substantial sedimentary pyrite burial occurred only in certain subregions, including the Bering-Chukchi Shelves, shallow portions of Barrow Canyon. Estimated accumulation rates of authigenic S, Mo, Cd and U, and total Re displayed marked spatial variability that was related to sedimentary redox conditions induced by the supply of labile C to the seabed, as shown by significant relationships between the accumulation rates and vertical C flux, estimated from regional primary production values and water depth at the coring sites. High primary production combined with shallow water columns drive elevated rates of authigenic trace element accumulation in sediments from the Bering-Chukchi Shelves whereas low production combined with moderately deep conditions drive low rates of accumulation in sediments in the Beaufort Shelf, Davis Strait and Canadian Archipelago. Using the average authigenic trace element accumulation rates in sediments from the various regions, we submit that the shelves along the NAAM margin are important sinks in global marine biogeochemical budgets.

Tracing iron-carbon redox from surface to core

NASA Astrophysics Data System (ADS)

McCammon, C. A.; Cerantola, V.; Bykova, E.; Kupenko, I.; Bykov, M.; Chumakov, A. I.; Rüffer, R.; Dubrovinsky, L. S.

2017-12-01

Numerous redox reactions separate the Earth's oxidised surface from its reduced core. Many involve iron, the Earth's most abundant element and the mantle's most abundant transition element. Most iron redox reactions (although not all) also involve other elements, including carbon, where iron-carbon interactions drive a number of important processes within the Earth, for example diamond formation. Many of the Earth's redox boundaries are sharp, much like the seismic properties that define them, for example between the lower mantle and the core. Other regions that appear seismically homogeneous, for example the lower mantle, harbour a wealth of reactions between oxidised and reduced phases of iron and carbon. We have undertaken many experiments at high pressure and high temperature on phases containing iron and carbon using synchrotron-based X-rays to probe structures and iron oxidation states. Results demonstrate the dominant role that crystal structures play in determining the stable oxidation states of iron and carbon, even when oxygen fugacity (and common sense) would suggest otherwise. Iron in bridgmanite, for example, occurs predominantly in its oxidised form (ferric iron) throughout the lower mantle, despite the inferred reducing conditions. Newly discovered structures of iron carbonate also stabilise ferric iron, while simultaneously reducing some carbon to diamond to balance charge. Other high-pressure iron carbonates appear to be associated with the emerging zoo of iron oxide phases, involving transitions between ferrous and ferric iron through the exchange of oxygen. The presentation will trace redox relations between iron and carbon from the Earth's surface to its core, with an emphasis on recent experimental results.

Trace element mobility and transfer to vegetation within the Ethiopian Rift Valley lake areas.

PubMed

Kassaye, Yetneberk A; Skipperud, Lindis; Meland, Sondre; Dadebo, Elias; Einset, John; Salbu, Brit

2012-10-26

To evaluate critical trace element loads in native vegetation and calculate soil-to-plant transfer factors (TFs), 11 trace elements (Cr, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Pb and Mn) have been determined in leaves of 9 taxonomically verified naturally growing terrestrial plant species as well as in soil samples collected around 3 Ethiopian Rift Valley lakes (Koka, Ziway and Awassa). The Cr concentration in leaves of all the plant species was higher than the "normal" range, with the highest level (8.4 mg per kg dw) being observed in Acacia tortilis from the Lake Koka area. Caper species (Capparis fascicularis) and Ethiopian dogstooth grass (Cynodon aethiopicus) from Koka also contained exceptionally high levels of Cd (1 mg per kg dw) and Mo (32.8 mg per kg dw), respectively. Pb, As and Cu concentrations were low in the plant leaves from all sites. The low Cu level in important fodder plant species (Cynodon aethiopicus, Acacia tortilis and Opuntia ficus-indicus) implies potential deficiency in grazing and browsing animals. Compared to the Canadian environmental quality guideline and maximum allowable concentration in agricultural soils, the total soil trace element concentrations at the studied sites are safe for agricultural crop production. Enrichment factor was high for Zn in soils around Lakes Ziway and Awassa, resulting in moderate to high transfer of Zn to the studied plants. A six step sequential extraction procedure on the soils revealed a relatively high mobility of Cd, Se and Mn. Strong association of most trace elements with the redox sensitive fraction and mineral lattice was also confirmed by partial redundancy analysis. TF (mg per kg dw plants/mg per kg dw soil) values based on the total (TF(total)) and mobile fractions (TF(mobile)) of soil trace element concentrations varied widely among elements and plant species, with the averaged TF(total) and TF(mobile) values ranging from 0.01-2 and 1-60, respectively. Considering the mobile fraction in soils should be available to plants, TF(mobile) values could reflect trace elements transfer to plants in the most realistic way. However, the present study indicates that TF(total) values also reflect the transfer of elements such as Mn, Cd and Se to plants more realistically than TF(mobile) values did.

Trace elements geochemistry of fractured basement aquifer in southern Malawi: A case of Blantyre rural

NASA Astrophysics Data System (ADS)

Mapoma, Harold Wilson Tumwitike; Xie, Xianjun; Nyirenda, Mathews Tananga; Zhang, Liping; Kaonga, Chikumbusko Chiziwa; Mbewe, Rex

2017-07-01

In this study, twenty one (21) trace elements in the basement complex groundwater of Blantyre district, Malawi were analyzed. The majority of the analyzed trace elements in the water were within the standards set by World Health Organization (WHO) and Malawi Standards Board (MSB). But, iron (Fe) (BH16 and 21), manganese (Mn) (BH01) and selenium (Se) (BH02, 13, 18, 19 and 20) were higher than the WHO and MSB standards. Factor analysis (FA) revealed up to five significant factors which accounted for 87.4% of the variance. Factor 1, 2 and 3 suggest evaporite dissolution and silicate weathering processes while the fourth factor may explain carbonate dissolution and pH influence on trace element geochemistry of the studied groundwater samples. According to PHREEQC computed saturation indices, dissolution, precipitation and rock-water-interaction control the levels of trace elements in this aquifer. Elevated concentrations of Fe, Mn and Se in certain boreholes are due to the geology of the aquifer and probable redox status of groundwater. From PHREEQC speciation results, variations in trace element species were observed. Based on this study, boreholes need constant monitoring and assessment for human consumption to avoid health related issues.

Whole rock and discrete pyrite geochemistry as complementary tracers of ancient ocean chemistry: An example from the Neoproterozoic Doushantuo Formation, China

NASA Astrophysics Data System (ADS)

Gregory, Daniel D.; Lyons, Timothy W.; Large, Ross R.; Jiang, Ganqing; Stepanov, Aleksandr S.; Diamond, Charles W.; Figueroa, Maria C.; Olin, Paul

2017-11-01

The trace element content of pyrite is a recently developed proxy for metal abundance in paleo-oceans. Previous studies have shown that the results broadly match those of whole rock studies through geologic time. However, no detailed study has evaluated the more traditional proxies for ocean chemistry for comparison to pyrite trace element data from the same samples. In this study we compare pyrite trace element data from 14 samples from the Wuhe section of the Ediacaran-age Doushantuo Formation, south China, measured by laser ablation inductively coupled plasma mass spectrometry with new and existing whole rock trace element concentrations; total organic carbon; Fe mineral speciation; S isotope ratios; and pyrite textural relationships. This approach allows for comparison of data for individual trace elements within the broader environmental context defined by the other chemical parameters. The results for discrete pyrite analyses show that several chalcophile and siderophile elements (Ag, Sb, Se, Pb, Cd, Te, Bi, Mo, Ni, and Au) vary among the samples with patterns that mirror those of the independent whole rock data. A comparison with existing databases for sedimentary and hydrothermal pyrite allows us to discriminate between signatures of changing ocean conditions and those of known hydrothermal sources. In the case of the Wuhe samples, the observed patterns for trace element variation point to primary marine controls rather than higher temperature processes. Specifically, our new data are consistent with previous arguments for pulses of redox sensitive trace elements interpreted to be due to marine oxygenation against a backdrop of mostly O2-poor conditions in the Ediacaran ocean-with important implications for the availability of bioessential elements. The agreement between the pyrite and whole rock data supports the use of trace element content of pyrite as a tracer of ocean chemistry in ways that complement existing approaches, while also opening additional windows of opportunity. For example, unlike the potential vulnerability of whole rock data to secondary alteration, the pyrite record may survive greenschist facies metamorphism. Furthermore, early-formed pyrite can be identified through textural relationships as a proxy of primary marine chemistry even in the presence of hydrothermal overprints on whole rock chemistry via secondary fluids. Finally, pyrite analyses may allow for the possibility of more quantitative interpretations of the ancient ocean once the elemental partitioning between the mineral and host fluids are better constrained. Collectively, these advances can greatly increase the number of basins that may be investigated for early ocean chemistry, especially those of Precambrian age.

Redox Regulation of Cell Contacts by Tricellulin and Occludin: Redox-Sensitive Cysteine Sites in Tricellulin Regulate Both Tri- and Bicellular Junctions in Tissue Barriers as Shown in Hypoxia and Ischemia.

PubMed

Cording, Jimmi; Günther, Ramona; Vigolo, Emilia; Tscheik, Christian; Winkler, Lars; Schlattner, Isabella; Lorenz, Dorothea; Haseloff, Reiner F; Schmidt-Ott, Kai M; Wolburg, Hartwig; Blasig, Ingolf E

2015-11-01

Tight junctions (TJs) seal paracellular clefts in epithelia/endothelia and form tissue barriers for proper organ function. TJ-associated marvel proteins (TAMPs; tricellulin, occludin, marvelD3) are thought to be relevant to regulation. Under normal conditions, tricellulin tightens tricellular junctions against macromolecules. Traces of tricellulin occur in bicellular junctions. As pathological disturbances have not been analyzed, the structure and function of human tricellulin, including potentially redox-sensitive Cys sites, were investigated under reducing/oxidizing conditions at 3- and 2-cell contacts. Ischemia, hypoxia, and reductants redistributed tricellulin from 3- to 2-cell contacts. The extracellular loop 2 (ECL2; conserved Cys321, Cys335) trans-oligomerized between three opposing cells. Substitutions of these residues caused bicellular localization. Cys362 in transmembrane domain 4 contributed to bicellular heterophilic cis-interactions along the cell membrane with claudin-1 and marvelD3, while Cys395 in the cytosolic C-terminal tail promoted homophilic tricellullar cis-interactions. The Cys sites included in homo-/heterophilic bi-/tricellular cis-/trans-interactions contributed to cell barrier tightness for small/large molecules. Tricellulin forms TJs via trans- and cis-association in 3-cell contacts, as demonstrated electron and quantified fluorescence microscopically; it tightens 3- and 2-cell contacts. Tricellulin's ECL2 specifically seals 3-cell contacts redox dependently; a structural model is proposed. TAMP ECL2 and claudins' ECL1 share functionally and structurally similar features involved in homo-/heterophilic tightening of cell-cell contacts. Tricellulin is a specific redox sensor and sealing element at 3-cell contacts and may compensate as a redox mediator for occludin loss at 2-cell contacts in vivo and in vitro. Molecular interaction mechanisms were proposed that contribute to tricellulin's function. In conclusion, tricellulin is a junctional redox regulator for ischemia-related alterations.

Trace Elements in Manganese Minerals as Potential Biosignatures on Mars

NASA Astrophysics Data System (ADS)

Lanza, N.; Clegg, S. M.; Cousin, A.; Forni, O.; Kirk, M. F.; Lamm, S. N.; Ollila, A.; Wiens, R. C.

2017-12-01

Observations from the Curiosity rover in Gale crater, Mars have shown the presence of high abundances of manganese (>3 wt% MnO) within sedimentary rocks throughout the traverse. Such high Mn abundances point to the past presence of abundant liquid water and strongly oxidizing conditions. On Earth, these types of environments are almost always habitable and are frequently inhabited by microbes. Given its close association with life and habitable environments on Earth, manganese has long been considered a potential biosignature for Mars. However, high concentrations of martian Mn have only recently been observed. In addition to the observations in Gale crater, high abundances of Mn have also been observed in Endeavor crater by the Opportunity rover and in the paired martian meteorites NWA 7034 and 7533 (`Black Beauty'), suggesting that Mn deposits may be more widespread on Mars than previously thought. The goal of this work is to determine whether there are unique signatures from rover payload instruments that can distinguish Mn-rich deposits as biogenic in origin (i.e., produced by life) from abiogenic Mn deposits. Importantly, Mn-oxides are known to scavenge trace metals from water because of their surface charge properties. We hypothesize that the presence and abundance of specific trace elements are the critical, distinguishing evidence for identifying the biogenic origin of Mn-bearing materials. A suite of natural rocks containing Mn-rich minerals with a range of Mn redox states was selected for analysis with laser-induced breakdown spectroscopy (LIBS). Samples with a biogenic origin had mixed valence redox states between Mn3+ and Mn4+ as inferred by mineralogy. Trace elements Ba, Li, Sr, and Rb were quantified and the presence or absence of Zn and Cu was ascertained by examining key LIBS peaks. Results show that samples with a known microbial origin had moderate Mn abundances >30 wt% MnO and higher Li and Ba. These results suggest that high Mn abundance alone is not sufficient evidence of a biosignatures. However, the presence of trace elements may help to infer the redox state of Mn, which may in turn point to samples that are more likely to have a biogenic origin.

Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters

USGS Publications Warehouse

Nordstrom, D. Kirk

2011-01-01

Mobility of potential or actual contaminants from mining and mineral processing activities depends on (1) occurrence: is the mineral source of the contaminant actually present? (2) abundance: is the mineral present in sufficient quantity to make a difference? (3) reactivity: what are the energetics, rates, and mechanisms of sorption and mineral dissolution and precipitation relative to the flow rate of the water? and (4) hydrology: what are the main flow paths for contaminated water? Estimates of relative proportions of minerals dissolved and precipitated can be made with mass-balance calculations if minerals and water compositions along a flow path are known. Combined with discharge, these mass-balance estimates quantify the actual weathering rate of pyrite mineralization in the environment and compare reasonably well with laboratory rates of pyrite oxidation except when large quantities of soluble salts and evaporated mine waters have accumulated underground. Quantitative mineralogy with trace-element compositions can substantially improve the identification of source minerals for specific trace elements through mass balances. Post-dissolution sorption and precipitation (attenuation) reactions depend on the chemical behavior of each element, solution composition and pH, aqueous speciation, temperature, and contact-time with mineral surfaces. For example, little metal attenuation occurs in waters of low pH (2, and redox-sensitive oxyanions (As, Sb, Se, Mo, Cr, V). Once dissolved, metal and metalloid concentrations are strongly affected by redox conditions and pH. Iron is the most reactive because it is rapidly oxidized by bacteria and archaea and Fe(III) hydrolyzes and precipitates at low pH (1–3) which is related directly to its first hydrolysis constant, pK1 = 2.2. Several insoluble sulfate minerals precipitate at low pH including anglesite, barite, jarosite, alunite and basaluminite. Aluminum hydrolyzes near pH 5 (pK1 = 5.0) and provides buffering and removal of Al by mineral precipitation from pH 4–5.5. Dissolved sulfate behaves conservatively because the amount removed from solution by precipitation is usually too small relative to the high concentrations in the water column and relative to the flow rate of the water.

Rare earth elements in the water column of Lake Vanda, McMurdo Dry Valleys, Antarctica

NASA Astrophysics Data System (ADS)

De Carlo, Eric Heinen; Green, William J.

2002-04-01

We present data on the composition of water from Lake Vanda, Antarctica. Vanda and other lakes in the McMurdo Dry Valleys of Antarctica are characterized by closed basins, permanent ice covers, and deep saline waters. The meromictic lakes provide model systems for the study of trace metal cycling owing to their pristine nature and the relative simplicity of their biogeochemical systems. Lake Vanda, in the Wright Valley, is supplied by a single input, the Onyx River, and has no output. Water input to the lake is balanced by sublimation of the nearly permanent ice cap that is broken only near the shoreline during the austral summer. The water column is characterized by an inverse thermal stratification of anoxic warm hypersaline water underlying cold oxic freshwater. Water collected under trace-element clean conditions was analyzed for its dissolved and total rare earth element (REE) concentrations by inductively coupled plasma mass spectrometry. Depth profiles are characterized by low dissolved REE concentrations (La, Ce, <15 pM) in surface waters that increase slightly (La, 70 pM; Ce, 20 pM) with increasing depth to ∼55 m, the limit of the fresh oxic waters. Below this depth, a sharp increase in the concentrations of strictly trivalent REE (e.g., La, 5 nM) is observed, and a submaximum in redox sensitive Ce (2.6 nM) is found at 60- to 62-m depth. At a slightly deeper depth, a sharper Ce maximum is observed with concentrations exceeding 11 nM at a 67-m depth, immediately above the anoxic zone. The aquatic concentrations of REE reported here are ∼50-fold higher than previously reported for marine oxic/anoxic boundaries and are, to our knowledge, the highest ever observed at natural oxic/anoxic interfaces. REE maxima occur within stable and warm saline waters. All REE concentrations decrease sharply in the sulfidic bottom waters. The redox-cline in Lake Vanda is dominated by diffusional processes and vertical transport of dissolved species driven by concentration gradients. Furthermore, because the ultraoligotrophic nature of the lake limits the potential for organic phases to act as metal carriers, metal oxide coatings and sulfide phases appear to largely govern the distribution of trace elements. We discuss REE cycling in relation to the roles of redox reactions and competitive scavenging onto Mn- and Fe-oxides coatings on clay sized particles in the upper oxic water column and their release by reductive dissolution near the anoxic/oxic interface.

Human semen as an early, sensitive biomarker of highly polluted living environment in healthy men: A pilot biomonitoring study on trace elements in blood and semen and their relationship with sperm quality and RedOx status.

PubMed

Bergamo, Paolo; Volpe, Maria Grazia; Lorenzetti, Stefano; Mantovani, Alberto; Notari, Tiziana; Cocca, Ennio; Cerullo, Stefano; Di Stasio, Michele; Cerino, Pellegrino; Montano, Luigi

2016-12-01

The Campania region in Italy is facing an environmental crisis due to the illegal disposal of toxic waste. Herein, a pilot study (EcoFoodFertility initiative) was conducted to investigate the use of human semen as an early biomarker of pollution on 110 healthy males living in various areas of Campania with either high or low environmental impact. The semen from the "high impact" group showed higher zinc, copper, chromium and reduced iron levels, as well as reduced sperm motility and higher sperm DNA Fragmentation Index (DFI). Redox biomarkers (total antioxidant capacity, TAC, and glutathione, GSH) and the activity of antioxidant enzymes in semen were lower in the "high impact" group. The percentage of immotile spermatozoa showed a significant inverse correlation with TAC and GSH. Overall, several semen parameters (reduced sperm quality and antioxidant defenses, altered chemical element pattern), which were associated with residence in a high polluted environment, could be used in a further larger scale study, as early biomarkers of environmental pollution. Copyright © 2016 Elsevier Inc. All rights reserved.

The Redox Dynamics of Iron in a Seasonally Waterlogged Forest Soil (Chaux Forest, Eastern France) Traced with Rare Earth Element Distribution Patterns

NASA Astrophysics Data System (ADS)

Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.

2014-12-01

The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.

Association of Serum Concentration of Different Trace Elements with Biomarkers of Systemic Oxidant Status in Dairy Cattle.

PubMed

Abuelo, Angel; Hernandez, Joaquín; Alves-Nores, Víctor; Benedito, José L; Castillo, Cristina

2016-12-01

There has been some recent criticism about the reliability of the assays commonly used to measure oxidant status in cattle, because some recent publications suggested that the concentration of different trace elements influences the results of these assays. The aim of this study was to test the correlation in 502 bovine serum samples between the concentration of several trace elements (Br, Co, Cr, Cu, Fe, I, Mn, Mo, Ni, Se, Sr, V and Zn) and markers of oxidant status (reactive oxygen species (ROS) and total serum antioxidant capacity (SAC)). The Oxidative Stress index (OSi) was also calculated as ROS/SAC. Some significant correlations were found, although weak (|ρ| < 0.50). Therefore, the relationships observed might be attributed to the different pro- and antioxidant effect of the different elements rather than to the assays detecting these elements instead of the oxidised molecules or total antioxidant potential, respectively. The OSi was poorly correlated (|ρ| ≤ 0.36) with the concentration of the studied trace elements, and therefore, its use is recommended to assess shifts in the systemic redox balance.

Ancient Oceans Had Less Oxygen

ERIC Educational Resources Information Center

King, Angela G.

2004-01-01

The amount of dissolved oxygen in the oceans in the mid-Proterozoic period has evolutionary implications since essential trace metals are redox sensitive. The findings suggest that there is global lack of oxygen in seawater.

Protective effect of magnesium acetyltaurate against NMDA-induced retinal damage involves restoration of minerals and trace elements homeostasis.

PubMed

Jafri, Azliana Jusnida Ahmad; Arfuzir, Natasha Najwa Nor; Lambuk, Lidawani; Iezhitsa, Igor; Agarwal, Renu; Agarwal, Puneet; Razali, Norhafiza; Krasilnikova, Anna; Kharitonova, Maria; Demidov, Vasily; Serebryansky, Evgeny; Skalny, Anatoly; Spasov, Alexander; Yusof, Ahmad Pauzi Md; Ismail, Nafeeza Mohd

2017-01-01

Glutamate-mediated excitotoxicity involving N-methyl-d-aspartate (NMDA) receptors has been recognized as a final common outcome in pathological conditions involving death of retinal ganglion cells (RGCs). Overstimulation of NMDA receptors results in influx of calcium (Ca) and sodium (Na) ions and efflux of potassium (K). NMDA receptors are blocked by magnesium (Mg). Such changes due to NMDA overstimulation are also associated with not only the altered levels of minerals but also that of trace elements and redox status. Both the decreased and elevated levels of trace elements such as iron (Fe), zinc (Zn), copper (Cu) affect NMDA receptor excitability and redox status. Manganese (Mn), and selenium (Se) are also part of antioxidant defense mechanisms in retina. Additionally endogenous substances such as taurine also affect NMDA receptor activity and retinal redox status. Therefore, the aim of this study was to evaluate the effect of Mg acetyltaurate (MgAT) on the retinal mineral and trace element concentration, oxidative stress, retinal morphology and retinal cell apoptosis in rats after-NMDA exposure. One group of Sprague Dawley rats received intravitreal injection of vehicle while 4 other groups similarly received NMDA (160nmolL -1 ). Among the NMDA injected groups, 3 groups also received MgAT (320nmolL -1 ) as pre-treatment, co-treatment or post-treatment. Seven days after intravitreal injection, rats were sacrificed, eyes were enucleated and retinae were isolated for estimation of mineral (Ca, Na, K, Mg) and trace element (Mn, Cu, Fe, Se, Zn) concentration using Inductively Coupled Plasma (DRC ICP-MS) techniques (NexION 300D), retinal oxidative stress using Elisa, retinal morphology using H&E staining and retinal cell apoptosis using terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL). Intravitreal NMDA injection resulted in increased concentration of Ca (4.6 times, p<0.0001), Mg (1.5 times, p<0.01), Na (3 times, p<0.0001) and K (2.3 times, p<0.0001) compared to vehicle injected group. This was accompanied with significant increase of Ca/Mg and Na/K ratios, 3 and 1.27 times respectively, compared to control group. The trace elements such as Cu, Fe and Zn also showed a significant increase amounting to 3.3 (p<0.001), 2.3 (p<0.0001) and 3 (p<0.0001) times respectively compared to control group. Se was increased by 60% (p<0.005). Pre-treatment with MgAT abolished effect of NMDA on minerals and trace elements more effectively than co- and post-treatment. Similar observations were made for retinal oxidative stress, retinal morphology and retinal cell apoptosis. In conclusion, current study demonstrated the protective effect of MgAT against NMDA-induced oxidative stress and retinal cell apoptosis. This effect of MgAT was associated with restoration of retinal concentrations of minerals and trace elements. Further studies are warranted to explore the precise molecular targets of MgAT. Nevertheless, MgAT seems a potential candidate in the management of diseases involving NMDA-induced excitotoxicity. Copyright © 2016 Elsevier GmbH. All rights reserved.

Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China.

PubMed

Bu, Hongmei; Song, Xianfang; Guo, Fen

2017-01-15

Dissolved trace element concentrations (Ba, Fe, Mn, Si, Sr, and Zn) were investigated in the Haicheng River near to the Liaodong Bay in Northeast China during 2010. Dissolved Ba, Fe, Mn, and Sr showed significant spatial variation, whereas dissolved Fe, Mn, and Zn displayed seasonal variations. Conditions such as water temperature, pH, and dissolved oxygen were found to have an important impact on redox reactions involving dissolved Ba, Fe, and Zn. Dissolved Fe and Mn concentrations were regulated by adsorption or desorption of Fe/Mn oxyhydroxides and the effects of organic carbon complexation on dissolved Ba and Sr were found to be significant. The sources of dissolved trace elements were found to be mainly from domestic sewage, industrial waste, agricultural surface runoff, and natural origin, with estimated seasonal and annual river fluxes established as important inputs of dissolved trace elements from the Haicheng River into the Liaodong Bay or Bohai Sea. Copyright © 2016 Elsevier Ltd. All rights reserved.

Trace Element Cycling in Lithogenic Particles at Station ALOHA

NASA Astrophysics Data System (ADS)

Morton, P. L.; Weisend, R.; Landing, W. M.; Fitzsimmons, J. N.; Hayes, C. T.; Boyle, E. A.

2014-12-01

Trace element cycling in marine particles is influenced by atmospheric deposition, vertical export, biological uptake and remineralization, scavenging, and lateral transport processes. To investigate the cycling of lithogenic particles in the central North Pacific Ocean, surface and vertical profile samples of marine suspended particulate matter (SPM) were collected July-August 2012 during the HOE-DYLAN cruises at Station ALOHA. In the late summer, atmospheric dust inputs from the Gobi desert (which peak during the spring, April-May) were sparse, as indicated by low surface particulate Ti (pTi) concentrations. In contrast, surface pAl concentrations did not follow pTi trends as expected, but appear to be dominated by scavenging/uptake of dissolved Al during diatom blooms. Surface pMn concentrations were low, but vertical profiles of pMn and pMn/pTi reveal a strong sedimentary source at 200 m, originating from the Hawaiian continental shelf through a combination of redox mobilization and resuspension processes. The redox active elements Ce and Co can have chemistries similar to that of Mn, but in these samples the pCe and pCo distributions were distinct from Mn and each other in both surface trends and vertical profiles. Surface pREE (e.g., La, Ce, Pr) were highest during the earliest sampling events and quickly decreased to consistently low concentrations, while vertical distributions were characterized by scavenging onto biotic particles and mid-depth inputs. The surface particulate Co trend is similar to those of pAl and pP, while the pCo vertical profiles reflect surface enrichment but low concentrations and little variability at depth. A second, complementary poster is also being presented which examines the biological influence over particulate trace element cycling (Weisend et al., "Particulate Trace Element Cycling in a Diatom Bloom at Station ALOHA").

Understanding the Marine Chromium Isotope Record from Modern and Ancient Carbonates

NASA Astrophysics Data System (ADS)

Parkinson, I. J.; Bonnand, P.; James, R. H.; Fairchild, I. J.; Dixon, S.

2011-12-01

Chromium isotopes may provide a powerful tool for reconstructing the redox state of ancient seawater because Cr isotope fractionation is large (up to 7% in δ53Cr) during the reduction of Cr(VI) to Cr(III) in natural waters [1]. Recent studies have demonstrated that although Cr(VI) is predicted to be the thermodynamically stable form in seawater (as CrO42-), significant amounts (5-20%) of Cr(III) may also be present in surface waters [2]. Therefore the δ53Cr of seawater could vary by up to 2%. Marine carbonates potentially provide a means to extracting information about the Cr isotopic composition of seawater in the geological past and we have developed a high-precision double-spike technique for analysing Cr isotopes in carbonates [3]. The δ53Cr of modern Bahamas Bank carbonates (+0.76%) is broadly consistent with these carbonates recording a seawater Cr signature. Moreover, these pure carbonates contain significant amounts of Cr (1-4 ppm), which indicates that Cr is strongly partitioned into calcium carbonate. Therefore carbonates are likely to provide a faithful record of the δ53Cr composition of seawater. Shallow marine carbonates from the Phanerozoic range in δ53Cr from +0.76 to +1.8%, and some Neoproterozoic carbonates also have heavy Cr isotopic compositions of +0.5 to +1.0 %. Such compositions may reflect changes in the inputs of Cr to the oceans and/or changes in the redox state of the oceans. However, to interpret Cr isotopic compositions in ancient carbonates additionally requires a careful assessment of their trace element contents. This study aims to demonstrate how a combination of redox sensitive trace elements, such as Ce, and Cr isotopes allow an assessment of the marine chromium isotope record. [1] Ellis et al., 2002, Science, 295, 2060-2062. [2] Connolly et al., 2006, Deep Sea Res. Part I, 2006 53, 1975-1988. [3] P. Bonnand, et al., 2011, J. Anal. At. Spectr., 26, 528-535.

Early diagenesis and trace element accumulation in North American Arctic margin sediments

NASA Astrophysics Data System (ADS)

Kuzyk, Zou Zou A.; Gobeil, Charles; Goñi, Miguel A.; Macdonald, Robie W.

2017-04-01

Concentrations of redox-sensitive elements (S, Mn, Mo, U, Cd, Re) were analyzed in a set of 27 sediment cores collected along the North American Arctic margin (NAAM) from the North Bering Sea to Davis Strait via the Canadian Archipelago. Sedimentary distributions and accumulation rates of the elements were used to evaluate early diagenesis in sediments along this section and to estimate the importance of this margin as a sink for key elements in the polar and global oceans. Distributions of Mn, total S and reduced inorganic S demonstrated that diagenetic conditions and thus sedimentary carbon turnover in the NAAM is organized regionally: undetectable or very thin layers (<0.5 cm) of surface Mn enrichment occurred in the Bering-Chukchi shelves; thin layers (1-5 cm) of surface Mn enrichment occurred in Barrow Canyon and Lancaster Sound; and thick layers (5-20 cm) of surface Mn enrichment occurred in the Beaufort Shelf, Canadian Archipelago, and Davis Strait. Inventories of authigenic S below the Mn-rich layer decreased about fivefold from Bering-Chukchi shelf and Barrow Canyon to Lancaster Sound and more than ten-fold from Bering-Chukchi shelf to Beaufort Shelf, Canadian Archipelago and Davis Strait. The Mn, total S and reduced inorganic S distributions imply strong organic carbon (OC) flux and metabolism in the Bering-Chukchi shelves, lower aerobic OC metabolism in Barrow Canyon and Lancaster Sound, and deep O2 penetration and much lower OC metabolism in the Beaufort Shelf, Canadian Archipelago, and Davis Strait. Accumulation rates of authigenic S, Mo, Cd, Re, and U displayed marked spatial variability along the NAAM reflecting the range in sedimentary redox conditions. Strong relationships between the accumulation rates and vertical carbon flux, estimated from regional primary production values and water depth at the coring sites, indicate that the primary driver in the regional patterns is the supply of labile carbon to the seabed. Thus, high primary production combined with a shallow water column (average 64 m) leads to high rates of authigenic trace element accumulation in sediments from the Bering-Chukchi shelves. High to moderate primary production combined with deep water (average 610 m) leads to moderate rates of authigenic trace element accumulation in sediments from Lancaster Sound. Low to very low primary production combined with moderate water depths (average 380 m) leads to low rates of authigenic trace element accumulation in sediments in the Beaufort Shelf, Davis Strait and Canadian Archipelago. Authigenic Mo accumulation rates show a significant relationship with vascular plant input to the sediments, implying that terrestrial organic matter contributes significantly to metabolism in Arctic margin sediments. Our results suggest that the broad and shallow shelf of the Chukchi Sea, which has high productivity sustained by imported nutrients, contributes disproportionately to global biogeochemical cycles.

Investigating Microbe-Mineral Interactions: Recent Advances in X-Ray and Electron Microscopy and Redox-Sensitive Methods

NASA Astrophysics Data System (ADS)

Miot, Jennyfer; Benzerara, Karim; Kappler, Andreas

2014-05-01

Microbe-mineral interactions occur in diverse modern environments, from the deep sea and subsurface rocks to soils and surface aquatic environments. They may have played a central role in the geochemical cycling of major (e.g., C, Fe, Ca, Mn, S, P) and trace (e.g., Ni, Mo, As, Cr) elements over Earth's history. Such interactions include electron transfer at the microbe-mineral interface that left traces in the rock record. Geomicrobiology consists in studying interactions at these organic-mineral interfaces in modern samples and looking for traces of past microbe-mineral interactions recorded in ancient rocks. Specific tools are required to probe these interfaces and to understand the mechanisms of interaction between microbes and minerals from the scale of the biofilm to the nanometer scale. In this review, we focus on recent advances in electron microscopy, in particular in cryoelectron microscopy, and on a panel of electrochemical and synchrotron-based methods that have recently provided new understanding and imaging of the microbe-mineral interface, ultimately opening new fields to be explored.

In situ trace metal analysis of Neoarchaean--Ordovician shallow-marine microbial-carbonate-hosted pyrites.

PubMed

Gallagher, M; Turner, E C; Kamber, B S

2015-07-01

Pre-Cambrian atmospheric and oceanic redox evolutions are expressed in the inventory of redox-sensitive trace metals in marine sedimentary rocks. Most of the currently available information was derived from deep-water sedimentary rocks (black shale/banded iron formation). Many of the studied trace metals (e.g. Mo, U, Ni and Co) are sensitive to the composition of the exposed land surface and prevailing weathering style, and their oceanic inventory ultimately depends on the terrestrial flux. The validity of claims for increased/decreased terrestrial fluxes has remained untested as far as the shallow-marine environment is concerned. Here, the first systematic study of trace metal inventories of the shallow-marine environment by analysis of microbial carbonate-hosted pyrite, from ca. 2.65-0.52 Ga, is presented. A petrographic survey revealed a first-order difference in preservation of early diagenetic pyrite. Microbial carbonates formed before the 2.4 Ga great oxygenation event (GOE) are much richer in pyrite and contain pyrite grains of greater morphological variability but lesser chemical substitution than samples deposited after the GOE. This disparity in pyrite abundance and morphology is mirrored by the qualitative degree of preservation of organic matter (largely as kerogen). Thus, it seems that in microbial carbonates, pyrite formation and preservation were related to presence and preservation of organic C. Several redox-sensitive trace metals show interpretable temporal trends supporting earlier proposals derived from deep-water sedimentary rocks. Most notably, the shallow-water pyrite confirms a rise in the oceanic Mo inventory across the pre-Cambrian-Cambrian boundary, implying the establishment of efficient deep-ocean ventilation. The carbonate-hosted pyrite also confirms the Neoarchaean and early Palaeoproterozoic ocean had higher Ni concentration, which can now more firmly be attributed to a greater proportion of magnesian volcanic rock on land rather than a stronger hydrothermal flux of Ni. Additionally, systematic trends are reported for Co, As, and Zn, relating to terrestrial flux and oceanic productivity. © 2015 John Wiley & Sons Ltd.

Trace metal cycling and 238U/235U in New Zealand's fjords: Implications for reconstructing global paleoredox conditions in organic-rich sediments

NASA Astrophysics Data System (ADS)

Hinojosa, Jessica L.; Stirling, Claudine H.; Reid, Malcolm R.; Moy, Christopher M.; Wilson, Gary S.

2016-04-01

Reconstructing the history of ocean oxygenation provides insight into links between ocean anoxia, biogeochemical cycles, and climate. Certain redox-sensitive elements respond to changes in marine oxygen content through phase shifts and concomitant isotopic fractionation, providing new diagnostic proxies of past ocean hypoxia. Here we explore the behavior and inter-dependence of a suite of commonly utilized redox-sensitive trace metals (U, Mo, Fe, and Mn) and the emerging ;stable; isotope system of U (238U/235U, or δ238U) in New Zealand fjords. These semi-restricted basins have chemical conditions spanning the complete redox spectrum from fully oxygenated to suboxic to intermittently anoxic/euxinic. In the anoxic water column, U and Mo concentrations decrease, while Fe and Mn concentrations increase. Similarly, signals of past euxinic conditions can be found by U, Mo, Fe, and Mn enrichment in the underlying sediments. The expected U isotopic shift toward a lower δ238U in the anoxic water column due to U(VI)-U(IV) reduction is not observed; instead, water column δ238U profiles are consistent in fjords of all oxygen content, falling within previously reported ranges for open ocean seawater (δ238U = -0.42 ± 0.07‰). Additionally, surface sediment δ238U results show evidence for competing U isotope fractionation processes. One site indicates increased export of 238U from seawater to the underlying sediments (fractionation between aqueous seawater U and particulate sediment U, or ΔU(aq)-U(solid) = -0.25‰), consistent with redox-driven fractionation. Another site suggests potential U(VI) adsorption-driven fractionation, reflecting increased export of 235U from seawater to sediments (ΔU(aq)-U(solid) = 0.25‰). We discuss several potential factors that could alter δ238U in waters and sediments beyond redox-driven shifts, including adsorption to organic matter in waters of high primary productivity, reaction rates for competing processes of U adsorption and release, and isotopic constraints of U coming into the system from terrestrial environments. These potential complications should be understood and constrained through observations, experiments, and models before future application of δ238U as a global paleoredox tracer can achieve its full potential.

TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

EPA Science Inventory

Iron (hydr)oxides often control the mobility of inorganic contaminants in soils and sediments. A poorly ordered form of ferrihydrite is commonly produced during rapid oxidation of ferrous iron at sharp redox fronts encountered during discharge of anoxic/suboxic waters into terre...

Selected elements in major minerals from bituminous coal as determined by INAA: Implications for removing environmentally sensitive elements from coal

USGS Publications Warehouse

Palmer, C.A.; Lyons, P.C.

1996-01-01

The four most abundant minerals generally found in Euramerican bituminous coals are quartz, kaolinite, illite and pyrite. These four minerals were isolated by density separation and handpicking from bituminous coal samples collected in the Ruhr Basin, Germany and the Appalachian basin, U.S.A. Trace-element concentrations of relatively pure (??? 99+%) separates of major minerals from these coals were determined directly by using instrumental neutron activation analysis (INAA). As expected, quartz contributes little to the trace-element mass balance. Illite generally has higher trace-element concentrations than kaolinite, but, for the concentrates analyzed in this study, Hf, Ta, W, Th and U are in lower concentrations in illite than in kaolinite. Pyrite has higher concentrations of chalcophile elements (e.g., As and Se) and is considerably lower in lithophile elements as compared to kaolinite and illite. Our study provides a direct and sensitive method of determining trace-element relationships with minerals in coal. Mass-balance calculations suggest that the trace-element content of coal can be explained mainly by three major minerals: pyrite, kaolinite and illite. This conclusion indicates that the size and textural relationships of these major coal minerals may be a more important consideration as to whether coal cleaning can effectively remove the most environmentally sensitive trace elements in coal than what trace minerals are present.

Empirical links between trace metal cycling and marine microbial ecology during a large perturbation to Earth's carbon cycle

NASA Astrophysics Data System (ADS)

Owens, Jeremy D.; Reinhard, Christopher T.; Rohrssen, Megan; Love, Gordon D.; Lyons, Timothy W.

2016-09-01

Understanding the global redox state of the oceans and its cause-and-effect relationship with periods of widespread organic-carbon deposition is vital to interpretations of Earth's climatic and biotic feedbacks during periods of expanded oceanic oxygen deficiency. Here, we present a compilation of new and published data from an organic-rich locality within the proto-North Atlantic Ocean during the Cenomanian-Turonian boundary event that shows a dramatic drawdown of redox-sensitive trace elements. Iron geochemistry independently suggests euxinic deposition (i.e., anoxic and sulfidic bottom waters) for the entire section, thus confirming its potential as an archive of global marine metal inventories. In particular, depleted molybdenum (Mo) and vanadium (V) concentrations effectively record the global expansion of euxinic and oxygen-deficient but non-sulfidic waters, respectively. The V drawdown precedes the OAE, fingerprinting an expansion of oxygen deficiency prior to an expansion of euxinia. Molybdenum drawdown, in contrast, is delayed with respect to V and coincides with the onset of OAE2. Parallel lipid biomarker analyses provide evidence for significant and progressive reorganization of marine microbial ecology during the OAE in this region of the proto-North Atlantic, with the smallest relative eukaryotic contributions to total primary production occurring during metal-depleted intervals. This relationship may be related to decreasing supplies of enzymatically important trace elements. Similarly, box modeling suggests that oceanic drawdown of Mo may have approached levels capable of affecting marine nitrogen fixation. Predictions of possible nitrogen stress on eukaryotic production, locally and globally, are consistent with the low observed levels of Mo and a rise in 2-methylhopane index values during the peak of the OAE. At the same time, the environmental challenge presented by low dissolved oxygen and euxinia coincides with increased turnover rates of radiolarian clades, calcareous nanofossils, and foraminifera, suggesting that the temporal patterns of anoxia/euxinia and associated nutrient limitation may have contributed to the fabric of OAE2-related turnover.

Impact of anaerobic oxidation of methane on the geochemical cycle of redox-sensitive elements at cold-seep sites of the northern South China Sea

NASA Astrophysics Data System (ADS)

Hu, Yu; Feng, Dong; Liang, Qianyong; Xia, Zhen; Chen, Linying; Chen, Duofu

2015-12-01

Cold hydrocarbon seepage is a frequently observed phenomenon along continental margins worldwide. However, little is known about the impact of seeping fluids on the geochemical cycle of redox-sensitive elements. Pore waters from four gravity cores (D-8, D-5, D-7, and D-F) collected from cold-seep sites of the northern South China Sea were analyzed for SO42-, Mg2+, Ca2+, Sr2+, dissolved inorganic carbon (DIC), δ13CDIC, dissolved Fe, Mn, and trace elements (e.g. Mo, U). The sulfate concentration-depth profiles, δ13CDIC values and (ΔDIC+ΔCa2++ΔMg2+)/ΔSO42- ratios suggest that organoclastic sulfate reduction (OSR) is the dominant process in D-8 core. Besides OSR, anaerobic oxidation of methane (AOM) is partially responsible for depletion of sulfate at D-5 and D-7 cores. The sulfate consumption at D-F core is predominantly caused by AOM. The depth of sulfate-methane interface (SMI) and methane diffusive flux of D-F core are calculated to be ~7 m and 0.035 mol m-2 yr-1, respectively. The relatively shallow SMI and high methane flux at D-F core suggest the activity of gas seepage in this region. The concentrations of dissolved uranium (U) were inferred to decrease significantly within the iron reduction zone. It seems that AOM has limited influence on the U geochemical cycling. In contrast, a good correlation between the consumption of sulfate and the removal of molybdenum (Mo) suggests that AOM has a significantly influence on the geochemical cycle of Mo at cold seeps. Accordingly, cold seep environments may serve as an important potential sink in the marine geochemical cycle of Mo.

The effect of titanite crystallisation on Eu and Ce anomalies in zircon and its implications for the assessment of porphyry Cu deposit fertility

NASA Astrophysics Data System (ADS)

Loader, Matthew A.; Wilkinson, Jamie J.; Armstrong, Robin N.

2017-08-01

The redox sensitivity of Ce and Eu anomalies in zircon has been clearly demonstrated by experimental studies, and these may represent an important tool in the exploration for porphyry Cu deposits which are thought to be derived from oxidised magmas. These deposits are significant because they are the source of much of the world's copper and almost all of the molybdenum and rhenium, key elements in many modern technologies. However, Ce and Eu anomalies in zircon are also affected by the co-crystallisation of REE bearing phases, such as titanite. Here, we report the trace element chemistry of zircons from titanite-bearing intrusions associated with mineralisation at the world class Oyu Tolgoi porphyry Cu-Au deposit (Mongolia). Based on these data, we suggest that neither zircon Eu/Eu*, nor Ce4+/Ce3+ are robust proxies for melt redox conditions, because they are both too strongly dependent on melt REE concentrations, which are usually poorly constrained and controlled by the crystallisation of titanite and other REE-bearing phases. In spite of this, Eu/Eu* can broadly distinguish between fertile and barren systems, so may still be an indicator of porphyry magma fertility, and a useful tool for exploration.

Biological control of trace metal and organometal benthic fluxes in a eutrophic lagoon (Thau Lagoon, Mediterranean Sea, France)

NASA Astrophysics Data System (ADS)

Point, D.; Monperrus, M.; Tessier, E.; Amouroux, D.; Chauvaud, L.; Thouzeau, G.; Jean, F.; Amice, E.; Grall, J.; Leynaert, A.; Clavier, J.; Donard, O. F. X.

2007-04-01

In situ benthic chamber experiments were conducted in the Thau Lagoon that allowed the simultaneous determination of the benthic exchanges of trace metals (Cd, Co, Cu, Mn, Pb and U) and mercury species (iHg and MMHg). Fluxes of organotin compounds (MBT, DBT and TBT) were also investigated for the first time. The benthic incubations were performed during two campaigns at four stations that presented different macrobenthic and macrophytic species distribution and abundance (see [Thouzeau, G., Grall, J., Clavier, J., Chauvaud, L., Jean, F., Leynaert, A., Longpuirt, S., Amice, E., Amouroux, D., 2007. Spatial and temporal variability of benthic biogeochemical fluxes associated with macrophytic and macrofaunal distributions in the Thau lagoon (France). Estuarine, Coastal and Shelf Science 72 (3), 432 446.]). The results indicate that most of the flux intensity as well as the temporal and spatial variability can be explained by the combined influence of microscale and macroscale processes. Microscale changes were identified using Mn flux as a good indicator of the redox conditions at the sediment water interface, and by extension, as an accurate proxy of benthic fluxes for most trace metals and mercury species. We also observed that the redox gradient at the interface is promoted by both microbial and macrobenthic species activity that governs O2 budgets. Macroscale processes have been investigated considering macrobenthic organisms activity (macrofauna and macroalgal cover). The density of such macroorganisms is able to explain most of the spatial and temporal variability of the benthic metal fluxes within a specific site. A tentative estimation of the flux of metals and organometals associated with deposit feeder and suspension feeder activity was found to be in the range of the flux determined within the chambers for most considered elements. Furthermore, a light/dark incubation investigating a dense macroalgal cover present at the sediment surface illustrates the role of photosynthetic activity in controlling benthic exchanges. Significant changes in benthic flux intensity and/or direction were reported for all redox sensitive elements (Cd, Co, Cu, Mn, Pb, U, and iHg). For MMHg and organotin species, other complimentary processes such as photodegradation/uptake and hydrophobic absorption/desorption need to be considered. This work demonstrates that the processes governing benthic exchanges are complex and that benthic organisms play a major role in the significant seasonal, diurnal and spatial variability of trace metals and organometals benthic fluxes in the lagoon.

Mobility of major and trace elements in a coupled groundwater-surface water system: Merced River, CA

NASA Astrophysics Data System (ADS)

Wildman, R. A.; Domagalski, J. L.; Hering, J. G.

2004-12-01

Trace element transport in coupled surface water/groundwater systems is controlled not only by advective flow, but also by redox reactions that affect the partitioning of various elements between mobile and immobile phases. These processes have been examined in the context of a field project conducted by the U.S. Geological Survey (USGS) as part of the National Water-Quality Assessment (NAWQA) program. The Merced River flows out of Yosemite National Park and the Sierra Nevada foothills and into California's Central Valley, where it joins the San Joaquin River. Our field site is approximately twenty river kilometers from the confluence with the San Joaquin River. This deep alluvial plain has minimal topography. Agricultural development characterizes the land surrounding this reach of river; consequently, the hydrology is heavily influenced by irrigation. Riverbed groundwater samples were collected from ten wells aligned in two transects across the river located approximately 100 m apart. The wells were sampled from depths of 0.5 m, 1 m, and 3 m below the sediment-water interface. Groundwater flowpath samples were taken from wells positioned on a path perpendicular to the river and located 100 m, 500 m, and 1000 m from the river. The saturated groundwater system exists from 7 to 40 m below the surface and is confined below by a clay layer. Each well location samples from 3-5 depths in this surface aquifer. Samples were collected in December 2003, March-April, June-July, and October 2004. This served to provide an evenly-spaced sampling frequency over the course of a year, and also to allow observation of trends coinciding with the onset of winter, the spring runoff, and early and late summer irrigation. An initial survey of the elements in the riverbed samples was conducted using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS). Elements for further study were selected based on variability in this survey, either with respect to depth or location, as well as to cover a range of expected geochemical behaviors. Further ICP-MS measurements focused on eight elements: strontium, barium, uranium, molybdenum, manganese, iron, phosphorus, and bromine. Bromine is a conservative tracer. Molybdenum, manganese, and iron will precipitate when oxidized, and uranium will precipitate when reduced. Strontium and barium are not redox-active but may be affected by dissolution-precipitation and sorption reactions. Phosphorus is a nutrient that will cycle actively in areas of biological productivity. Generally, these elements appear to behave as expected based on physical waterflow and assumed redox conditions. The two transects of wells across the river bracket a zone of known denitrification, which implies that sediment conditions favor oxidation upriver and reduction downriver. This trend is borne out both by the redox-sensitive elements at each transect, and by the strontium and barium, which bind to precipitated iron and manganese oxides in oxidizing conditions and are released into the dissolved state in reducing conditions. The flowpath samples appear to be enriched in strontium, phosphorus, and bromine when compared to the riverbed samples, and they are depleted in manganese and iron.

Trace- and rare-earth element geochemistry and Pb-Pb dating of black shales and intercalated Ni-Mo-PGE-Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

NASA Astrophysics Data System (ADS)

Jiang, Shao-Yong; Chen, Yong-Quan; Ling, Hong-Fei; Yang, Jing-Hong; Feng, Hong-Zhen; Ni, Pei

2006-08-01

The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb-Pb isotope dating for the Ni-Mo-PGE-Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni-Mo-PGE-Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb-Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni-Mo-PGE-Au sulfide ores, and two Pb-Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni-Mo-PGE-Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.

The provenance of low-calcic black shales

NASA Astrophysics Data System (ADS)

Quinby-Hunt, M. S.; Wilde, P.

1991-04-01

The elemental concentration of sedimentary rocks depends on the varying reactivity of each element as it goes from the source through weathering, deposition, diagenesis, lithification, and even low rank metamorphism. However, non-reactive components of detrital particles ideally are characteristic of the original igneous source and thus are useful in provenance studies. To determine the source of detrital granitic and volcanic components of low-calcic (<1% CaCO3) marine black shales, the concentrations of apparently non-reactive (i.e. unaffected by diagenetic, redox and/or low-rank metamorphic processes) trace elements were examined using standard trace element discrimination diagrams developed for igneous rocks. The chemical data was obtained by neutron activation analyses of about 200 stratigraphically well-documented black shale samples from the Cambrian through the Jurassic. A La-Th-Sc ternary diagram distinguishes among contributions from the upper and bulk continental crust and the oceanic crust (Taylor and McLennan 1985). All the low-calcic black shales cluster within the region of the upper crust. Th-Hf-Co ternary diagrams also are commonly used to distinguish among the upper and bulk continental crust and the oceanic crust (Taylor and McLennan 1985). As Co is redox sensitive in black shale environments, it was necessary to substitute an immobile element (i.e. example Rb) in the diagram. With this substitution of black shales all cluster in the region of the upper continental crust. To determine the provenance of the granitic component (Pearce et al. 1984), plots of Ta vs Yb and Rb vs Yb + Ta shows a cluster at the junction of the boundaries separating the volcanic arc granite (VAG), syn-collision granite (syn-COLG), and within-plate granite (WPG) fields. The majority fall within the VAG field. There are no occurrences of ocean ridge granite (ORG). The minimal contribution of basalts to marine black shales is confirmed by the ternary Wood diagram Th-Hf/3-Ta (Wood et al. 1979). The black shales plot in a cluster in a high Th region outside the various basalt fields, which suggests contribution from the continental crust.

Assessment of major ions and trace elements in groundwater supplied to the Monterrey metropolitan area, Nuevo León, Mexico.

PubMed

Mora, Abrahan; Mahlknecht, Jürgen; Rosales-Lagarde, Laura; Hernández-Antonio, Arturo

2017-08-01

The Monterrey metropolitan area (MMA) is the third greatest urban area and the second largest economic city of Mexico. More than four million people living in this megacity use groundwater for drinking, industrial and household purposes. Thus, major ion and trace element content were assessed in order to investigate the main hydrochemical properties of groundwater and determine if groundwater of the area poses a threat to the MMA population. Hierarchical cluster analysis using all the groundwater chemical data showed five groups of water. The first two groups were classified as recharge waters (Ca-HCO 3 ) coming from the foothills of mountain belts. The third group was also of Ca-HCO 3 water type flowing through lutites and limestones. Transition zone waters of group four (Ca-HCO 3 -SO 4 ) flow through the valley of Monterrey, whereas discharge waters of group 5 (Ca-SO 4 ) were found toward the north and northeast of the MMA. Principal component analysis performed in groundwater data indicates four principal components (PCs). PC1 included major ions Si, Co, Se, and Zn, suggesting that these are derived by rock weathering. Other trace elements such as As, Mo, Mn, and U are coupled in PC2 because they show redox-sensitive properties. PC3 indicates that Pb and Cu could be the less mobile elements in groundwater. Although groundwater supplied to MMA showed a high-quality, high mineralized waters of group 5 have NO 3 - concentrations higher than the maximum value proposed by international guidelines and SO 4 2- , NO 3 - , and total dissolved solid concentrations higher than the maximum levels allowed by the Mexican normative.

Risk assessment of trace metals in an extreme environment sediment: shallow, hypersaline, alkaline, and industrial Lake Acıgöl, Denizli, Turkey.

PubMed

Budakoglu, Murat; Karaman, Muhittin; Kumral, Mustafa; Zeytuncu, Bihter; Doner, Zeynep; Yildirim, Demet Kiran; Taşdelen, Suat; Bülbül, Ali; Gumus, Lokman

2018-02-23

The major and trace element component of 48 recent sediment samples in three distinct intervals (0-10, 10-20, and 20-30 cm) from Lake Acıgöl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the < 60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Acıgöl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.

Cycling of oxyanion-forming trace elements in groundwaters from a freshwater deltaic marsh

NASA Astrophysics Data System (ADS)

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk; Kolker, Alexander S.; Cable, Jaye E.; Johannesson, Karen H.

2018-05-01

Pore waters and surface waters were collected from a freshwater system in southeastern Louisiana to investigate the geochemical cycling of oxyanion-forming trace elements (i.e., Mo, W, As, V). A small bayou (Bayou Fortier) receives input from a connecting lake (Lac des Allemands) and groundwater input at the head approximately 5 km directly south of the Mississippi River. Marsh groundwaters exchange with bayou surface water but are otherwise relatively isolated from outside hydrologic forcings, such as tides, storms, and effects from local navigation canals. Rather, redox processes in the marsh groundwaters appear to drive changes in trace element concentrations. Elevated dissolved S(-II) concentrations in marsh groundwaters suggest greater reducing conditions in the late fall and winter as compared to the spring and late summer. The data suggest that reducing conditions in marsh groundwaters initiate the dissolution of Fe(III)/Mn(IV) oxide/hydroxide minerals, which releases adsorbed and/or co-precipitated trace elements into solution. Once in solution, the fate of these elements is determined by complexation with aqueous species and precipitation with iron sulfide minerals. The trace elements remain soluble in the presence of Fe(III)- and SO42-- reducing conditions, suggesting that either kinetic limitations or complexation with aqueous ligands obfuscates the correlation between V and Mo sequestration in sediments with reducing or euxinic conditions.

Source/process apportionment of major and trace elements in sinking particles in the Sargasso sea

NASA Astrophysics Data System (ADS)

Huang, S.; Conte, M. H.

2009-01-01

Elemental composition of the particle flux at the Oceanic Flux Program (OFP) time-series site off Bermuda was measured from January 2002 to March 2005. Eighteen elements (Mg, Al, Si, P, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Sr, Cd, Ba and Pb) in sediment trap material from 500, 1500 and 3200 m depths were quantified using fusion-HR-ICPMS. Positive Matrix Factorization (PMF) was used to elucidate sources, elemental associations and processes that affect geochemical behavior in the water column. Results provide evidence for intense elemental cycling between the sinking flux material and the dissolved and suspended pools within mesopelagic and bathypelagic waters. Biological processing and remineralization rapidly deplete the sinking flux material in organic matter and associated elements (N, P, Cd, Zn) between 500 and 1500 m depth. Suspended particle aggregation, authigenic mineral precipitation, and chemical scavenging enriches the flux material in lithogenic minerals, barite and redox sensitive elements (Mn, Co, V, Fe). A large increase in the flux of lithogenic elements is observed with depth and confirms that the northeast Sargasso is a significant sink for advected continental materials, likely supplied via Gulf Stream circulation. PMF resolved major sources that contribute to sinking flux at all depths (carbonate, high-Mg carbonate, opal, organic matter, lithogenic material, and barite) as well as additional depth-specific elemental associations that contribute about half of the compositional variability in the flux. PMF solutions indicate close geochemical associations of barite-opal, Cd-P, Zn-Co, Zn-Pb and redox sensitive elements in the sinking flux material at 500 m depth. Major reorganizations of element associations occur as labile carrier phases break down and elements redistribute among new carrier phases deeper in the water column. Factor scores show strong covariation and similar temporal phasing among the three trap depths and indicate a tight coupling in particle flux compositional variability throughout the water column. Seasonality in flux composition is primarily driven by dilution of the lithogenic component with freshly-produced biogenic material during the late winter primary production maximum. Temporal trends in scores reveal subtle non-seasonal changes in flux composition occurring on month long timescales. This non-seasonal variability may be driven by changes in the biogeochemical properties of intermediate water masses that pass through the region and which affect rates of chemical scavenging and/or aggregation within the water column.

Contrasting Cu-Au and Sn-W Granite Metallogeny through the Zircon Geochemical and Isotopic Record

NASA Astrophysics Data System (ADS)

Gardiner, Nicholas; Hawkesworth, Chris; Robb, Laurence; Whitehouse, Martin; Roberts, Nick; Kirkland, Chris

2017-04-01

Magmatic genesis and evolution - mediated by geodynamic setting - exert a primary control on the propensity of granites to be metal fertile. A revolution in our understanding of these petrogenetic processes has been made through a range of mineral-based tools, most notably the common accessory mineral zircon. There is consequently considerable interest in whether the geochemical and isotopic compositions of zircon can be applied to metallogenic problems. The paired magmatic belts of Myanmar have broadly contrasting metallogenic affinities (Sn-W versus Cu-Au), and are interpreted to have formed on the accretionary margin of the subducting Neo-Tethys Ocean. They therefore present the opportunity to geochemically compare and contrast the zircon compositions in two end-member types of granite-hosted mineral deposits generated in collisional settings. We present an integrated zircon isotope (U-Pb, Lu-Hf, O) and trace element dataset that fingerprint: (a) source; (b) redox conditions; and (c) degree of fractionation. These variables all impact on magma fertility, and our key question to address is whether they can be reliably traced and calibrated within the Myanmar zircon record. Granitoid-hosted zircons from the I-type copper arc have juvenile ɛHf (+7 to +12) and mantle-like δ18O (5.3 ‰), whereas zircons from the S-type tin belt have low ɛHf (-7 to -13) and heavier δ18O (6.2-7.7 ‰). Plotting Hf versus U/Yb reaffirms that the tin belt magmas contain greater crustal contributions than the copper arc rocks. Links between whole rock Rb/Sr and zircon Eu/Eu* highlights that the latter can be used to monitor magma fractionation in systems that crystallize plagioclase (low Sr/Y). Ce/Ce* and Eu/Eu* in zircon are thus sensitive to redox and fractionation respectively, and can be used to evaluate the sensitivity of zircons to the metallogenic affinity of their host rocks. Tin contents that exceed the solubility limit are required in order to make a magmatic-hydrothermal deposit, and empirical observations suggest that this threshold may be marked by zircon Eu/Eu* values of ca. < 0.08. The isotope and trace element signatures of both magmatic and detrital zircons can be developed into a useful exploration tool.

Strontium and Trace Metals in the Mississippi River Mixing Zone

NASA Astrophysics Data System (ADS)

Xu, Y.; Marcantonio, F.

2001-12-01

Strontium is generally believed to be a conservative element, i.e., it is assumed that dissolved Sr moves directly from rivers through estuaries to the ocean. More recently, however, detailed sampling of rivers suggests a weak non-conservative behavior for Sr. Here, we present dissolved and suspended load Sr and trace metal data for samples retrieved along salinity transects in the estuarine mixing zone of the Mississippi River. Our cruises took place during times representing high, falling, and low Mississippi River discharge. Sr concentration and isotopic composition were analyzed for both dissolved particulate loads. Selected particle-reactive or redox-sensitive trace metals (Mn, Fe, U, V, Mo, Ti, and Pb) were analyzed simultaneously. In the dissolved load, Sr showed conservative behavior in both high- and low- discharge periods. Non-conservative behavior of Sr predominated during falling discharge in the summer. Significant positive correlations were found between Sr, Mo and Ti. U and V distributions were found to be essentially controlled by mixing of river water and seawater, but with significantly lower riverine concentrations during high-flow stage. Particulate element concentrations can be quite variable and heterogeneous. In this study, strong correlations were found between particulate Mn (and Fe) concentrations and particulate concentrations of Ti, U, V, and Pb. No such correlations with Mn (or Fe) were found for particulate Sr and Mo. There is a vast hypoxic zone along the coast of Louisiana in the Gulf of Mexico that exists during the summer months. Based on the Sr isotope systematics and the relationships between Sr and trace metals, we believe that this eutrophication may contribute to the non-conservative behaviors of Sr and other trace metals. We discuss the potential implications of this hypothesis on the Sr mass balance of present-day and past seawater.

A highly redox-heterogeneous ocean in South China during the early Cambrian (˜529-514 Ma): Implications for biota-environment co-evolution

NASA Astrophysics Data System (ADS)

Jin, Chengsheng; Li, Chao; Algeo, Thomas J.; Planavsky, Noah J.; Cui, Hao; Yang, Xinglian; Zhao, Yuanlong; Zhang, Xingliang; Xie, Shucheng

2016-05-01

The ;Cambrian Explosion; is known for rapid increases in the morphological disparity and taxonomic diversity of metazoans. It has been widely proposed that this biological event was a consequence of oxygenation of the global ocean, but this hypothesis is still under debate. Here, we present high-resolution Fe-S-C-Al-trace element geochemical records from the Jinsha (outer shelf) and Weng'an (outer shelf) sections of the early Cambrian Yangtze Platform, integrating these results with previously published data from six correlative sections representing a range of water depths (Xiaotan, Shatan, Dingtai, Yangjiaping, Songtao, and Longbizui). The integrated iron chemistry and redox-sensitive trace element data suggest that euxinic mid-depth waters dynamically coexisted with oxic surface waters and ferruginous deep waters during the earliest Cambrian, but that stepwise expansion of oxic waters commenced during Cambrian Stage 3 (∼ 521- 514 Ma). Combined with data from lower Cambrian sections elsewhere, including Oman, Iran and Canada, we infer that the global ocean exhibited a high degree of redox heterogeneity during the early Cambrian, consistent with low atmospheric oxygen levels (∼ 10- 40% of present atmospheric level, or PAL). A large spatial gradient in pyrite sulfur isotopic compositions (δ34Spy), which vary from a mean of - 12.0 ‰ in nearshore areas to + 22.5 ‰ in distal deepwater sections in lower Cambrian marine units of South China imply low concentrations and spatial heterogeneity of seawater sulfate, which is consistent with a limited oceanic sulfate reservoir globally. By comparing our reconstructed redox chemistry with fossil records from the lower Cambrian of South China, we infer that a stepwise oxygenation of shelf and slope environments occurred concurrently with a gradual increase in ecosystem complexity. However, deep waters remained anoxic and ferruginous even as macrozooplankton and suspension-feeding mesozooplankton appeared during Cambrian Stage 3. These findings suggest that the ;Cambrian Explosion; in South China may have been primarily a consequence of locally improved oxygenation of the ocean-surface layer rather than of the full global ocean. Our observations are inconsistent with predicted changes in ocean chemistry driven by early Cambrian animals, suggesting that the influence of early Cambrian animals on contemporaneous ocean chemistry, as proposed in previous studies, may be overly exaggerated.

Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

PubMed

Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

2014-02-15

The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Depositional environment and organic matter accumulation of Upper Ordovician–Lower Silurian marine shale in the Upper Yangtze Platform, South China

USGS Publications Warehouse

Li, Yangfang; Zhang, Tongwei; Ellis, Geoffrey S.; Shao, Deyong

2017-01-01

The main controlling factors of organic matter accumulation in the Upper Ordovician Wufeng–Lower Silurian Longmaxi Formations are complex and remain highly controversial. This study investigates the vertical variation of total organic carbon (TOC) content as well as major and trace element concentrations of four Ordovician–Silurian transition sections from the Upper Yangtze Platform of South China to reconstruct the paleoenvironment of these deposits and to improve our understanding of those factors that have influenced organic matter accumulation in these deposits.The residual TOC content of the Wufeng Formation averages 3.2% and ranges from 0.12 to 6.0%. The overlying lower Longmaxi Formation displays higher TOC content (avg. 4.4%), followed upsection by consistent and lower values that average 1.6% in the upper Longmaxi Formation. The concentration and covariation of redox-sensitive trace elements (Mo, U and V) suggest that organic-rich intervals of the Wufeng Formation accumulated under predominantly anoxic conditions. Organic-rich horizons of the lower Longmaxi Formation were deposited under strongly anoxic to euxinic conditions, whereas organic-poor intervals of the upper Longmaxi Formation accumulated under suboxic conditions. Positive correlations between redox proxies and TOC contents suggest that organic matter accumulation was predominantly controlled by preservation. Barium excess (Baxs) values indicate high paleoproductivity throughout the entire depositional sequence, with an increase in the lower Longmaxi Formation. Increased productivity may have been induced by enhanced P recycling, as evidenced by elevated Corg/Ptot ratios. Mo–U covariation and Mo/TOC values reveal that the Wufeng Formation was deposited under extremely restricted conditions, whereas the Longmaxi Formation accumulated under moderately restricted conditions. During the Late Ordovician, the extremely restricted nature of ocean circulation on the Upper Yangtze Platform in tandem with enhanced stratification of the water column promoted anoxic conditions favorable for the preservation of organic matter. During Early Silurian time, organic matter accumulation was principally controlled by changes in sea level, which affected terrigenous flux, redox conditions, and the degree of nutrition recycling.

Spatial distribution pattern of vanadium in hydric landscapes

NASA Astrophysics Data System (ADS)

Fiedler, Sabine; Breuer, Jörn; Palmer, Iris; Berger, Jochen

2010-05-01

The geochemical behavior of the trace element vanadium (V) is strongly influenced by its oxidation state (+2 to +5). Consequently, oxidation/reduction reactions play an important role in controlling the mobilization and immobilization of V in soils. Translocation processes of V within soil profiles (pedons), including podzolization and clay illuviation, are well-documented. With regard to its lateral redistribution in landscapes, V is widely regarded as being immobile. Our investigation focused on the fate of V along a moisture gradient in different temperate humid spruce forest ecosystems in Southwest Germany (MAP 1,200-1,600 mm, MAT 6°C). The areas under investigation are characterized by lateral water flow, caused by a physically pre-weathered periglacial layer with poor water-permeability characteristics at the interface between pedo- and lithosphere. We selected different catenas derived from sandstone, gneiss, and granite, respectively. The soil associations occur along moderately inclined slopes and include common forest soils of three redox categories: an anaerobic Histosol, oxic Cambisols, and Stagnosols with an intermediate redox state. The soils are linked to each other by the lateral subsurface transport of solutes, which allows the investigation of the horizontal (i.e. within pedons) and lateral redistribution (i.e. between pedons) of the redox-sensitive elements V and iron (Fe). The redox potential of V and Fe in different soil depths along the hydrological pathway was both measured in the field and subsequently analyzed in 48 soil horizons to deduce the total content of V and Fe using aqua-regia digestion and element spectrometry (ICP-OES and ICP-MS). The different parent materials result in significant differences in V content. The V content in the sandstone soils (0.2 - 30 mg kg-1) was lower than the V content in granite and gneiss soils (up to 75 and 100 mg kg-1, respectively). Our results demonstrate that V is a highly mobile element in hydric landscapes. Independent from the parent material, we found a distinct spatial pattern of V, which reflected that of the local redox environment: Horizons/pedons with oxic conditions revealed a positive correlation between V content and Fe content. In this case, iron oxides act as an important sink for dissolved V which originated from other locations of the catena. Poorly drained soils, such as Stagnosols for example, promote both Fe and V reduction, which is coupled to their removal from the pedons by leaching. It can be demonstrated that the element-specific Eh window for differential reduction is very narrow. The spatial distribution of both elements shows that high V contents are often associated with low Fe contents. It is therefore assumed that a reducing environment promotes Fe3+ reduction, while maintaining while maintaining V stable.

Quantification of trace elements and speciation of iron in atmospheric particulate matter

NASA Astrophysics Data System (ADS)

Upadhyay, Nabin

Trace metal species play important roles in atmospheric redox processes and in the generation of oxidants in cloud systems. The chemical impact of these elements on atmospheric and cloud chemistry is dependent on their occurrence, solubility and speciation. First, analytical protocols have been developed to determine trace elements in particulate matter samples collected for carbonaceous analysis. The validated novel protocols were applied to the determination of trace elements in particulate samples collected in the remote marine atmosphere and urban areas in Arizona to study air pollution issues. The second part of this work investigates on solubility and speciation in environmental samples. A detailed study on the impact of the nature and strength of buffer solutions on solubility and speciation of iron lead to a robust protocol, allowing for comparative measurements in matrices representative of cloud water conditions. Application of this protocol to samples from different environments showed low iron solubility (less than 1%) in dust-impacted events and higher solubility (5%) in anthropogenically impacted urban samples. In most cases, Fe(II) was the dominant oxidation state in the soluble fraction of iron. The analytical protocol was then applied to investigate iron processing by fogs. Field observations showed that only a small fraction (1%) of iron was scavenged by fog droplets for which each of the soluble and insoluble fraction were similar. A coarse time resolution limited detailed insights into redox cycling within fog system. Overall results suggested that the major iron species in the droplets was Fe(1I) (80% of soluble iron). Finally, the occurrence and sources of emerging organic pollutants in the urban atmosphere were investigated. Synthetic musk species are ubiquitous in the urban environment (less than 5 ng m-3) and investigations at wastewater treatment plants showed that wastewater aeration basins emit a substantial amount of these species to the atmosphere.

Selective separation of iron from uranium in quantitative determination of traces of uranium by alpha spectrometry in soil/sediment sample.

PubMed

Singhal, R K; Narayanan, Usha; Karpe, Rupali; Kumar, Ajay; Ranade, A; Ramachandran, V

2009-04-01

During this work, controlled redox potential methodology was adopted for the complete separation of traces of uranium from the host matrix of mixed hydroxide of Iron. Precipitates of Fe(+2) and Fe(+3) along with other transuranic elements were obtained from acid leached solution of soil by raising the pH to 9 with 14N ammonia solution. The concentration of the uranium observed in the soil samples was 200-600 ppb, whereas in sediment samples, the concentration range was 61-400 ppb.

Selenium as a versatile center in fluorescence probe for the redox cycle between HClO oxidative stress and H2S repair.

PubMed

Lou, Zhangrong; Li, Peng; Han, Keli

2015-01-01

Selenium is a biologically important trace element and acts as an active center of glutathione peroxidase (GPx). GPx is the important antioxidant enzyme to protect organisms from oxidative damage via catalyzing the reaction between ROS and glutathione (GSH). Mimicking the oxidation-reduction cycles of the versatile selenium core in GPx, we can develop fluorescence probes to detect oxidation and reduction events in living systems. The cellular redox balance between hypochloric acid (HClO) and hydrogen sulfide (H2S) has broad implications in human health and diseases, such as Alzheimer's disease (AD). Therefore, to further investigate the roles of this redox balance and understand the pathogenesis of neurodegenerative diseases, it is necessary to detect the redox state between HClO and H2S in real time. We have developed a reversible fluorescence probe MPhSe-BOD for imaging of the redox cycle between HClO and H2S based on oxidation and reduction of selenide in living cells.

Catechol-chitosan redox capacitor for added amplification in electrochemical immunoanalysis.

PubMed

Yan, Kun; Liu, Yi; Guan, Yongguang; Bhokisham, Narendranath; Tsao, Chen-Yu; Kim, Eunkyoung; Shi, Xiao-Wen; Wang, Qin; Bentley, William E; Payne, Gregory F

2018-05-22

Antibodies are common recognition elements for molecular detection but often the signals generated by their stoichiometric binding must be amplified to enhance sensitivity. Here, we report that an electrode coated with a catechol-chitosan redox capacitor can amplify the electrochemical signal generated from an alkaline phosphatase (AP) linked immunoassay. Specifically, the AP product p-aminophenol (PAP) undergoes redox-cycling in the redox capacitor to generate amplified oxidation currents. We estimate an 8-fold amplification associated with this redox-cycling in the capacitor (compared to detection by a bare electrode). Importantly, this capacitor-based amplification is generic and can be coupled to existing amplification approaches based on enzyme-linked catalysis or magnetic nanoparticle-based collection/concentration. Thus, the capacitor should enhance sensitivities in conventional immunoassays and also provide chemical to electrical signal transduction for emerging applications in molecular communication. Copyright © 2018 Elsevier B.V. All rights reserved.

Marine chemistry of the permian phosphoria formation and basin, Southeast Idaho

USGS Publications Warehouse

Piper, D.Z.

2001-01-01

Major components in the Meade Peak Member of the Phosphoria Formation are apatite, dolomite, calcite, organic matter, and biogenic silica-a marine fraction; and aluminosilicate quartz debris-a terrigenous fraction. Samples from Enoch Valley, in southeast Idaho, have major element oxide abundances of Al2O3, Fe2O3, K2O, and TiO2 that closely approach the composition of the world shale average. Factor analysis further identifies the partitioning of several trace elements-Ba, Ga, Li, Sc, and Th and, at other sites in southeast Idaho and western Wyoming, B, Co, Cs, Hf, Rb, and Ta-totally into this fraction. Trace elements that fail to show such correlations or factor loadings include Ag, As, Cd, Cr, Cu, Mo, Ni, Se, the rare earth elements (REE), U, V, and Zn. Their terrigenous contribution is determined from minimum values of trace elements versus the terrigenous fraction. These minima too define trace element concentrations in the terrigenous fraction that approximately equal their concentrations in the world shale average. The marine fraction of trace elements represents the difference between the bulk trace element content of a sample and the terrigenous contribution. Of the trace elements enriched above a terrigenous contribution, Ag, Cr, Cu, Mo, and Se show strong loadings on the factor with an organic matter loading and U and the REE on the factor with a strong apatite loading. Cd, Ni, V, and Zn do not show a strong correlation with any of the marine components but are, nonetheless, strongly enriched above a terrigenous contribution. Interelement relationships between the trace elements identify two seawater sources-planktonic debris and basinal bottom water. Relationships between Cd, Cu, Mo, Zn, and possibly Ni and Se suggest a solely biogenic source. Their accumulation rates, and that of PO3-4, further identify the level of primary productivity as having been moderate and the residence time of water in the basin at 4.5 yr. Enrichments of Cr, U, V, and the REE, above both terrigenous and biogenic contributions, define bottom-water redox conditions as having been oxygen depleted, that is, denitrifying but not sulfate reducing.

The geochemistry of redox sensitive trace metals in sediments

NASA Astrophysics Data System (ADS)

Morford, Jennifer L.; Emerson, Steven

1999-06-01

We analyzed the redox sensitive elements V, Mo, U, Re and Cd in surface sediments from the Northwest African margin, the U.S. Northwest margin and the Arabian Sea to determine their response under a range of redox conditions. Where oxygen penetrates 1 cm or less into the sediments, Mo and V diffuse to the overlying water as Mn is reduced and remobilized. Authigenic enrichments of U, Re and Cd are evident under these redox conditions. With the onset of sulfate reduction, all of the metals accumulate authigenically with Re being by far the most enriched. General trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes: oxic, reducing where oxygen penetrates ≤1 cm, and anoxic conditions. Using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations, we calculate the area of sediments below 1000 m water depth in which oxygen penetration is ≤1 cm to be 4% of the ocean floor. We conclude that sediments where oxygen penetrates ≤1 cm release Mn, V and Mo to seawater at rates of 140%-260%, 60%-150% and 5%-10% of their respective riverine fluxes, using the authigenic metal concentrations and accumulation rates from this work and other literature. These sediments are sinks for Re, Cd and U, with burial fluxes of 70%-140%, 30%-80% and 20%-40%, respectively, of their dissolved riverine inputs. We modeled the sensitivity of the response of seawater Re, Cd and V concentrations to changes in the area of reducing sediments where oxygen penetrates ≤1 cm. Our analysis suggests a negligible change in seawater Re concentration, whereas seawater concentrations of Cd and V could have decreased and increased, respectively, by 5%-10% over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10%-20% if the area increased by a factor of 3. The concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of Cd/Ca and V/Ca ratios observed in foraminifera shells over the last 40 kyr. This implies that the area of reducing sediments in the ocean deeper than 1000 m (4%) has not been greater than twice the present value in the recent past.

Fate of redox-sensitive elements in two different East-African wetland systems

NASA Astrophysics Data System (ADS)

Glasner, Björn; Fiedler, Sabine

2017-04-01

We expect that an intensified cropping alters soil pH and Eh, and negatively affects the production potential of wetlands. Therefore, we investigated the redox-conditions in combination with the fate of different redox-sensitive elements in two prototypical wetland systems that show a high potential for food production in East-Africa. While the floodplains (observed near Ifakara, Kilombero District/Tanzania) serve as major crop producing areas in the region, the Inland Valleys (observed in Namulonge, Central District/Uganda) show a high potential for future production. Both systems have been divided into three positions; the fringe near to the slope, the center near to the river and the middle in between these two positions. In order to get a better understanding of the two systems we installed continuously measuring redox-electrodes in three different positions within both systems. Additionally, the fate of mineral elements was measured using ion-exchange resins with an installation period of 3-4 months. At the Tanzanian field sites the Eh-potential shows one major dry period with moderately reducing to well drained conditions in all sampling depths (10, 30, and 50 cm below ground) in all three positions during the measuring period from March 2015 to Dec 2016. Starting with the rains the Eh-potential drops from 700 mV (in 10 and 30 cm depth) to reducing conditions at all three sites - with intermediate brakes in the middle and fringe positions, showing that there has been no rain during these periods. At the Ugandan field sites the Eh-potential shows more fluctuations during the measuring period, especially in the center position in 2015 ( 750 to -200 mV in 30 and 50 cm depth). Having just the Eh-potential from the first 30 cm below ground it is not really possible to differentiate between dry- and rainy-seasons at the sites. The fate of redox-sensitive elements (Fe, Mn, and P) does not always correlate with the overall Eh-conditions (median) of the installation period. Short time events may play a crucial role in the fate of these elements.

Geochemistry of environmentally sensitive trace elements in Permian coals from the Huainan coalfield, Anhui, China

USGS Publications Warehouse

Chen, J.; Liu, Gaisheng; Jiang, M.; Chou, C.-L.; Li, H.; Wu, B.; Zheng, Lingyun; Jiang, D.

2011-01-01

To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals. ?? 2011 Elsevier B.V.

Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite

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

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-03-26

Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occursmore » near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.« less

Origin of enormous trace metal enrichments in weathering mantles of Jurassic carbonates: evidence from Sr, Nd and Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, C.; Stille, P.; Juilleret, J.; Iffly, J.; Perrone, T.; Morvan, G.

2013-12-01

Weathering mantels are widespread worldwide and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved carbonate rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual content of associated trace elements in this type of weathering mantle. For instance, these enrichments can represent about five times the content of the underlying Bajocian to Oxfordian limestone/marl complexes, which have been relatively poorly studied compared to weathering mantle developed on magmatic bedrocks. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources (saprolite, Bajocian silty marls and limestones, atmospheric particles deposition...). Of special interest has also been the origin of trace metals and the processes causing their enrichments. Especially Rare Earth Element (REE) distribution patterns and Sr, Nd and Pb isotope ratios are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments shall help to identify mobile phases in the soil system. This may inform on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. Trace metal migration and enrichments were studied on a cambisol developing on an underlying Jurassic limestone. The base is strongly enriched among others in rare earth elements (ΣREE: 2640ppm) or redox-sensitive elements such as Fe (44 wt.%), V (920ppm), Cr (700ppm), Zn (550ppm), As (260ppm), Co (45ppm) and Cd (2.4ppm). The underlying limestone and marl show, compared to average world carbonates, enrichments in the same elements and trace element distribution patterns similar to the soil suggesting their close genetic relationship. Pb, Sr and Nd isotope data allow to identify three principal components in the soil: a silicate-rich phase at close to the surface, a strongly trace metal enriched component at the bottom of the soil profile and an anthropogenic, atmosphere- derived component detected in the soil leachates. The isotopic mixing curves defined by the soil samples point to the close genetic connection between upper and lowermost soil horizons. The Nd isotopic composition of the leachates of all soil horizons are in contrast to the untreated soil and residual soil samples very homogeneous suggesting that the leachable phases of the upper and lower soil horizons are genetically connected. The downward migration of the trace metals is stopped at this soil level due to the presence of important secondary calcite precipitations, smectite and Fe-oxide accumulations. Mass balance calculations indicate that the enrichment process goes along with a volume increase relative to the bottom soil horizons.

Redox-mediated signal transduction by cardiovascular Nox NADPH oxidases.

PubMed

Brandes, Ralf P; Weissmann, Norbert; Schröder, Katrin

2014-08-01

The only known function of the Nox family of NADPH oxidases is the production of reactive oxygen species (ROS). Some Nox enzymes show high tissue-specific expression and the ROS locally produced are required for synthesis of hormones or tissue components. In the cardiovascular system, Nox enzymes are low abundant and function as redox-modulators. By reacting with thiols, nitric oxide (NO) or trace metals, Nox-derived ROS elicit a plethora of cellular responses required for physiological growth factor signaling and the induction and adaptation to pathological processes. The interactions of Nox-derived ROS with signaling elements in the cardiovascular system are highly diverse and will be detailed in this article, which is part of a Special Issue entitled "Redox Signalling in the Cardiovascular System". Copyright © 2014 Elsevier Ltd. All rights reserved.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India.

PubMed

Gurumurthy, G P; Balakrishna, K; Tripti, M; Audry, Stéphane; Riotte, Jean; Braun, J J; Udaya Shankar, H N

2014-04-01

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Arsenic, vanadium, iron, and manganese biogeochemistry in a deltaic wetland, southern Louisiana, USA

DOE PAGES

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk; ...

2017-04-05

Geochemical cycling of the redox-sensitive trace elements arsenic (As) and vanadium (V) was examined in shallow pore waters from a marsh in an interdistributary embayment of the lower Mississippi River Delta. In particular, we explore how redox changes with depth and distance from the Mississippi River affect As and V cycling in the marsh pore waters. Previous geophysical surveys and radon mass balance calculations suggested that Myrtle Grove Canal and bordering marsh receive fresh groundwater, derived in large part from seepage of the Mississippi River, which subsequently mixes with brackish waters of Barataria Bay. In addition, the redox geochemistry ofmore » pore waters in the wetlands is affected by Fe and S cycling in the shallow subsurface (0-20 cm). Sediments with high organic matter content undergo SO 4 2- reduction, a process ubiquitous in the shallow subsurface but largely absent at greater depths (~3 m). Instead, at depth, in the absence of organic-rich sediments, Fe concentrations are elevated, suggesting that reduction of Fe(III) oxides/oxyhydroxides buffers redox conditions. Arsenic and V cycling in the shallow subsurface are decoupled from their behavior at depth, where both V and As appear to be removed from solution by either diffusion or adsorption onto, or co-precipitation with, authigenic minerals within the deeper aquifer sediments. Pore water As concentrations are greatest in the shallow subsurface (e.g., up to 315 nmol kg -1 in the top ~20 cm of the sediment) but decrease with depth, reaching values <30 nmol kg -1 at depths between 3 and 4 m. Vanadium concentrations appear to be tightly coupled to Fe cycling in the shallow subsurface, but at depth, V may be adsorbed to clay or sedimentary organic matter (SOM). Diffusive fluxes are calculated to examine the export of trace elements from the shallow marsh pore waters to the overlying canal water that floods the marsh. The computed fluxes suggest that the shallow sediment serves as a source of Fe, Mn, and As to the surface waters, whereas the sediments act as a sink for V. Iron and Mn fluxes are substantial, ranging from 50 to 30,000 and 770 to 4,300 nmol cm -2 day -1, respectively, whereas As fluxes are much less, ranging from 2.1 to 17 nmol cm -2 day -1. Vanadium fluxes range from 3.0 nmol cm -2 day -1 directed into the sediment to 1.7 nmol cm -2 day -1 directed out of the sediment« less

Arsenic, vanadium, iron, and manganese biogeochemistry in a deltaic wetland, southern Louisiana, USA

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

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk

Geochemical cycling of the redox-sensitive trace elements arsenic (As) and vanadium (V) was examined in shallow pore waters from a marsh in an interdistributary embayment of the lower Mississippi River Delta. In particular, we explore how redox changes with depth and distance from the Mississippi River affect As and V cycling in the marsh pore waters. Previous geophysical surveys and radon mass balance calculations suggested that Myrtle Grove Canal and bordering marsh receive fresh groundwater, derived in large part from seepage of the Mississippi River, which subsequently mixes with brackish waters of Barataria Bay. In addition, the redox geochemistry ofmore » pore waters in the wetlands is affected by Fe and S cycling in the shallow subsurface (0-20 cm). Sediments with high organic matter content undergo SO 4 2- reduction, a process ubiquitous in the shallow subsurface but largely absent at greater depths (~3 m). Instead, at depth, in the absence of organic-rich sediments, Fe concentrations are elevated, suggesting that reduction of Fe(III) oxides/oxyhydroxides buffers redox conditions. Arsenic and V cycling in the shallow subsurface are decoupled from their behavior at depth, where both V and As appear to be removed from solution by either diffusion or adsorption onto, or co-precipitation with, authigenic minerals within the deeper aquifer sediments. Pore water As concentrations are greatest in the shallow subsurface (e.g., up to 315 nmol kg -1 in the top ~20 cm of the sediment) but decrease with depth, reaching values <30 nmol kg -1 at depths between 3 and 4 m. Vanadium concentrations appear to be tightly coupled to Fe cycling in the shallow subsurface, but at depth, V may be adsorbed to clay or sedimentary organic matter (SOM). Diffusive fluxes are calculated to examine the export of trace elements from the shallow marsh pore waters to the overlying canal water that floods the marsh. The computed fluxes suggest that the shallow sediment serves as a source of Fe, Mn, and As to the surface waters, whereas the sediments act as a sink for V. Iron and Mn fluxes are substantial, ranging from 50 to 30,000 and 770 to 4,300 nmol cm -2 day -1, respectively, whereas As fluxes are much less, ranging from 2.1 to 17 nmol cm -2 day -1. Vanadium fluxes range from 3.0 nmol cm -2 day -1 directed into the sediment to 1.7 nmol cm -2 day -1 directed out of the sediment« less

Levels of major and trace elements, including rare earth elements, and ²³⁸U in Croatian tap waters.

PubMed

Fiket, Željka; Rožmarić, Martina; Krmpotić, Matea; Benedik, Ljudmila

2015-05-01

Concentrations of 46 elements, including major, trace, and rare earth elements, and (238)U in Croatian tap waters were investigated. Selected sampling locations include tap waters from various hydrogeological regions, i.e., different types of aquifers, providing insight into the range of concentrations of studied elements and (238)U activity concentrations in Croatian tap waters. Obtained concentrations were compared with the Croatian maximum contaminant levels for trace elements in water intended for human consumption, as well as WHO and EPA drinking water standards. Concentrations in all analyzed tap waters were found in accordance with Croatian regulations, except tap water from Šibenik in which manganese in concentration above maximum permissible concentration (MPC) was measured. Furthermore, in tap water from Osijek, levels of arsenic exceeded the WHO guidelines and EPA regulations. In general, investigated tap waters were found to vary considerably in concentrations of studied elements, including (238)U activity concentrations. Causes of variability were further explored using statistical methods. Composition of studied tap waters was found to be predominately influenced by hydrogeological characteristics of the aquifer, at regional and local level, the existing redox conditions, and the household plumbing system. Rare earth element data, including abundances and fractionation patterns, complemented the characterization and facilitated the interpretation of factors affecting the composition of the analyzed tap waters.

Trace elemental analysis of human breast cancerous blood by advanced PC-WDXRF technique

NASA Astrophysics Data System (ADS)

Singh, Ranjit; Kainth, Harpreet Singh; Prasher, Puneet; Singh, Tejbir

2018-03-01

The objective of this work is to quantify the trace elements of healthy and non-healthy blood samples by using advanced polychromatic source based wavelength dispersive X-ray fluorescence (PC-WDXRF) technique. The imbalances in trace elements present in the human blood directly or indirectly lead to the carcinogenic process. The trace elements 11Na, 12Mg, 15P, 16S, 17Cl, 19K, 20Ca, 26Fe, 29Cu and 30Zn are identified and their concentrations are estimated. The experimental results clearly discuss the variation and role of various trace elements present in the non-healthy blood samples relative to the healthy blood samples. These results establish future guidelines to probe the possible roles of essential trace elements in the breast carcinogenic processes. The instrumental sensitivity and detection limits for measuring the elements in the atomic range 11 ≤ Z ≤ 30 have also been discussed in the present work.

The influence of stream bed geomorphology on chemical species within the hyporheic zone over time and space

NASA Astrophysics Data System (ADS)

Quick, A. M.; Reeder, W. J.; Farrell, T. B.; Benner, S. G.; Tonina, D.; Feris, K. P.

2017-12-01

The hyporheic zone is well established as an important zone of biogeochemical activity in streams and rivers. Multiple large scale flume experiments were carried out to mimic bedform-controlled hyporheic zones in small streams. The laboratory setting allowed for geochemical measurement resolution and replicates that would not be possible in a natural setting. Two flume experiments that consisted of three small streams with variable sizes of bedform dunes were carried out in which chemical species were measured in the surface water and along hyporheic flow lines in the subsurface. The species measured included dissolved oxygen, pH, alkalinity, major cations (Na+, Mg2+, Ca2+, K+, Si4+, Al3+), anions (NO3-, NO2-, SO42-, PO43-, Cl-), and many trace elements (As, Sr, Co, Ni, Cu, Zn, Pb, U, V). Observed spatial and temporal trends reflect microbiological processes, changing redox conditions, and chemical weathering. In general, microbial respiration causes DO to decrease with residence time, leading to aerobic and anaerobic zones that influence redox-sensitive species and pH gradients that influence mineral solubility. Most other species concentrations, including those of major cations and trace elements, increase with residence time and generally decrease over time elapsed during the experiment. The different dune morphologies dictate flow velocities in the hyporheic zone; for most species, steeper dunes with higher velocities had lower concentrations at the end of the experiment, indicating the role of dune shape in the weathering rates of minerals in hyporheic sediment and the concentrations of dissolved species entering the surface water over time. Many of the observed trends can be applied, at least qualitatively, to understanding how these species will behave in natural settings. This insight will contribute to the understanding of many of the applications of the hyporheic zone (e.g. bioremediation, habitat, greenhouse gas emissions, etc.).

Simultaneous cryo X-ray ptychographic and fluorescence microscopy of green algae

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

Deng, Junjing; Vine, David J.; Chen, Si

Trace metals play important roles in normal and in disease-causing biological functions. X-ray fluorescence microscopy reveals trace elements with no dependence on binding affinities (unlike with visible light fluorophores) and with improved sensitivity relative to electron probes. However, X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular material. Here we show that X-ray ptychography can be combined with fluorescence to image both cellular structure and trace element distribution in frozen-hydrated cells at cryogenic temperatures, with high structural and chemical fidelity. Ptychographic reconstruction algorithms deliver phase and absorption contrast images at a resolutionmore » beyond that of the illuminating lens or beam size. Using 5.2-keV X-rays, we have obtained sub-30-nm resolution structural images and ~90-nm-resolution fluorescence images of several elements in frozen-hydrated green algae. Finally, this combined approach offers a way to study the role of trace elements in their structural context.« less

Simultaneous cryo X-ray ptychographic and fluorescence microscopy of green algae

DOE PAGES

Deng, Junjing; Vine, David J.; Chen, Si; ...

2015-02-24

Trace metals play important roles in normal and in disease-causing biological functions. X-ray fluorescence microscopy reveals trace elements with no dependence on binding affinities (unlike with visible light fluorophores) and with improved sensitivity relative to electron probes. However, X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular material. Here we show that X-ray ptychography can be combined with fluorescence to image both cellular structure and trace element distribution in frozen-hydrated cells at cryogenic temperatures, with high structural and chemical fidelity. Ptychographic reconstruction algorithms deliver phase and absorption contrast images at a resolutionmore » beyond that of the illuminating lens or beam size. Using 5.2-keV X-rays, we have obtained sub-30-nm resolution structural images and ~90-nm-resolution fluorescence images of several elements in frozen-hydrated green algae. Finally, this combined approach offers a way to study the role of trace elements in their structural context.« less

Simultaneous cryo X-ray ptychographic and fluorescence microscopy of green algae

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

Deng, Junjing; Vine, David J.; Chen, Si

Trace metals play important roles in normal and in disease-causing biological functions. X-ray fluorescence microscopy reveals trace elements with no dependence on binding affinities (unlike with visible light fluorophores) and with improved sensitivity relative to electron probes. However, X-ray fluorescence is not very sensitive for showing the light elements that comprise the majority of cellular material. Here we show that X-ray ptychography can be combined with fluorescence to image both cellular structure and trace element distribution in frozen-hydrated cells at cryogenic temperatures, with high structural and chemical fidelity. Ptychographic reconstruction algorithms deliver phase and absorption contrast images at a resolutionmore » beyond that of the illuminating lens or beam size. Using 5.2-keV X-rays, we have obtained sub-30-nm resolution structural images and similar to 90-nm-resolution fluorescence images of several elements in frozen-hydrated green algae. This combined approach offers a way to study the role of trace elements in their structural context.« less

Bioessential element-depleted ocean following the euxinic maximum of the end-Permian mass extinction

NASA Astrophysics Data System (ADS)

Takahashi, Satoshi; Yamasaki, Shin-ichi; Ogawa, Yasumasa; Kimura, Kazuhiko; Kaiho, Kunio; Yoshida, Takeyoshi; Tsuchiya, Noriyoshi

2014-05-01

We describe variations in trace element compositions that occurred on the deep seafloor of palaeo-superocean Panthalassa during the end-Permian mass extinction based on samples of sedimentary rock from one of the most continuous Permian-Triassic boundary sections of the pelagic deep sea exposed in north-eastern Japan. Our measurements revealed low manganese (Mn) enrichment factor (normalised by the composition of the average upper continental crust) and high cerium anomaly values throughout the section, suggesting that a reducing condition already existed in the depositional environment in the Changhsingian (Late Permian). Other redox-sensitive trace-element (vanadium [V], chromium [Cr], molybdenum [Mo], and uranium [U]) enrichment factors provide a detailed redox history ranging from the upper Permian to the end of the Permian. A single V increase (representing the first reduction state of a two-step V reduction process) detected in uppermost Changhsingian chert beds suggests development into a mildly reducing deep-sea condition less than 1 million years before the end-Permian mass extinction. Subsequently, a more reducing condition, inferred from increases in Cr, V, and Mo, developed in overlying Changhsingian grey siliceous claystone beds. The most reducing sulphidic condition is recognised by the highest peaks of Mo and V (second reduction state) in the uppermost siliceous claystone and overlying lowermost black claystone beds, in accordance with the end-Permian mass extinction event. This significant increase in Mo in the upper Changhsingian led to a high Mo/U ratio, much larger than that of modern sulphidic ocean regions. This trend suggests that sulphidic water conditions developed both at the sediment-water interface and in the water column. Above the end-Permian mass extinction horizon, Mo, V and Cr decrease significantly. On this trend, we provide an interpretation of drawdown of these elements in seawater after the massive element precipitation event during the end-Permian maximum development of the reducing water column. A decrease in the Mo/U ratio despite enrichment of Mo and U also supports that of Mo. Calculations of the total amounts of these elements precipitated compared with the global seawater inventory suggest that when more than 6-10% of the global ocean became euxinic as much as the study section, most of the dissolved elements would precipitate into sediments, resulting in a global element-depleted seawater condition. Mo, V, and Cr act as bioessential elements for both primary producers and animals. The continuing reducing water column and the lack of bioessential elements could have had a considerable effect on primary producer turnover and marine life metabolism not only in the pelagic environment, but also in surrounding marine environments.

Statistical analysis of iron geochemical data suggests limited late Proterozoic oxygenation

NASA Astrophysics Data System (ADS)

Sperling, Erik A.; Wolock, Charles J.; Morgan, Alex S.; Gill, Benjamin C.; Kunzmann, Marcus; Halverson, Galen P.; MacDonald, Francis A.; Knoll, Andrew H.; Johnston, David T.

2015-07-01

Sedimentary rocks deposited across the Proterozoic-Phanerozoic transition record extreme climate fluctuations, a potential rise in atmospheric oxygen or re-organization of the seafloor redox landscape, and the initial diversification of animals. It is widely assumed that the inferred redox change facilitated the observed trends in biodiversity. Establishing this palaeoenvironmental context, however, requires that changes in marine redox structure be tracked by means of geochemical proxies and translated into estimates of atmospheric oxygen. Iron-based proxies are among the most effective tools for tracking the redox chemistry of ancient oceans. These proxies are inherently local, but have global implications when analysed collectively and statistically. Here we analyse about 4,700 iron-speciation measurements from shales 2,300 to 360 million years old. Our statistical analyses suggest that subsurface water masses in mid-Proterozoic oceans were predominantly anoxic and ferruginous (depleted in dissolved oxygen and iron-bearing), but with a tendency towards euxinia (sulfide-bearing) that is not observed in the Neoproterozoic era. Analyses further indicate that early animals did not experience appreciable benthic sulfide stress. Finally, unlike proxies based on redox-sensitive trace-metal abundances, iron geochemical data do not show a statistically significant change in oxygen content through the Ediacaran and Cambrian periods, sharply constraining the magnitude of the end-Proterozoic oxygen increase. Indeed, this re-analysis of trace-metal data is consistent with oxygenation continuing well into the Palaeozoic era. Therefore, if changing redox conditions facilitated animal diversification, it did so through a limited rise in oxygen past critical functional and ecological thresholds, as is seen in modern oxygen minimum zone benthic animal communities.

Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples.

PubMed

Boulyga, Sergei F; Heilmann, Jens; Prohaska, Thomas; Heumann, Klaus G

2007-10-01

A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for (35)Cl+ to more than 6 x 10(5) cps for (238)U+ for 1 microg of trace element per gram of coal sample. Detection limits vary from 450 ng g(-1) for chlorine and 18 ng g(-1) for sulfur to 9.5 pg g(-1) for mercury and 0.3 pg g(-1) for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis.

Geochemistry of East Antarctic Margin Sediments Spanning the Eocene Oligocene Transition.

NASA Astrophysics Data System (ADS)

Light, J. J.; Passchier, S.

2016-12-01

The Eocene Oligocene Transition (EOT) 34 million years ago (Ma), marked the global climate change from greenhouse to icehouse, and the full establishment of the East Antarctic Ice Sheet (EAIS). The initiation of the EAIS during the EOT is believed to have been a step-wise transition; however, data resolution is low and merits the need for further study. The purpose of this study is to expand upon existing knowledge of EAIS dynamics spanning the EOT by creating a higher resolution geochemical record of cores taken from continental shelf sites 1166 in Prydz Bay and U1360 from the Wilkes Land margin. We used Inductively Coupled Plasma Optical Emission Spectrometry and Mass Spectrometry (ICP-OES/ ICP-MS) to determine the bulk chemical composition of samples. Results were used to calculate the Chemical Index of Alteration (CIA), Al2O3/TiO2 ratios, and trace elemental variation down core. CIA values for the early Oligocene in Site U1360 indicate an arid colder environment less likely to be chemically weathered. In contrast, Hole 1166A shows values similar to average shales that increase up core and abruptly decrease at the overlying Neogene diamict, suggesting a warmer more humid environment at Prydz Bay during the late Eocene. Al2O3/TiO2 ratios were used to evaluate mud provenance changes at each site. At site 1166 redox sensitive elements (Cr, Ni, and V) show similar down core distributions to one another. The changes in elemental intensities are likely being controlled by factors such as sediment provenance, changes in redox conditions and surficial weathering. We expect the outcomes of this study to allow us to interpret regional depositional environments at a higher resolution, as well as to shed light on the EAIS's step-wise initiation.

A highly oxidized atmosphere-ocean system and oceanic molybdenum drawdown during the Paleoproterozoic

NASA Astrophysics Data System (ADS)

Goto, K. T.; Ito, T.; Suzuki, K.; Anbar, A. D.; Gordon, G. W.; Kashiwabara, T.; Takaya, Y.; Shimoda, G.; Nozaki, T.; Kiyokawa, S.; Tetteh, G. M.; Nyame, F. K.

2014-12-01

Multiple lines of evidence suggest that the first major oxidation of the atmosphere-ocean system occurred during the Paleoproterozoic. However, the course of this redox transition remains elusive. A number of large Mn deposits are distributed in Paleoproterozoic sedimentary successions. As Mn is a redox-sensitive element characterized by high redox potential, knowledge of the Mn cycle in Paleoproterozoic seawater may provide insight into redox evolution during this period. Here, we investigate the Mn cycle in Paleoproterozoic seawater based on the Re-Os and Mo isotope compositions, and the abundance of major and trace elements, in Mn-rich sedimentary rocks from the Nsuta deposit of the Birimian Supergroup, Ghana. The Mn ore is composed mainly of rhodochrosite and is distributed at the boundaries between sedimentary rocks and tholeiitic volcanic rocks. The Re-Os isochron age (2217 ± 100 Ma) we obtained was consistent with U-Pb zircon ages of the volcanic rocks. The manganophile elements, except for Mo, show no enrichment, which is similar to modern hydrothermal Mn oxides. The PAAS-normalized REE compositions show positive Ce anomaly, indicative of Ce enrichment due to the oxidation of Ce(III) by Mn(IV). These findings suggest that Mn ore formed from primary precipitation of Mn oxides from hydrothermal fluids as they were mixed with bottom seawater at ~2.2 Ga. Thus, the bottom seawater would have been sufficiently oxygenated for the precipitation of Mn oxides at ~2.2 Ga. The Nsuta ore samples exhibit slight Mo enrichment, but Mo/Mn ratios are orders of magnitude lower than those in modern hydrothermal Mn oxides. We also found that the Mo isotopes in the Nsuta ore are ~0.7‰ heavier than those in modern hydrothermal and hydrogenous Mn oxides. As Mo in hydrothermal Mn oxides is sourced primarily from seawater (Goto et al., in prep), these results may reflect smaller oceanic Mo inventory and heavier seawater Mo isotope composition at 2.2 Ga than those of present-day. Our calculation using a simple mass balance model suggests that substantial removal of light Mo by Mn oxides may have caused such oceanic conditions. Our findings are consistent with the recently proposed 'oxygen overshoot' model (Bekker and Holland, 2012) and low Mo contents in ~2.2-Ga black shales and sedimentary pyrites (e.g., Scott et al., 2008).

Nuclear microscopy of diffuse plaques in the brains of transgenic mice

NASA Astrophysics Data System (ADS)

Rajendran, Reshmi; Ren, Minqin; Casadesus, Gemma; Smith, Mark A.; Perry, George; Huang, En; Ong, Wei Yi; Halliwell, Barry; Watt, Frank

2005-04-01

Using nuclear microscopy, extracellular diffuse amyloid deposits in fresh unstained brain tissue from Alzheimer's disease transgenic mice Tg2576 have been identified and analyzed for trace element content. Off-axis scanning transmission ion microscopy (STIM) images can be obtained which are similar to the images produced using direct STIM. Since the proton beam current required for off-axis STIM is compatible with PIXE and RBS, we can identify the plaque location and analyze for trace elements simultaneously. Analysis of the diffuse plaques showed an increase in the transition metals iron and zinc compared with the surrounding area of comparable areal density. This supports the theory that redox interactions between Aβ and metals could be at the heart of a pathological feedback system wherein Aβ amyloidosis and oxidative stress promote each other, possibly via Fenton chemistry.

A high-resolution record of Holocene millennial-scale oscillations of surface water, foraminiferal paleoecology and sediment redox chemistry in the SE Brazilian margin

NASA Astrophysics Data System (ADS)

Dias, B. B.; Barbosa, C. F.; Albuquerque, A. L.; Piotrowski, A. M.

2014-12-01

Holocene millennial-scale oscillations and Bond Events (Bond et al. 1997) are well reported in the North Atlantic as consequence of fresh water input and weaking of the Atlantic Meridional Overturning Circulation (AMOC). It has been hypothesized that the effect of weaking of AMOC would lead to warming in the South Atlantic due to "heat piracy", causing surface waters to warm and a reorganization of surface circulation. There are few reconstructions of AMOC strength in the South Atlantic, and none with a high resolution Holocene record of changes of productivity and the biological pump. We reconstruct past changes in the surface water mass hydrography, productivity, and sediment redox changes in high-resolution in the core KCF10-01B, located 128 mbsl water depth off Cabo Frio, Brazil, a location where upwelling is strongly linked to surface ocean hydrography. We use Benthic Foraminiferal Accumulation Rate (BFAR) to reconstruct productivity, which reveals a 1.3kyr cyclicity during the mid- and late-Holocene. The geochemistry of trace and rare earth elements on foraminiferal Fe-Mn oxide coatings show changes in redox-sensitive elements indicating that during periods of high productivity there were more reducing conditions in sediment porewaters, producing a Ce anomaly and reduction and re-precipitation of Mn oxides. Bond events 1-7 were identified by a productivity increase along with reducing sediment conditions which was likely caused by Brazil Current displacement offshore allowing upwelling of the nutritive bottom water South Atlantic Central Waters (SACW) to the euphotic zone and a stronger local biological pump. In a global context, correlation with other records show that this occurred during weakened AMOC and southward displacement of the ITCZ. We conclude that Bond climatic events and millennial-scale variability of AMOC caused sea surface hydrographic changes off the Brazilian Margin leading to biological and geochemical changes recorded in coastal records. The 8.2kyr climatic event is reported here for the first time in South American coastal sediment records as high productivity conditions and a rapid change in porewater redox chemistry.

Involvement of Redox State in the Aging of Drosophila melanogaster

PubMed Central

Radyuk, Svetlana N.; Sohal, Rajindar S.

2013-01-01

Abstract Significance: The main objective of this review was to provide an exposition of investigations, conducted in Drosophila melanogaster, on the role of reactive oxygen species and redox state in the aging process. While early transgenic studies did not clearly support the validity of the oxidative stress hypothesis of aging, predicated on the accumulation of structural damage, they spawned a broader search for redox-related effects that might impact the aging process. Recent Advances: Initial evidence implicating the thiol redox state as a possible causative factor in aging has been obtained in Drosophila. Overexpression of genes, such as GCL, G6PD, Prx2, and Prx5, which are involved in the maintenance of thiol redox homeostasis, has strong positive effects on longevity. Further, the depletion of peroxiredoxin activity in the mitochondria through the double knockdown of Prx5 and Prx3 not only results in a redox crisis but also elicits a rapid aging phenotype. Critical Issues: Herein, we summarize the present status of knowledge about the main components of the machinery controlling thiol redox homeostasis and describe how age-related redox fluctuations might impact aging more acutely through disruption of the redox-sensitive signaling mechanisms rather than via the simple accumulation of structural damage. Future Directions: Based on these initial insights into the plausible impact of redox fluctuations on redox signaling, future studies should focus on the pathways that have been explicitly implicated in aging, such as insulin signaling, TOR, and JNK/FOXO, with particular attention to elements that are redox sensitive. Antioxid. Redox Signal. 19, 788–803. PMID:23458359

Redox state of recycled crustal lithologies in the convective upper mantle constrained using oceanic basalt CO2-trace element systematics

NASA Astrophysics Data System (ADS)

Eguchi, J.; Dasgupta, R.

2017-12-01

Investigating the redox state of the convective upper mantle remains challenging as there is no way of retrieving samples from this part of the planet. Current views of mantle redox are based on Fe3+/∑Fe of minerals in mantle xenoliths and thermodynamic calculations of fO2 [1]. However, deep xenoliths are only recoverable from continental lithospheric mantle, which may have different fO2s than the convective oceanic upper mantle [1]. To gain insight on the fO2 of the deep parts of the oceanic upper mantle, we probe CO2-trace element systematics of basalts that have been argued to receive contributions from subducted crustal lithologies that typically melt deeper than peridotite. Because CO2 contents of silicate melts at graphite saturation vary with fO2 [2], we suggest CO2-trace element systematics of oceanic basalts which sample deep heterogeneities may provide clues about the fO2 of the convecting mantle containing embedded heterogeneities. We developed a new model to predict CO2 contents in nominally anhydrous silicate melts from graphite- to fluid-saturation over a range of P (0.05- 5 GPa), T (950-1600 °C), and composition (foidite-rhyolite). We use the model to calculate CO2 content as a function of fO2 for partial melts of lithologies that vary in composition from rhyolitic sediment melt to silica-poor basaltic melt of pyroxenites. We then use modeled CO2 contents in mixing calculations with partial melts of depleted mantle to constrain the fO2 required for partial melts of heterogeneities to deliver sufficient CO2 to explain CO2-trace element systematics of natural basalts. As an example, Pitcairn basalts, which show evidence of a subducted crustal component [3] require mixing of 40% of partial melts of a garnet pyroxenite at ΔFMQ -1.75 at 3 GPa. Mixing with a more silicic composition such as partial melts of a MORB-eclogite cannot deliver enough CO2 at graphite saturation, so in this scenario fO2 must be above the EMOG/D buffer at 4 GPa. Results suggest convecting upper mantle may be more oxidized than continental lithospheric mantle, and fO2 profiles of continental lithospheric mantle may not be applicable to convective upper mantle.[1] Frost, D, McCammon, C. 2008. An Rev E & P Sci. (36) p.389-420; [2] Holloway, J, et al. 1992. Eu J. Min. (4) p. 105-114; [3] Woodhead, J, Devey C. 1993. EPSL. (116) p. 81-99.

Holocene and late glacial palaeoceanography and palaeolimnology of the Black Sea: Changing sediment provenance and basin hydrography over the past 20,000 years

USGS Publications Warehouse

Piper, David Z.; Calvert, S.E.

2011-01-01

The elemental geochemistry of Late Pleistocene and Holocene sediments of the Black Sea, recovered in box cores from the basin margins and a 5-m gravity core from the central abyssal region of the basin, identifies two terrigenous sediment sources over the last 20 kyrs. One source region includes Anatolia and the southern Caucasus; the second region is the area drained by rivers entering the Black Sea from Eastern Europe. Alkali metal:Al and heavy:light rare-earth element ratios reveal that the relative contribution of the two sources shifted abruptly every few thousand years during the late glacial and early Holocene lacustrine phase of the basin. The shifts in source were coeval with changes in the lake level as determined from the distribution of quartz and the heavy mineral-hosted trace elements Ti and Zr.The geochemistry of the abyssal sediments further recorded a sequence of changes to the geochemistry of the water column following the lacustrine phase, when high salinity Mediterranean water entered the basin beginning 9.3 kyrs BP. Bottom water that had been oxic throughout the lake phase became anoxic at approximately 8.4 kyrs BP, as recorded by the accumulation from the water column of several redox-sensitive trace metals (Mo, Re, U). The accumulation of organic carbon and several trace nutrients (Cd, Cu, Ni, Zn) increased sharply ca. 0.4 kyrs later, at 8.0 kyrs BP, reflecting an increase of primary productivity. Its increase was coeval with a shift in the dinoflagellate ecology from stenohaline to euryhaline assemblages. During this profound environmental change from the lacustrine to the marine phase, the accumulation rate of the lithogenous sediment fraction decreased as much as 10-fold in response to the rise of the water level in the basin from a low stand ca. 9.3 ka to its current level.

Holocene and late glacial palaeoceanography and palaeolimnology of the Black Sea: Changing sediment provenance and basin hydrography over the past 20,000 years

USGS Publications Warehouse

Piper, D.Z.; Calvert, S.E.

2011-01-01

The elemental geochemistry of Late Pleistocene and Holocene sediments of the Black Sea, recovered in box cores from the basin margins and a 5-m gravity core from the central abyssal region of the basin, identifies two terrigenous sediment sources over the last 20. kyrs. One source region includes Anatolia and the southern Caucasus; the second region is the area drained by rivers entering the Black Sea from Eastern Europe. Alkali metal:Al and heavy:light rare-earth element ratios reveal that the relative contribution of the two sources shifted abruptly every few thousand years during the late glacial and early Holocene lacustrine phase of the basin. The shifts in source were coeval with changes in the lake level as determined from the distribution of quartz and the heavy mineral-hosted trace elements Ti and Zr. The geochemistry of the abyssal sediments further recorded a sequence of changes to the geochemistry of the water column following the lacustrine phase, when high salinity Mediterranean water entered the basin beginning 9.3. kyrs BP. Bottom water that had been oxic throughout the lake phase became anoxic at approximately 8.4. kyrs BP, as recorded by the accumulation from the water column of several redox-sensitive trace metals (Mo, Re, U). The accumulation of organic carbon and several trace nutrients (Cd, Cu, Ni, Zn) increased sharply ca. 0.4. kyrs later, at 8.0. kyrs BP, reflecting an increase of primary productivity. Its increase was coeval with a shift in the dinoflagellate ecology from stenohaline to euryhaline assemblages. During this profound environmental change from the lacustrine to the marine phase, the accumulation rate of the lithogenous sediment fraction decreased as much as 10-fold in response to the rise of the water level in the basin from a low stand ca. 9.3. ka to its current level.

Potential role of peroxisome proliferator activated receptor gamma activation on serum visfatin and trace elements in high fat diet induced type 2 diabetes mellitus.

PubMed

Tabassum, Arshia; Zaidi, Syeda Nuzhat Fatima; Yasmeen, Kausar; Mahboob, Tabassum

2018-07-15

Electrolytes and trace elements dysregulation play an important role in the progression of obesity and diabetes complications. The present study was designed to evaluate the insulin sensitizing effects of peroxisomes proliferators activated receptor gamma (PPAR-γ) agonist on trace elements in obesity induced type 2 diabetes mellitus and correlate with serum visfatin. Wistar rats were categorized into five groups. Group I served as control; Group II fed on high fat diet (HFD); Group III fed on HFD and treated with rosiglitazone (3 mg/kg) for 7 days; Group IV were T2DM rats induce by HFD and low dose of streptozotocin (i.p. 35 mg/kg); Group V was T2DM rats treated with rosiglitazone (3 mg/kg) for 7 days. Serum and tissues electrolytes levels and renal, hepatic and cardiac tissues trace elements were estimated by flame photometer and atomic absorption spectroscopy. Serum visfatin was estimated by ELISA. Pearson correlations were analyzed among fasting blood glucose (FBG), serum visfatin and tissues trace elements. Results of the current study showed hyponatremia, hyperkalemia, hypomagnesemia and hypercalcemia in HFD and T2DM groups. HFD and T2DM also showed elevated copper and iron levels; however, zinc and selenium levels were decreased. Rosiglitazone treatment increased the insulin sensitization and altered these changes. A Strong association was observed among FBG, serum visfatin and trace elements levels of HFD and T2DM. Obesity and diabetes mellitus disturbed visfatin, electrolytes and trace elements homeostasis. Rosiglitazone treatment restored these changes. The results of the study could serve as a basis for further studies for the prevention of diabetic complications. Copyright © 2018 Elsevier Inc. All rights reserved.

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.; Goldhaber, M.B.

2009-01-01

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Trace analysis of high-purity graphite by LA-ICP-MS.

PubMed

Pickhardt, C; Becker, J S

2001-07-01

Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a very efficient and sensitive technique for the direct analysis of solids. In this work the capability of LA-ICP-MS was investigated for determination of trace elements in high-purity graphite. Synthetic laboratory standards with a graphite matrix were prepared for the purpose of quantifying the analytical results. Doped trace elements, concentration 0.5 microg g(-1), in a laboratory standard were determined with an accuracy of 1% to +/- 7% and a relative standard deviation (RSD) of 2-13%. Solution-based calibration was also used for quantitative analysis of high-purity graphite. It was found that such calibration led to analytical results for trace-element determination in graphite with accuracy similar to that obtained by use of synthetic laboratory standards for quantification of analytical results. Results from quantitative determination of trace impurities in a real reactor-graphite sample, using both quantification approaches, were in good agreement. Detection limits for all elements of interest were determined in the low ng g(-1) concentration range. Improvement of detection limits by a factor of 10 was achieved for analyses of high-purity graphite with LA-ICP-MS under wet plasma conditions, because the lower background signal and increased element sensitivity.

Mechanisms of Arsenic Mobilization and Attenuation in Subsurface Sediments

NASA Astrophysics Data System (ADS)

O'Day, P. A.; Illera, V.; Root, R.; Choi, S.; Vlassopoulos, D.

2007-12-01

This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited in labile or available S and/or Fe that remove As by precipitation or adsorption. In subsurface sediments with low labile S and Fe, laboratory experiments and spectroscopic studies suggest that sediment Mn minerals are important in the oxidation of sorbed As(III) to As(V), but that they have a limited oxidation capacity. Arsenic attenuation and mobilization in the subsurface are affected by seasonal variations when hydraulic conditions are influenced by surface infiltration, which may induce transitions from oxidized to reduced conditions (or vice versa) in porewater.

Biomonitoring of Urban Pollution Using Silicon-Accumulating Species, Phyllostachys aureosulcata 'Aureocaulis'.

PubMed

Morina, Filis; Vidović, Marija; Srećković, Tatjana; Radović, Vesela; Veljović-Jovanović, Sonja

2017-12-01

We investigated metal accumulation in bamboo leaves during three seasons at three urban locations differing in pollution levels. The higher content of Cu, Pb, and Zn in the leaves was in correlation with the highest bioavailable content of these elements in the soil at the most polluted location. The content of leaf trace elements was higher in summer and autumn compared to spring. Scanning electron microscopy with energy dispersive X-ray spectroscopy showed that Si accumulation in bamboo leaves was the highest in epidermis and vascular tissue, and was co-localized with trace metals. Analysis of phytoliths showed co-deposition of Al, C, and Si, implying the involvement of Si in metal detoxification. Compared to a common urban tree, linden, bamboo showed better capacity to maintain cellular redox homeostasis under deteriorated environmental conditions. The results suggest that bamboo can be efficiently used for biomonitoring of air and soil metal pollution and remediation in urban areas.

Massive sulfide deposition and trace element remobilization in the Middle Valley sediment-hosted hydrothermal system, northern Juan de Fuca Rdge

USGS Publications Warehouse

Houghton, J.L.; Shanks, Wayne C.; Seyfried, W.E.

2004-01-01

The Bent Hill massive sulfide deposit and ODP Mound deposit in Middle Valley at the northernmost end of the Juan de Fuca Ridge are two of the largest modern seafloor hydrothermal deposits yet explored. Trace metal concentrations of sulfide minerals, determined by laser-ablation ICP-MS, were used in conjunction with mineral paragenetic studies and thermodynamic calculations to deduce the history of fluid-mineral reactions during sulfide deposition. Detailed analyses of the distribution of metals in sulfides indicate significant shifts in the physical and chemical conditions responsible for the trace element variability observed in these sulfide deposits. Trace elements (Mn, Co, Ni, As, Se, Ag, Cd, Sb, Pb, and Bi) analyzed in a representative suite of 10 thin sections from these deposits suggest differences in conditions and processes of hydrothermal alteration resulting in mass transfer of metals from the center of the deposits to the margins. Enrichments of some trace metals (Pb, Sb, Cd, Ag) in sphalerite at the margins of the deposits are best explained by dissolution/reprecipitation processes consistent with secondary remineralization. Results of reaction-path models clarify mechanisms of mass transfer during remineralization of sulfide deposits due to mixing of hydrothermal fluids with seawater. Model results are consistent with patterns of observed mineral paragenesis and help to identify conditions (pH, redox, temperature) that may be responsible for variations in trace metal concentrations in primary and secondary minerals. Differences in trace metal distributions throughout a single deposit and between nearby deposits at Middle Valley can be linked to the history of metal mobilization within this active hydrothermal system that may have broad implications for sulfide ore formation in other sedimented and unsedimented ridge systems. ?? 2004 Elsevier Ltd.

Three-dimensional flow and trace metal mobility in shallow Chalk groundwater, Dorset, United Kingdom

NASA Astrophysics Data System (ADS)

Schürch, Marc; Edmunds, W. Michael; Buckley, David

2004-06-01

The three-dimensional groundwater flow and the hydrogeochemical regime have been determined in the Bere Stream valley, North Dorset Downs, southern England. The dual porosity characteristics of the Portsdown Chalk have been established using geophysical and hydrochemical borehole logging. Chemical properties have been established using major and trace element analyses of depth samples and groundwaters. The study site is located at the unconfined-confined boundary of the Chalk aquifer, where it is overflowing in the observation boreholes. The Chalk dips locally at about 5 m/km to the south-east under Palaeogene confining beds and three distinctive flow horizons may be recognised. The Chalk groundwater is of Ca-HCO 3 type and three separate geochemical groundwater zones were also determined with depth, having different oxygen levels and trace element characteristics. (1) A shallow O 2-rich zone with around 80% dissolved O 2 and low trace element concentrations. (2) A mixing and transition zone with significant concentrations of trace elements and high trace metal concentrations at its base: manganese 29 μg/l, nickel 55 μg/l, cadmium 146 μg/l, and zinc 214 μg/l. (3) A deeper zone with depleted oxygen (5-20% dissolved O 2) and with longer water residence times shown by higher Mg/Ca and K/Na ratios as well as higher Sr and F. The groundwater geochemistry in the Chalk aquifer is dominated by incongruent reactions with the fine-grained carbonate sediments, which release trace element impurities to the water. Some of the metals are co-precipitated with Mn- and Fe-oxide phases on fissure surfaces, whilst producing a purer calcite. During subsequent recrystallisation to purer iron- and manganese-oxides on fissure surfaces under specific geochemical and hydrodynamic conditions, trace metals are released into the fissure water. The results demonstrate the need to monitor quality stratification and the changes in the groundwater baseline chemistry in areas close to the redox boundary which, in the dual porosity Chalk is likely to be a diffuse zone with exchange between oxygen poor matrix waters and more oxic water flowing through the fissures.

Ultra-Sensitive Elemental Analysis Using Plasmas 7.Application to Criminal Investigation

NASA Astrophysics Data System (ADS)

Suzuki, Yasuhiro

This paper describes the application of trace elemental analysis using ICP-AES and ICP-MS to criminal investigation. The comparison of trace elements, such as Rb, Sr, Zr, and so on, is effective for the forensic discrimination of glass fragments, which can be important physical evidence for connecting a suspect to a crime scene or to a victim. This procedure can be applied also to lead shotgun pellets by the removal of matrix lead as the sulfate precipitate after the dissolution of a pellet sample. The determination of a toxic element in bio-logical samples is required to prove that a victim ingested this element. Arsenous acids produced in Japan, China, Germany and Switzerland show characteristic patterns of trace elements characteristic to each country.

Biological forcing controls the chemistry of reef-building coral skeleton

NASA Astrophysics Data System (ADS)

Meibom, Anders; Mostefaoui, Smail; Cuif, Jean-Pierre; Dauphin, Yannicke; Houlbreque, Fanny; Dunbar, Robert; Constantz, Brent

2007-01-01

We present analyses of major elements C and Ca and trace elements N, S, Mg and Sr in a Porites sp. exoskeleton with a spatial resolution better than ˜150 nm. Trace element variations are evaluated directly against the ultra-structure of the skeleton and are ascribed to dynamic biological forcing. Individual growth layers in the bulk fibrous aragonite skeleton form on sub-daily timescales. Magnesium concentration variations are dramatically correlated with the growth layers, but are uncorrelated with Sr concentration variations. Observed (sub)seasonal relationships between water temperature and skeletal trace-element chemistry are secondary, mediated by sensitive biological processes to which classical thermodynamic formalism does not apply.

Electrostatic Discharge Effects on Thin Film Resistors

NASA Technical Reports Server (NTRS)

Sampson, Michael J.; Hull, Scott M.

1999-01-01

Recently, open circuit failures of individual elements in thin film resistor networks have been attributed to electrostatic discharge (ESD) effects. This paper will discuss the investigation that came to this conclusion and subsequent experimentation intended to characterize design factors that affect the sensitivity of resistor elements to ESD. The ESD testing was performed using the standard human body model simulation. Some of the design elements to be evaluated were: trace width, trace length (and thus width to length ratio), specific resistivity of the trace (ohms per square) and resistance value. However, once the experiments were in progress, it was realized that the ESD sensitivity of most of the complex patterns under evaluation was determined by other design and process factors such as trace shape and termination pad spacing. This paper includes pictorial examples of representative ESD failure sites, and provides some options for designing thin film resistors that are ESD resistant. The risks of ESD damage are assessed and handling precautions suggested.

Tracing redox processes during paleoclimatic changes in the Neoproterozoic: Stable chromium isotopic results from the Arroyo del Soldado Group (Ediacaran, Uruguay)

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2007-12-01

Positive δ13C carbonate values, combined with the occurrence of Fe-rich cherts (oxide-facies BIF) and organic-rich black shales within the late Ediacaran (ca. 580-560 Ma) Yerbal Fm. of the Arroyo del Soldato Group (Uruguay) are compatible with paleoclimatic models which postulate that enhanced bioproductivity due to higher availability of nutrient (P, N, Fe) was essential for controlling Neoproterozoic glaciations. Tracing of associated redox processes (f.e. linked to oxygenation of bottom waters in restricted basins) that might have been responsible for the deposition of Fe-rich cherts (BIFs) is therefore an important tool to better understand the seawater changes during cold-warm periods. Besides the traditionally used Fe and Mo isotopic systems, the redox-sensitive element Cr (Cr(III); Cr(IV)) and its stable isotopes offer another complementary system to trace paleo-redox processes. We have applied Cr stable isotope systematics to a sequence of samples from a late Ediacaran sedimentary sequence in Uruguay, using a 52Cr-54Cr double spike (Schoenberg et al., Chem..Geol., subm.). The middle Yerbal Fm. is dominated by organic-rich, black shales and black dolostones (δ53Cr = -0.05‰), followed by organic-rich cherts (δ53Cr = +1.83 - +4.49 ‰) and BIF (δ53Cr = -0.31 +0.90 ‰) gradually changing into Fe-bearing, organic-rich cherts and shales (δ53Cr = -0.28 - -0.01 ‰), and another sequence with BIF and organic-rich cherts topped by carbonates of the lower Polanco Fm. (δ53Cr = -0.17 to -0.27 ‰). The strongly positively fractionated Cr isotopic signatures in organic-rich and Fe-rich cherts in the Yerbal Fm. may point to significant oxidation processes either directly in the seawater column and/or during early diagenetic processes at the sediment-water interface. While these strongly positive δ53Cr values are the first to be reported from Neoproterozoic sedimentary sequence, the exact nature of the chemical process that produced these anomalies is not yet understood. However, the occurrence of these anomalies in organic-rich and Fe-rich chemical sediments that were deposited in a period following a glacial (Gaskiers?) event is compatible with "Snowball Earth" scenarios whereby impulsive oxidation of the upper seawater was in response to ice cover retraction which allowed booming of the biosphere and concomitant oxidation of accumulated Fe2+ and subsequent precipitation of the Fe-oxyhydroxides to form the "BIF" during such epochs. Schoenberg et al. (subm.) The stable Cr isotope inventory of solid earth reservoirs determined by double-spike MC-ICP-MS. Chemical Geology

Geological and Chemical Factors that Impacted the Biological Utilization of Cobalt in the Archean Eon

NASA Astrophysics Data System (ADS)

Moore, Eli K.; Hao, Jihua; Prabhu, Anirudh; Zhong, Hao; Jelen, Ben I.; Meyer, Mike; Hazen, Robert M.; Falkowski, Paul G.

2018-03-01

The geosphere and biosphere coevolved and influenced Earth's biological and mineralogical diversity. Changing redox conditions influenced the availability of different transition metals, which are essential components in the active sites of oxidoreductases, proteins that catalyze electron transfer reactions across the tree of life. Despite its relatively low abundance in the environment, cobalt (Co) is a unique metal in biology due to its importance to a wide range of organisms as the metal center of vitamin B12 (aka cobalamin, Cbl). Cbl is vital to multiple methyltransferase enzymes involved in energetically favorable metabolic pathways. It is unclear how Co availability is linked to mineral evolution and weathering processes. Here we examine important biological functions of Co, as well as chemical and geological factors that may have influenced the utilization of Co early in the evolution of life. Only 66 natural minerals are known to contain Co as an essential element. However, Co is incorporated as a minor element in abundant rock-forming minerals, potentially representing a reliable source of Co as a trace element in marine systems due to weathering processes. We developed a mineral weathering model that indicates that dissolved Co was potentially more bioavailable in the Archean ocean under low S conditions than it is today. Mineral weathering, redox chemistry, Co complexation with nitrogen-containing organics, and hydrothermal environments were crucial in the incorporation of Co in primitive metabolic pathways. These chemical and geological characteristics of Co can inform the biological utilization of other trace metals in early forms of life.

Paleo-Productivity across the Paleocene-Eocene Thermal Maximum, Walvis Ridge Transect (ODP Sites 1262, 1263, and 1266)

NASA Astrophysics Data System (ADS)

Chun, C. O.; Delaney, M. L.; Zachos, J. C.

2005-12-01

Walvis Ridge transect (Ocean Drilling Program (ODP) Leg 208) provides the first high-resolution depth-transect of deep-sea sediments recovered from the south Atlantic across the P/E boundary. A geographically restricted depth transect (~ 2.2 km, water depths between 2500 and 4770 m) allows us to constrain the surface waters by assuming marine productivity conditions in the overlying water column are similar across all sites. The sediment record will reveal variations for processes that are water-depth dependent. We use the geochemical tracers; biogenic barium, phosphorus, calcium carbonate, and the redox sensitive trace elements manganese and uranium, to reconstruct nutrient burial, paleoproductivity, and bottom water redox chemistry across the Paleocene-Eocene Thermal Maximum (PETM). We calculate our concentrations on a calcium carbonate-free basis to account for dilution by non-carbonate sediments. Trace metal enrichment factors (EFs) are calculated relative to bulk crustal averages. We chose three sites from the depth transect: the shallowest (Site 1263, 2717 m water depth), an intermediate site (Site 1266, 3798 m water depth), and the deepest site (Site 1262, 4755 m water depth). We sampled each site at a sample resolution of ~ 1-2 kyr for 5 m.y. centered at 55 Ma. Uranium EFs at the shallow site exhibits values ~ 5 pre-event and drop to values near crustal averages during and after the carbon isotope excursion (CIE). No dramatic changes in U EFs across the P/E boundary are recorded at the deep and intermediate sites. Mn EFs range between 2.9 -8.6 prior to the event across all three sites, suggesting an oxygenated depositional environment. At the boundary, Mn EFs drop to crustal averages at all sites, then gradually return to pre-event values, indicating more reducing environments during the CIE, a possible explanation for the benthic extinction event (BEE) observed across this transect. Ba excess and reactive phosphorus exhibit decreased concentrations during the CIE with gradual return to pre-event values at the shallowest and deepest sites. We will compare the paleo-productivity and redox chemistry response at the Walvis Ridge sites across the PETM.

Quantifying trace element and isotope fluxes at the ocean-sediment boundary: a review.

PubMed

Homoky, William B; Weber, Thomas; Berelson, William M; Conway, Tim M; Henderson, Gideon M; van Hulten, Marco; Jeandel, Catherine; Severmann, Silke; Tagliabue, Alessandro

2016-11-28

Quantifying fluxes of trace elements and their isotopes (TEIs) at the ocean's sediment-water boundary is a pre-eminent challenge to understand their role in the present, past and future ocean. There are multiple processes that drive the uptake and release of TEIs, and properties that determine their rates are unevenly distributed (e.g. sediment composition, redox conditions and (bio)physical dynamics). These factors complicate our efforts to find, measure and extrapolate TEI fluxes across ocean basins. GEOTRACES observations are unveiling the oceanic distributions of many TEIs for the first time. These data evidence the influence of the sediment-water boundary on many TEI cycles, and underline the fact that our knowledge of the source-sink fluxes that sustain oceanic distributions is largely missing. Present flux measurements provide low spatial coverage and only part of the empirical basis needed to predict TEI flux variations. Many of the advances and present challenges facing TEI flux measurements are linked to process studies that collect sediment cores, pore waters, sinking material or seawater in close contact with sediments. However, such sampling has not routinely been viable on GEOTRACES expeditions. In this article, we recommend approaches to address these issues: firstly, with an interrogation of emergent data using isotopic mass-balance and inverse modelling techniques; and secondly, by innovating pursuits of direct TEI flux measurements. We exemplify the value of GEOTRACES data with a new inverse model estimate of benthic Al flux in the North Atlantic Ocean. Furthermore, we review viable flux measurement techniques tailored to the sediment-water boundary. We propose that such activities are aimed at regions that intersect the GEOTRACES Science Plan on the basis of seven criteria that may influence TEI fluxes: sediment provenance, composition, organic carbon supply, redox conditions, sedimentation rate, bathymetry and the benthic nepheloid inventory.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2015 The Authors.

Quantifying trace element and isotope fluxes at the ocean-sediment boundary: a review

NASA Astrophysics Data System (ADS)

Homoky, William B.; Weber, Thomas; Berelson, William M.; Conway, Tim M.; Henderson, Gideon M.; van Hulten, Marco; Jeandel, Catherine; Severmann, Silke; Tagliabue, Alessandro

2016-11-01

Quantifying fluxes of trace elements and their isotopes (TEIs) at the ocean's sediment-water boundary is a pre-eminent challenge to understand their role in the present, past and future ocean. There are multiple processes that drive the uptake and release of TEIs, and properties that determine their rates are unevenly distributed (e.g. sediment composition, redox conditions and (bio)physical dynamics). These factors complicate our efforts to find, measure and extrapolate TEI fluxes across ocean basins. GEOTRACES observations are unveiling the oceanic distributions of many TEIs for the first time. These data evidence the influence of the sediment-water boundary on many TEI cycles, and underline the fact that our knowledge of the source-sink fluxes that sustain oceanic distributions is largely missing. Present flux measurements provide low spatial coverage and only part of the empirical basis needed to predict TEI flux variations. Many of the advances and present challenges facing TEI flux measurements are linked to process studies that collect sediment cores, pore waters, sinking material or seawater in close contact with sediments. However, such sampling has not routinely been viable on GEOTRACES expeditions. In this article, we recommend approaches to address these issues: firstly, with an interrogation of emergent data using isotopic mass-balance and inverse modelling techniques; and secondly, by innovating pursuits of direct TEI flux measurements. We exemplify the value of GEOTRACES data with a new inverse model estimate of benthic Al flux in the North Atlantic Ocean. Furthermore, we review viable flux measurement techniques tailored to the sediment-water boundary. We propose that such activities are aimed at regions that intersect the GEOTRACES Science Plan on the basis of seven criteria that may influence TEI fluxes: sediment provenance, composition, organic carbon supply, redox conditions, sedimentation rate, bathymetry and the benthic nepheloid inventory. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Quantifying trace element and isotope fluxes at the ocean–sediment boundary: a review

PubMed Central

Berelson, William M.; Severmann, Silke

2016-01-01

Quantifying fluxes of trace elements and their isotopes (TEIs) at the ocean's sediment–water boundary is a pre-eminent challenge to understand their role in the present, past and future ocean. There are multiple processes that drive the uptake and release of TEIs, and properties that determine their rates are unevenly distributed (e.g. sediment composition, redox conditions and (bio)physical dynamics). These factors complicate our efforts to find, measure and extrapolate TEI fluxes across ocean basins. GEOTRACES observations are unveiling the oceanic distributions of many TEIs for the first time. These data evidence the influence of the sediment–water boundary on many TEI cycles, and underline the fact that our knowledge of the source–sink fluxes that sustain oceanic distributions is largely missing. Present flux measurements provide low spatial coverage and only part of the empirical basis needed to predict TEI flux variations. Many of the advances and present challenges facing TEI flux measurements are linked to process studies that collect sediment cores, pore waters, sinking material or seawater in close contact with sediments. However, such sampling has not routinely been viable on GEOTRACES expeditions. In this article, we recommend approaches to address these issues: firstly, with an interrogation of emergent data using isotopic mass-balance and inverse modelling techniques; and secondly, by innovating pursuits of direct TEI flux measurements. We exemplify the value of GEOTRACES data with a new inverse model estimate of benthic Al flux in the North Atlantic Ocean. Furthermore, we review viable flux measurement techniques tailored to the sediment–water boundary. We propose that such activities are aimed at regions that intersect the GEOTRACES Science Plan on the basis of seven criteria that may influence TEI fluxes: sediment provenance, composition, organic carbon supply, redox conditions, sedimentation rate, bathymetry and the benthic nepheloid inventory. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035270

Arsenic speciation and trace element analysis of the volcanic río Agrio and the geothermal waters of Copahue, Argentina.

PubMed

Farnfield, Hannah R; Marcilla, Andrea L; Ward, Neil I

2012-09-01

Surface water originating from the Copahue volcano crater-lake was analysed for total arsenic and four arsenic species: arsenite (iAs(III)), arsenate (iAs(V)), monomethylarsonic acid (MA(V)) and dimethylarsinic acid (DMA(V)) and other trace elements (Fe, Mn, V, Cr, Ni, Zn). A novel in-field technique for the preconcentration and separation of four arsenic species was, for the first time, used for the analysis of geothermal and volcanic waters. Total arsenic levels along the río Agrio ranged from <0.2-3783 μg/l As(T). The highest arsenic levels were recorded in the el Vertedero spring (3783 μg/l As(T)) on the flank of the Copahue volcano, which feeds the acidic río Agrio. Arsenite (H(3)AsO(3)) predominated along the upper río Agrio (78.9-81.2% iAs(III)) but the species distribution changed at lago Caviahue and arsenate (H(2)AsO(4)(-)) became the main species (51.4-61.4% iAs(V)) up until Salto del Agrio. The change in arsenic species is potentially a result of an increase in redox potential and the formation of iron-based precipitates. Arsenic speciation showed a statistically significant correlation with redox potential (r=0.9697, P=0.01). Both total arsenic and arsenic speciation displayed a statistically significant correlation with vanadium levels along the river (r=0.9961, P=0.01 and r=0.8488, P=0.05, respectively). This study highlights that chemical speciation analysis of volcanic waters is important in providing ideas on potential chemical toxicity. Furthermore there is a need for further work evaluating how arsenic (and other trace elements), released in volcanic and geothermal streams/vents, impacts on both biota and humans (via exposure in thermal pools or consuming commercial drinking water). Copyright © 2012 Elsevier B.V. All rights reserved.

Mobility of nutrients and trace metals during weathering in the late Archean

NASA Astrophysics Data System (ADS)

Hao, Jihua; Sverjensky, Dimitri A.; Hazen, Robert M.

2017-08-01

The evolution of the geosphere and biosphere depends on the availability of bio-essential nutrients and trace metals. Consequently, the chemical and isotopic variability of trace elements in the sedimentary record have been widely used to infer the existence of early life and fluctuations in the near-surface environment on the early Earth, particularly fluctuations in the redox state of the atmosphere. In this study, we applied late Archean weathering models (Hao et al., 2017), developed to estimate the behavior of major elements and the composition of late Archean world average river water, to explore the behavior of nutrient and trace metals and their potential for riverine transport. We focused on P, Mn, Cr, and Cu during the weathering of olivine basalt. In our standard late Archean weathering model (pCO2,g = 10-1.5 bars, pH2,g = 10-5.0 bars), crustal apatite was totally dissolved by the acidic rainwater during weathering. Our model quantitatively links the pCO2,g of the atmosphere to phosphate levels transported by rivers. The development of late Archean river water (pH = 6.4) resulted in riverine phosphate of at least 1.7 μmolar, much higher than at the present-day. At the end of the early Proterozoic snowball Earth event when pCO2,g could be 0.01-0.10 bars, river water may have transported up to 70 μmolar phosphate, depending on the availability of apatite, thereby stimulating high levels of oxygenic photosynthesis in the marine environment. Crustal levels of Mn in olivine dissolved completely during weathering, except at large extents of weathering where Mn was stored as a component of a secondary carbonate mineral. The corresponding Mn content of river water, about 1.2 μmolar, is higher than in modern river water. Whiffs of 10-5 mole O2 gas or HNO3 kg-1 H2O resulted in the formation of pyrolusite (MnO2) and abundant hematite and simultaneous dramatic decreases in the concentration of Mn(II) in the river water. Chromite dissolution resulted in negligible dissolved Cr in Archean river water. However, amorphous Cr(OH)3 representing easily-weatherable Cr-bearing minerals dissolved totally during the weathering simulations, resulting in concentrations of Cr(III) in the river water of up to 0.14 μmolar, higher than at the present-day. Late Archean weathering of accessory chalcopyrite produced chalcocite and bornite, and extremely low concentrations of Cu (<10-15 molar) because of the low solubilities of the copper sulfides. However, pulses of either O2,g or HNO3 produced native copper, chalcocite, and bornite, much more hematite, and river water containing levels of dissolved Cu comparable to the present-day. Copper mineralogy predicted by weathering models might provide a new correlation with evidence from studies of copper mineral evolution. Overall, our results implied that the redox state of the atmosphere, the pH of surface waters, and the availability of easily-weatherable minerals are all important factors controlling the dissolution of trace elements in river water. Interpretation of the sedimentary signatures of trace elements should consider not only the redox state but also the pH and availability of accessory minerals.

In Situ Determination of Trace Elements in Fish Otoliths by Laser Ablation Double Focusing Sector Field Inductively Coupled Plasma Mass Spectrometry Using a Solution Standard Addition Calibration Method

NASA Astrophysics Data System (ADS)

Chen, Z.; Jones, C. M.

2002-05-01

Microchemistry of fish otoliths (fish ear bones) is a very useful tool for monitoring aquatic environments and fish migration. However, determination of the elemental composition in fish otolith by ICP-MS has been limited to either analysis of dissolved sample solution or measurement of limited number of trace elements by laser ablation (LA)- ICP-MS due to low sensitivity, lack of available calibration standards, and complexity of polyatomic molecular interference. In this study, a method was developed for in situ determination of trace elements in fish otoliths by laser ablation double focusing sector field ultra high sensitivity Finnigan Element 2 ICP-MS using a solution standard addition calibration method. Due to the lack of matrix-match solid calibration standards, sixteen trace elements (Na, Mg, P, Cr, Mn, Fe, Ni, Cu, Rb, Sr, Y, Cd, La, Ba, Pb and U) were determined using a solution standard calibration with Ca as an internal standard. Flexibility, easy preparation and stable signals are the advantages of using solution calibration standards. In order to resolve polyatomic molecular interferences, medium resolution (M/delta M > 4000) was used for some elements (Na, Mg, P, Cr, Mn, Fe, Ni, and Cu). Both external calibration and standard addition quantification strategies are compared and discussed. Precision, accuracy, and limits of detection are presented.

Element-specific behaviour and sediment properties modulate transfer and bioaccumulation of trace elements in a highly-contaminated area (Augusta Bay, Central Mediterranean Sea).

PubMed

Signa, Geraldina; Mazzola, Antonio; Di Leonardo, Rossella; Vizzini, Salvatrice

2017-11-01

High sediment contamination in the coastal area of Priolo Bay, adjacent to the highly-polluted Augusta Harbour, poses serious risks for the benthic communities inhabiting the area. Nevertheless, the transfer of trace elements and consequent bioaccumulation in the biota is an overlooked issue. This study aimed to assess the transfer and bioaccumulation patterns of As, Cd, Ni and Hg to the dominant macroalgae and benthic invertebrates of Priolo Bay. Results revealed different patterns among trace elements (TEs), not driven by sediment contamination but rather by element-specific behaviour coupled with sediment physicochemical properties. Specifically, As accumulated in macroalgae but not in invertebrates, indicating bioavailability of dissolved As only, and a lack of effective trophic transfer. Ni was confined to surface sediment and transfer to biota was not highlighted. Cd and Hg showed the highest concentrations in invertebrates and bioaccumulated especially in filter feeders and carnivores, revealing the importance of suspended particulate and diet as transfer pathways. Total organic carbon (TOC), fine-grained sediments and redox potential were the most important sediment features in shaping the sediment contamination spatial patterns as well as those of TE transfer and bioaccumulation. In particular, As and Cd transfer to macroalgae, and especially Hg bioaccumulation in benthic invertebrates was controlled by sediment properties, resulting in limited transfer and accumulation in the most contaminated stations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rapid and Automated Analytical Methods for Redox Species Based on Potentiometric Flow Injection Analysis Using Potential Buffers

PubMed Central

Ohura, Hiroki; Imato, Toshihiko

2011-01-01

Two analytical methods, which prove the utility of a potentiometric flow injection technique for determining various redox species, based on the use of some redox potential buffers, are reviewed. The first is a potentiometric flow injection method in which a redox couple such as Fe(III)-Fe(II), Fe(CN)6 3−-Fe(CN)(CN)6 4−, and bromide-bromine and a redox electrode or a combined platinum-bromide ion selective electrode are used. The analytical principle and advantages of the method are discussed, and several examples of its application are reported. Another example is a highly sensitive potentiometric flow injection method, in which a large transient potential change due to bromine or chlorine as an intermediate, generated during the reaction of the oxidative species with an Fe(III)-Fe(II) potential buffer containing bromide or chloride, is utilized. The analytical principle and details of the proposed method are described, and examples of several applications are described. The determination of trace amounts of hydrazine, based on the detection of a transient change in potential caused by the reaction with a Ce(IV)-Ce(III) potential buffer, is also described. PMID:21584280

Element Distribution in Silicon Refining: Thermodynamic Model and Industrial Measurements

NASA Astrophysics Data System (ADS)

Næss, Mari K.; Kero, Ida; Tranell, Gabriella; Tang, Kai; Tveit, Halvard

2014-11-01

To establish an overview of impurity elemental distribution among silicon, slag, and gas/fume in the refining process of metallurgical grade silicon (MG-Si), an industrial measurement campaign was performed at the Elkem Salten MG-Si plant in Norway. Samples of in- and outgoing mass streams, i.e., tapped Si, flux and cooling materials, refined Si, slag, and fume, were analyzed by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS), with respect to 62 elements. The elemental distributions were calculated and the experimental data compared with equilibrium estimations based on commercial and proprietary, published databases and carried out using the ChemSheet software. The results are discussed in terms of boiling temperatures, vapor pressures, redox potentials, and activities of the elements. These model calculations indicate a need for expanded databases with more and reliable thermodynamic data for trace elements in general and fume constituents in particular.

Trace element abundance determinations by Synchrotron X Ray Fluorescence (SXRF) on returned comet nucleus mineral grains

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Sutton, S. R.

1989-01-01

Trace element analyses were performed on bulk cosmic dust particles by Proton Induced X Ray Emission (PIXE) and Synchrotron X Ray Fluorescence (SXRF). When present at or near chondritic abundances the trace elements K, Ti, Cr, Mn, Cu, Zn, Ga, Ge, Se, and Br are presently detectable by SXRF in particles of 20 micron diameter. Improvements to the SXRF analysis facility at the National Synchrotron Light Source presently underway should increase the range of detectable elements and permit the analysis of smaller samples. In addition the Advanced Photon Source will be commissioned at Argonne National Laboratory in 1995. This 7 to 8 GeV positron storage ring, specifically designed for high-energy undulator and wiggler insertion devices, will be an ideal source for an x ray microprobe with one micron spatial resolution and better than 100 ppb elemental sensitivity for most elements. Thus trace element analysis of individual micron-sized grains should be possible by the time of the comet nucleus sample return mission.

Oxygen Oases Before and After the GOE: Insights From Metals and Models

NASA Astrophysics Data System (ADS)

Olson, S. L.; Reinhard, C. T.; Planavsky, N. J.; Lyons, T. W.; Roy, M.; Anbar, A. D.

2014-12-01

The evolution of oxygenic photosynthesis fundamentally changed the structure of the marine biosphere and the chemistry of Earth's ocean-atmosphere system. Atmospheric oxygenation, however, was decoupled from the onset of biological O2 production—possibly lagging by as much as half a billion years—and O2 remained low for two billion years following initial O2 accumulation. Although uncertainties remain regarding the fate of biogenic O2 during the Precambrian, it is becoming clear that the consequences of oxygenesis were both spatially and temporally variable. Several lines of evidence support the existence of aerobic ecosystems associated with O2 oases within an otherwise anoxic Archean ocean; however—with notable exceptions—atmospheric O2 remained low enough to severely curtail oxidative weathering processes on long-term average throughout the Archean. During the subsequent Great Oxidation Event (GOE) in the early Paleoproterozoic, atmospheric O2 irreversibly increased above the sensitivity thresholds of several well-established proxies, but the level at which O2 eventually stabilized remains unclear. Consequently, the dynamics of O2 cycling are poorly characterized both before and after the GOE. Nevertheless, recent analytical and numerical results suggest exceptionally low O2 levels that may have favored Archean-style O2 oases in the mid-Proterozoic. We used Fe speciation and trace metal records from Precambrian shales, including data from two new cores that target the 2.7 Ga Roy Hill Shale, to investigate pre- and post- GOE redox heterogeneity in Earth's surface environments. Fe speciation supports the reconstruction of local marine redox conditions, and, in this context, trace metals can allow glimpses of redox conditions beyond the local environment, which may have throttled the supply of key redox-sensitive trace metals to the ocean. Then, using O2 constraints derived from these inorganic proxies, we use an Earth System model to explore C, O, and nutrient cycling in the late Archean and into the mid-Proterozoic. Although our results allow profound perturbation to several biogeochemical cycles and the climate system as a result of the GOE, we find that the GOE may have had only minor significance for the long-term average O2 content of typical surface seawater in the Proterozoic.

Impact of Elevated CO2 on Trace Element Release from Aquifer Sediments of the San Joaquin Valley, CA

NASA Astrophysics Data System (ADS)

Fox, P. M.; Nico, P. S.; Davis, J. A.; Spycher, N.

2014-12-01

Carbon capture and storage (CCS) is a promising technique for mitigating climate change by storing large volumes of carbon dioxide in deep saline aquifers. In California, the thick marine sediments of the Central and Salinas Valleys have been identified as prime targets for future CO2 storage. However, the potential impacts on water quality of overlying drinking-water aquifers must be studied before CCS can be implemented. In this study, we compare trace element release from San Joaquin Valley aquifer sediments with a wide range of textural and redox properties. Kinetic batch experiments were performed with artificial groundwater continuously equilibrated under CO2-saturated (at 1 atm) and background CO2 (0.002-0.006 atm) conditions, resulting in a shift of nearly 3 pH units. In addition, the reversibility of trace element release was studied by sequentially lowering the CO2 from 1.0 atm to 0.5 atm to background concentrations (0.002-0.006 atm) for CO2-saturated systems in order to mimic the dissipation of a CO2 plume in the aquifer. During exposure to high CO2, a number of elements displayed enhanced release compared to background CO2 experiments (Ca, Mg, Li, Si, B, As, Sr, Ni, Fe, Mn, V, Ti, and Co) with concentrations of As, Fe, and Mn exceeding EPA maximum contaminant levels in some cases. On the other hand, Mo and U showed suppressed release. Most intriguing, many of the elements showing enhanced release displayed at least some degree of irreversibility when CO2 concentrations were decreased to background levels. In fact, in some cases (i.e., for V), an element showed further release when CO2 concentrations were decreased. These results suggest that there may be longer-term effects on groundwater quality that persist even after the CO2 plume has dissipated. Several different mechanisms of trace element release including ion exchange, desorption, and carbonate mineral dissolution are explored. Preliminary modeling results suggest that carbonate mineral dissolution can play a key role in driving trace element release even in sediments where carbonates are in low abundance.

Polymer monolithic capillary microextraction combined on-line with inductively coupled plasma MS for the determination of trace rare earth elements in biological samples.

PubMed

Zhang, Lin; Chen, Beibei; He, Man; Hu, Bin

2013-07-01

A rapid and sensitive method based on polymer monolithic capillary microextraction combined on-line with microconcentric nebulization inductively coupled plasma MS has been developed for the determination of trace/ultratrace rare earth elements in biological samples. For this purpose, the iminodiacetic acid modified poly(glycidyl methacrylate-trimethylolpropane trimethacrylate) monolithic capillary was prepared and characterized by SEM and FTIR spectroscopy. Factors affecting the extraction efficiency, such as sample pH, sample flow rate, sample/eluent volume, and coexisting ions were investigated in detail. Under the optimal conditions, the LODs for rare earth elements were in the range of 0.08 (Er) to 0.97 ng/L (Nd) with a sampling frequency of 8.5 h(-1), and the RSDs were between 1.5% (Sm) and 7.4% (Nd) (c = 20 ng/L, n = 7). The proposed method was successfully applied to the analysis of trace/ultratrace rare earth elements in human urine and serum samples, and the recoveries for the spiked samples were in the range of 82-105%. The developed method was simple, rapid, sensitive, and favorable for the analysis of trace/ultratrace rare earth elements in biological samples with limited sample volume. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple Controls on the Paleoenvironment of the Early Cambrian Marine Black Shales in the Sichuan Basin, SW China: Geochemical and Organic Carbon Isotopic Evidence

NASA Astrophysics Data System (ADS)

Wang, S.; Zhang, G.; Dong, D.; Wang, Y.

2016-12-01

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V+Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ13Corg values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ13Corg values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.

The novel approach to the biomonitor survey using one- and two-dimensional Kohonen networks.

PubMed

Deljanin, Isidora; Antanasijević, Davor; Urošević, Mira Aničić; Tomašević, Milica; Perić-Grujić, Aleksandra; Ristić, Mirjana

2015-10-01

To compare the applicability of the leaves of horse chestnut (Aesculus hippocastanum) and linden (Tilia spp.) as biomonitors of trace element concentrations, a coupled approach of one- and two-dimensional Kohonen networks was applied for the first time. The self-organizing networks (SONs) and the self-organizing maps (SOMs) were applied on the database obtained for the element accumulation (Cr, Fe, Ni, Cu, Zn, Pb, V, As, Cd) and the SOM for the Pb isotopes in the leaves for a multiyear period (2002-2006). A. hippocastanum seems to be a more appropriate biomonitor since it showed more consistent results in the analysis of trace elements and Pb isotopes. The SOM proved to be a suitable and sensitive tool for assessing differences in trace element concentrations and for the Pb isotopic composition in leaves of different species. In addition, the SON provided more clear data on seasonal and temporal accumulation of trace elements in the leaves and could be recommended complementary to the SOM analysis of trace elements in biomonitoring studies.

High-Resolution Imaging of Selenium in Kidneys: A Localized Selenium Pool Associated with Glutathione Peroxidase 3

PubMed Central

Malinouski, Mikalai; Kehr, Sebastian; Finney, Lydia; Vogt, Stefan; Carlson, Bradley A.; Seravalli, Javier; Jin, Richard; Handy, Diane E.; Park, Thomas J.; Loscalzo, Joseph; Hatfield, Dolph L.

2012-01-01

Abstract Aim: Recent advances in quantitative methods and sensitive imaging techniques of trace elements provide opportunities to uncover and explain their biological roles. In particular, the distribution of selenium in tissues and cells under both physiological and pathological conditions remains unknown. In this work, we applied high-resolution synchrotron X-ray fluorescence microscopy (XFM) to map selenium distribution in mouse liver and kidney. Results: Liver showed a uniform selenium distribution that was dependent on selenocysteine tRNA[Ser]Sec and dietary selenium. In contrast, kidney selenium had both uniformly distributed and highly localized components, the latter visualized as thin circular structures surrounding proximal tubules. Other parts of the kidney, such as glomeruli and distal tubules, only manifested the uniformly distributed selenium pattern that co-localized with sulfur. We found that proximal tubule selenium localized to the basement membrane. It was preserved in Selenoprotein P knockout mice, but was completely eliminated in glutathione peroxidase 3 (GPx3) knockout mice, indicating that this selenium represented GPx3. We further imaged kidneys of another model organism, the naked mole rat, which showed a diminished uniformly distributed selenium pool, but preserved the circular proximal tubule signal. Innovation: We applied XFM to image selenium in mammalian tissues and identified a highly localized pool of this trace element at the basement membrane of kidneys that was associated with GPx3. Conclusion: XFM allowed us to define and explain the tissue topography of selenium in mammalian kidneys at submicron resolution. Antioxid. Redox Signal. 16, 185–192. PMID:21854231

Disorders of metal metabolism

PubMed Central

Ferreira, Carlos R.; Gahl, William A.

2017-01-01

Trace elements are chemical elements needed in minute amounts for normal physiology. Some of the physiologically relevant trace elements include iodine, copper, iron, manganese, zinc, selenium, cobalt and molybdenum. Of these, some are metals, and in particular, transition metals. The different electron shells of an atom carry different energy levels, with those closest to the nucleus being lowest in energy. The number of electrons in the outermost shell determines the reactivity of such an atom. The electron shells are divided in sub-shells, and in particular the third shell has s, p and d sub-shells. Transition metals are strictly defined as elements whose atom has an incomplete d sub-shell. This incomplete d sub-shell makes them prone to chemical reactions, particularly redox reactions. Transition metals of biologic importance include copper, iron, manganese, cobalt and molybdenum. Zinc is not a transition metal, since it has a complete d sub-shell. Selenium, on the other hand, is strictly speaking a nonmetal, although given its chemical properties between those of metals and nonmetals, it is sometimes considered a metalloid. In this review, we summarize the current knowledge on the inborn errors of metal and metalloid metabolism. PMID:29354481

Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

NASA Astrophysics Data System (ADS)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

2016-04-01

The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous rocks, calcite invariably has higher REE and LILE levels than dolomite. Hydrothermal reworking of carbonatites does not produce a unique geochemical fingerprint, leading instead to a variety of evolutionary trends that range from light-REE and LILE enrichment (Turiy Mys, Russia) to heavy-REE enrichment and LILE depletion (Bear Lodge, USA). These differences clearly attest to variations in the chemistry of carbonatitic fluids and, consequently, their ability to mobilize specific trace elements from earlier-crystallized minerals. An important telltale indicator of hydrothermal reworking is deviation from the primary, chondrite-like REE ratios (in particular, Y/Ho and Eu/Eu*), accompanied by a variety of other compositional changes depending on the redox state of the fluid (e.g., depletion of carbonates in Mn owing to its oxidation and sequestration by secondary oxides). The effect of supergene processes was studied on a single sample from Bear Lodge, which shows extreme depletion in Mn and Ce (both due to oxidation), coupled with enrichment in Pb and U, possibly reflecting an increased availability of Pb2+ and (UO2)2+ species in the system. On the basis of these findings, several avenues for future research can be outlined: (1) structural mechanisms of REE uptake by carbonates; (2) partitioning of REE and LILE between cogenetic calcite and dolomite; (3) the effects of fluorapatite, phlogopite and pyrochlore fractionation on the LILE budget of magmatic carbonates; (4) the cause(s) of coupled Mn-Ce depletion in some primary calcite; and (5) relations between fluid chemistry and compositional changes in hydrothermal carbonates.

Tracer sensitive tapes

NASA Technical Reports Server (NTRS)

Burrows, W. H.; Burrows, W. H.

1971-01-01

A leak detection system has been developed, consisting of a tape that can be wrapped around possible leak sites on a system pressurized with air or gaseous nitrogen. Carbon monoxide, at a level of 100 to 1000 parts per million is used as a trace gas in the pressurized system. The sensitive element of the tape is palladium chloride supported on specially prepared silica gel and specially dried. At a CO level of 100 ppm and a leak rate of 10-20 ml/hr, discoloration of the sensitive element is observed in 1.5 to 3 min. The tape and trace gas are compatible with aerospace hardware, safe to handle, and economically reasonable to produce and handle.

Selenium and trace element mobility affected by periodic displacement of stratification in the Great Salt Lake, Utah

USGS Publications Warehouse

Beisner, K.; Naftz, D.L.; Johnson, W.P.; Diaz, X.

2009-01-01

The Great Salt Lake (GSL) is a unique ecosystem in which trace element activity cannot be characterized by standard geochemical parameters due to the high salinity. Movement of selenium and other trace elements present in the lake bed sediments of GSL may occur due to periodic stratification displacement events or lake bed exposure. The water column of GSL is complicated by the presence of a chemocline persistent over annual to decadal time scales. The water below the chemocline is referred to as the deep brine layer (DBL), has a high salinity (16.5 to 22.9%) and is anoxic. The upper brine layer (UBL) resides above the chemocline, has lower salinity (12.6 to 14.7%) and is oxic. Displacement of the DBL may involve trace element movement within the water column due to changes in redox potential. Evidence of stratification displacement in the water column has been observed at two fixed stations on the lake by monitoring vertical water temperature profiles with horizontal and vertical velocity profiles. Stratification displacement events occur over periods of 12 to 24 h and are associated with strong wind events that can produce seiches within the water column. In addition to displacement events, the DBL shrinks and expands in response to changes in the lake surface area over a period of months. Laboratory tests simulating the observed sediment re-suspension were conducted over daily, weekly and monthly time scales to understand the effect of placing anoxic bottom sediments in contact with oxic water, and the associated effect of trace element desorption and (or) dissolution. Results from the laboratory simulations indicate that a small percentage (1%) of selenium associated with anoxic bottom sediments is periodically solubilized into the UBL where it potentially can be incorporated into the biota utilizing the oxic part of GSL.

Occurrence and Distribution of Iron, Manganese, and Selected Trace Elements in Ground Water in the Glacial Aquifer System of the Northern United States

USGS Publications Warehouse

Groschen, George E.; Arnold, Terri L.; Morrow, William S.; Warner, Kelly L.

2009-01-01

Dissolved trace elements, including iron and manganese, are often an important factor in use of ground water for drinking-water supplies in the glacial aquifer system of the United States. The glacial aquifer system underlies most of New England, extends through the Midwest, and underlies portions of the Pacific Northwest and Alaska. Concentrations of dissolved trace elements in ground water can vary over several orders of magnitude across local well networks as well as across regions of the United States. Characterization of this variability is a step toward a regional screening-level assessment of potential human-health implications. Ground-water sampling, from 1991 through 2003, of the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey determined trace element concentrations in water from 847 wells in the glacial aquifer system. Dissolved iron and manganese concentrations were analyzed in those well samples and in water from an additional 743 NAWQA land-use and major-aquifer survey wells. The samples are from monitoring and water-supply wells. Concentrations of antimony, barium, beryllium, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, selenium, strontium, thallium, uranium, and zinc vary as much within NAWQA study units (local scale; ranging in size from a few thousand to tens of thousands of square miles) as over the entire glacial aquifer system. Patterns of trace element concentrations in glacial aquifer system ground water were examined by using techniques suitable for a dataset with zero to 80 percent of analytical results reported as below detection. During the period of sampling, the analytical techniques changed, which generally improved the analytical sensitivity. Multiple reporting limits complicated the comparison of detections and concentrations. Regression on Order Statistics was used to model probability distributions and estimate the medians and other quantiles of the trace element concentrations. Strontium and barium were the most frequently detected and usually were present in the highest concentrations. Iron and manganese were the next most commonly detected and next highest in concentrations. Iron concentrations were the most variable with respect to the range of variations (both within local networks and aquifer-wide) and with respect to the disparity between magnitude of concentrations (detections) and the frequency of samples below reporting limits (nondetections). Antimony, beryllium, cadmium, silver, and thallium were detected too infrequently for substantial interpretation of their occurrence or distributions or potential human-health implications. For those elements that were more frequently detected, there are some geographic patterns in their occurrence that primarily reflect climate effects. The highest concentrations of several elements were found in the West-Central glacial framework area (High Plains and northern Plains areas). There are few important patterns for any element in relation to land use, well type, or network type. Shallow land-use (monitor) wells had iron concentrations generally lower than the glacial aquifer system wells overall and much lower than major-aquifer survey wells, which comprise mostly private- and public-supply wells. Unlike those for iron, concentration patterns for manganese were similar among shallow land-use wells and major-aquifer survey wells. An apparent relation between low pH and relatively low concentrations of many elements, except lead, may be more indicative of the relatively low dissolved-solids content in wells in the Northeastern United States that comprise the majority of low pH wells, than of a pH dependent pattern. Iron and manganese have higher concentrations and larger ranges of concentrations especially under more reducing conditions. Dissolved oxygen and well depth were related to iron and manganese concentrations. Redox conditions also affect several trace elements such

A Multi-Proxy Paradigm in the Pursuit of Ocean Paleoredox

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Duan, Y.; Kendall, B.; Reinhard, C.; Severmann, S.; Lyons, T. W.

2011-12-01

The geologic record provides abundant evidence for variations in ocean oxygenation throughout Earth history. Expansion of ocean anoxic zones is expected in the future as a consequence of global climate change, with attendant effects on global nutrient inventories, carbon cycling and fluxes of trace greenhouse gases to the atmosphere. Therefore, studying ancient ocean redox variations not only teaches us about the history of the Earth system, but also provides insights into how the system may respond to analogous human perturbations. However, the extent, duration, causes, and consequences of most past variations are poorly understood. This problem motivates the development of paleoredox proxies, including novel stable isotope systems such as Mo, Fe, U and Tl. Experience with these emerging isotope systems demonstrates great promise but also many challenges. The Mo isotope system is illustrative. To first order, the geochemical cycling and isotope systematics of this element are straightforward, making it a useful proxy. However, critical unresolved issues include: (a) uncertainties in the ocean inputs through time; (b) ambiguities about fractionation mechanisms; (c) inadequate understanding of how modern analogs map to ancient systems. Similar challenges confront all the novel isotope systems. The way forward requires integration of multiple isotopic proxies, as well as information gleaned from careful analyses of element concentrations. For example, an episode of Mo enrichment in the 2.5 Ga Mt. McRae Shale is generally interpreted as resulting from buildup of Mo in seawater due to oxidative weathering. This enrichment is therefore thought to indicate a "whiff" of O2 in the environment prior to the Great Oxidation Event that began at 2.4 Ga. Molybdenum isotopes are consistent with this interpretation. However, Mo enrichment due to enhanced input from low-T hydrothermal sources in an anoxic regime cannot be completely excluded given the current state of knowledge of Mo isotope systematics from such sources. By considering sedimentary Fe enrichments together with Fe isotopes, we find that the Mo enrichment correlates with the telltale signature of a shelf-to-basin Fe redox "shuttle". Uranium isotopes also exhibit variations indicative of redox transformations. This multi-proxy dataset therefore paints a robust picture of trace metal redox cycling consistent with the "whiff" interpretation.

Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS)

PubMed Central

Ginder-Vogel, Matthew; Landrot, Gautier; Fischel, Jason S.; Sparks, Donald L.

2009-01-01

Quantification of the initial rates of environmental reactions at the mineral/water interface is a fundamental prerequisite to determining reaction mechanisms and contaminant transport modeling and predicting environmental risk. Until recently, experimental techniques with adequate time resolution and elemental sensitivity to measure initial rates of the wide variety of environmental reactions were quite limited. Techniques such as electron paramagnetic resonance and Fourier transform infrared spectroscopies suffer from limited elemental specificity and poor sensitivity to inorganic elements, respectively. Ex situ analysis of batch and stirred-flow systems provides high elemental sensitivity; however, their time resolution is inadequate to characterize rapid environmental reactions. Here we apply quick-scanning x-ray absorption spectroscopy (Q-XAS), at sub-second time-scales, to measure the initial oxidation rate of As(III) to As(V) by hydrous manganese(IV) oxide. Using Q-XAS, As(III) and As(V) concentrations were determined every 0.98 s in batch reactions. The initial apparent As(III) depletion rate constants (t < 30 s) measured with Q-XAS are nearly twice as large as rate constants measured with traditional analytical techniques. Our results demonstrate the importance of developing analytical techniques capable of analyzing environmental reactions on the same time scale as they occur. Given the high sensitivity, elemental specificity, and time resolution of Q-XAS, it has many potential applications. They could include measuring not only redox reactions but also dissolution/precipitation reactions, such as the formation and/or reductive dissolution of Fe(III) (hydr)oxides, solid-phase transformations (i.e., formation of layered-double hydroxide minerals), or almost any other reaction occurring in aqueous media that can be measured using x-ray absorption spectroscopy. PMID:19805269

Profiling extractable and leachable inorganic impurities in ophthalmic drug containers by ICP-MS.

PubMed

Solomon, Paige; Nelson, Jenny

2018-03-01

In this study, we investigated the elemental impurities present in the plastic material of ophthalmic eye drop bottles using inductively coupled plasma-mass spectrometry (ICP-MS). Metallic contaminations, especially localized within the small cavity of the eye, can significantly perturb the ocular metallome. The concern is two-fold: first certain elements, for example heavy metals, can be toxic to humans at even trace levels, and second, these contaminations can have adverse reactions with other medicines or enzymatic processes in the eye. The implication of redox-active metals in cataract formation is one such biological consequence. The analysis demonstrated the effect of aggressive storage and transportation conditions on elemental extractable and leachable contamination, and posits that release of these elemental impurities can disrupt metallome equilibrium in the ocular compartment, leading to toxicity and disease.

Trace elements in agroecosystems and impacts on the environment.

PubMed

He, Zhenli L; Yang, Xiaoe E; Stoffella, Peter J

2005-01-01

Trace elements mean elements present at low concentrations (mg kg-1 or less) in agroecosystems. Some trace elements, including copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), molybdenum (Mo), and boron (B) are essential to plant growth and are called micronutrients. Except for B, these elements are also heavy metals, and are toxic to plants at high concentrations. Some trace elements, such as cobalt (Co) and selenium (Se), are not essential to plant growth but are required by animals and human beings. Other trace elements such as cadmium (Cd), lead (Pb), chromium (Cr), nickel (Ni), mercury (Hg), and arsenic (As) have toxic effects on living organisms and are often considered as contaminants. Trace elements in an agroecosystem are either inherited from soil parent materials or inputs through human activities. Soil contamination with heavy metals and toxic elements due to parent materials or point sources often occurs in a limited area and is easy to identify. Repeated use of metal-enriched chemicals, fertilizers, and organic amendments such as sewage sludge as well as wastewater may cause contamination at a large scale. A good example is the increased concentration of Cu and Zn in soils under long-term production of citrus and other fruit crops. Many chemical processes are involved in the transformation of trace elements in soils, but precipitation-dissolution, adsorption-desorption, and complexation are the most important processes controlling bioavailability and mobility of trace elements in soils. Both deficiency and toxicity of trace elements occur in agroecosystems. Application of trace elements in fertilizers is effective in correcting micronutrient deficiencies for crop production, whereas remediation of soils contaminated with metals is still costly and difficult although phytoremediation appears promising as a cost-effective approach. Soil microorganisms are the first living organisms subjected to the impacts of metal contamination. Being responsive and sensitive, changes in microbial biomass, activity, and community structure as a result of increased metal concentration in soil may be used as indicators of soil contamination or soil environmental quality. Future research needs to focus on the balance of trace elements in an agroecosystem, elaboration of soil chemical and biochemical parameters that can be used to diagnose soil contamination with or deficiency in trace elements, and quantification of trace metal transport from an agroecosystem to the environment.

Chemical characterization and toxicity of particulate matter emissions from roadside trash combustion in urban India

NASA Astrophysics Data System (ADS)

Vreeland, Heidi; Schauer, James J.; Russell, Armistead G.; Marshall, Julian D.; Fushimi, Akihiro; Jain, Grishma; Sethuraman, Karthik; Verma, Vishal; Tripathi, Sachi N.; Bergin, Michael H.

2016-12-01

Roadside trash burning is largely unexamined as a factor that influences air quality, radiative forcing, and human health even though it is ubiquitously practiced across many global regions, including throughout India. The objective of this research is to examine characteristics and redox activity of fine particulate matter (PM2.5) associated with roadside trash burning in Bangalore, India. Emissions from smoldering and flaming roadside trash piles (n = 24) were analyzed for organic and elemental carbon (OC/EC), brown carbon (BrC), and toxicity (i.e. redox activity, measured via the dithiothreitol "DTT" assay). A subset of samples (n = 8) were further assessed for toxicity by a cellular assay (macrophage assay) and also analyzed for trace organic compounds. Results show high variability of chemical composition and toxicity between trash-burning emissions, and characteristic differences from ambient samples. OC/EC ratios for trash-burning emissions range from 0.8 to 1500, while ambient OC/EC ratios were observed at 5.4 ± 1.8. Trace organic compound analyses indicate that emissions from trash-burning piles were frequently composed of aromatic di-acids (likely from burning plastics) and levoglucosan (an indicator of biomass burning), while the ambient sample showed high response from alkanes indicating notable representation from vehicular exhaust. Volume-normalized DTT results (i.e., redox activity normalized by the volume of air pulled through the filter during sampling) were, unsurprisingly, extremely elevated in all trash-burning samples. Interestingly, DTT results suggest that on a per-mass basis, fresh trash-burning emissions are an order of magnitude less redox-active than ambient air (13.4 ± 14.8 pmol/min/μgOC for trash burning; 107 ± 25 pmol/min/μgOC for ambient). However, overall results indicate that near trash-burning sources, exposure to redox-active PM can be extremely high.

Trace element abundances in major minerals of Late Permian coals from southwestern Guizhou province, China

USGS Publications Warehouse

Zhang, Jiahua; Ren, D.; Zheng, C.; Zeng, R.; Chou, C.-L.; Liu, J.

2002-01-01

Fourteen samples of minerals were separated by handpicking from Late Permian coals in southwestern Guizhou province, China. These 14 minerals were nodular pyrite, massive recrystallized pyrite, pyrite deposited from low-temperature hydrothermal fluid and from ground water; clay minerals; and calcite deposited from low-temperature hydrothermal fluid and from ground water. The mineralogy, elemental composition, and distribution of 33 elements in these samples were studied by optical microscopy, scanning electron microscope equipped with energy-dispersive X-ray spectrometer (SEM-EDX), X-ray diffraction (XRD), cold-vapor atomic absorption spectrometry (CV-AAS), atomic fluorescence spectrometry (AFS), inductively coupled-plasma mass spectrometry (ICP-MS), and ion-selective electrode (ISE). The results show that various minerals in coal contain variable amounts of trace elements. Clay minerals have high concentrations of Ba, Be, Cs, F, Ga, Nb, Rb, Th, U, and Zr. Quartz has little contribution to the concentration of trace elements in bulk coal. Arsenic, Mn, and Sr are in high concentrations in calcite. Pyrite has high concentrations of As, Cd, Hg, Mo, Sb, Se, Tl, and Zn. Different genetic types of calcite in coal can accumulate different trace elements; for example Ba, Co, Cr, Hg, Ni, Rb, Sn, Sr, and Zn are in higher concentrations in calcite deposited from low-temperature hydrothermal fluid than in that deposited from ground water. Furthermore, the concentrations of some trace elements are quite variable in pyrite; different genetic types of pyrites (Py-A, B, C, D) have different concentrations of trace elements, and the concentrations of trace elements are also different in pyrite of low-temperature hydrothermal origin collected from different locations. The study shows that elemental concentration is rather uniform in a pyrite vein. There are many micron and submicron mosaic pyrites in a pyrite vein, which is enriched in some trace elements, such as As and Mo. The content of trace element in pyrite vein depends upon the content of mosaic pyrite and of trace elements in it. Many environmentally sensitive trace elements are mainly contained in the minerals in coal, and hence the physical coal cleaning techniques can remove minerals from coal and decrease the emissions of potentially hazardous trace elements. ?? 2002 Elsevier Science B.V. All rights reserved.

Redox Conditions Among the Terrestrial Planets

NASA Technical Reports Server (NTRS)

Jones, J. H.

2004-01-01

Early solar system conditions should have been extremely reducing. The redox state of the early solar nebula was determined by the H2O/H2 of the gas, which is calculated (based on solar composition) to have been about IW-5. At high temperature under such conditions, ferrous iron would exist only as a trace element in silicates and the most common type of chondritic material should have been enstatite chondrites. The observation that E-chondrites form only a subset of the chondrite suite and that the terrestrial planets (Earth, Moon, Mars, Venus, 4 Vesta) contain ferrous and ferric iron as major and minor elements, respectively, implies that either most chondritic materials formed under conditions that were not solar or that early-formed metals oxidized at low temperature, producing FeO. For example, equilibrated ordinary chondrites (by definition, common chondritic materials), by their phase assemblage of olivine, orthopyroxene and metal, must fall not far from the QFI (Quartz-Fayalite-Iron) oxygen buffer. The QFI buffer is about IW-0.5 and, as we shall see, this fo2 is close to that inferred for many materials in the inner solar system.

Mo isotopes as redox indicators for the Southern Tethys during the PETM

NASA Astrophysics Data System (ADS)

Wouters, H.; Dickson, A.; Porcelli, D.; Hesselbo, S. P.; van den Boorn, S.; Gomez, V. G.; Mutterlose, J.

2014-12-01

As several ocean and climate models predict a decline in dissolved ocean oxygen concentrations associated with future global warming [1], recent research is increasingly focusing on past episodes of low ocean oxygen levels. Trace metals are generally enriched in organic-rich sediments deposited under such low oxygen conditions, and the concentration and isotopic signatures of several of these elements (e.g. Mo, U, Cr) may be applied as proxies to reconstruct the processes involved in these redox changes [2,3]. This project investigates the use of the molybdenum isotope system as a proxy for redox changes during an interval of abrupt environmental change spanning the Paleocene/Eocene boundary (the Paleocene/Eocene Thermal Maximum, PETM, ~56 Ma). The PETM is characterized by global warming and environmental and ecological changes including decreased ocean oxygen levels [4]. Study of the PETM can therefore offer us a valuable insight into how marine ecosystems and biogeochemical cycles may respond to future climate changes, and the predicted decrease of oxygen concentrations in seawater. The molybdenum concentrations and isotope compositions of organic-rich sediments spanning the PETM have been obtained from a Jordan oil shale drill core (OS-28). The obtained δ98/95Mo isotopic ratios range between -0.12‰ and 1.59‰ and coincide with significant fluctuations in trace metal abundances. The data together demonstrate that the global environmental changes associated with the PETM were manifest in the Jordanian basin as significant changes in basin hydrography and dissolved oxygen levels.

Trace element uptake and distribution in plants.

PubMed

Graham, Robin D; Stangoulis, James C R

2003-05-01

There are similarities between mammals and plants in the absorption and transport of trace elements. The chemistry of trace element uptake from food sources in both cases is based on the thermodynamics of adsorption on charged solid surfaces embedded in a solution phase of charged ions and metal-binding ligands together with redox systems in the case of iron and some other elements. Constitutive absorption systems function in nutrient uptake during normal conditions, and inducible "turbo" systems increase the supply of a particular nutrient during deficiency. Iron uptake is the most studied of the micronutrients, and divides the plant kingdom into two groups: dicotyledonous plants have a turbo system that is an upregulated version of the constitutive system, which consists of a membrane-bound reductase and an ATP-driven hydrogen ion extrusion pump; and monocotyledonous plants have a constitutive system similar to that of the dicots, but with an inducible system remarkably different that uses the mugeneic acid class of phytosiderophores (PS). The PS system may in fact be an important port of entry for iron from an iron-rich but exceedingly iron-insoluble lithosphere into the iron-starved biosphere. Absorption of trace metals in these graminaceous plants is normally via divalent ion channels after reduction in the plasma membrane. Once absorbed, iron can be stored in plants as phytoferritin or transported to active sites by transport-specific ligands. The transport of iron and zinc into seeds is dominated by the phloem sap system, which has a high pH that requires chelation of heavy metals. Loading into grains involves three or four genes each that control chelation, membrane transport and deposition as phytate.

The Review of Nuclear Microscopy Techniques: An Approach for Nondestructive Trace Elemental Analysis and Mapping of Biological Materials.

PubMed

Mulware, Stephen Juma

2015-01-01

The properties of many biological materials often depend on the spatial distribution and concentration of the trace elements present in a matrix. Scientists have over the years tried various techniques including classical physical and chemical analyzing techniques each with relative level of accuracy. However, with the development of spatially sensitive submicron beams, the nuclear microprobe techniques using focused proton beams for the elemental analysis of biological materials have yielded significant success. In this paper, the basic principles of the commonly used microprobe techniques of STIM, RBS, and PIXE for trace elemental analysis are discussed. The details for sample preparation, the detection, and data collection and analysis are discussed. Finally, an application of the techniques to analysis of corn roots for elemental distribution and concentration is presented.

Spatial variability of organic matter molecular composition and elemental geochemistry in surface sediments of a small boreal Swedish lake

NASA Astrophysics Data System (ADS)

Tolu, Julie; Rydberg, Johan; Meyer-Jacob, Carsten; Gerber, Lorenz; Bindler, Richard

2017-04-01

The composition of sediment organic matter (OM) exerts a strong control on biogeochemical processes in lakes, such as those involved in the fate of carbon, nutrients and trace metals. While between-lake spatial variability of OM quality is increasingly investigated, we explored in this study how the molecular composition of sediment OM varies spatially within a single lake and related this variability to physical parameters and elemental geochemistry. Surface sediment samples (0-10 cm) from 42 locations in Härsvatten - a small boreal forest lake with a complex basin morphometry - were analyzed for OM molecular composition using pyrolysis gas chromatography mass spectrometry for the contents of 23 major and trace elements and biogenic silica. We identified 162 organic compounds belonging to different biochemical classes of OM (e.g., carbohydrates, lignin and lipids). Close relationships were found between the spatial patterns of sediment OM molecular composition and elemental geochemistry. Differences in the source types of OM (i.e., terrestrial, aquatic plant and algal) were linked to the individual basin morphometries and chemical status of the lake. The variability in OM molecular composition was further driven by the degradation status of these different source pools, which appeared to be related to sedimentary physicochemical parameters (e.g., redox conditions) and to the molecular structure of the organic compounds. Given the high spatial variation in OM molecular composition within Härsvatten and its close relationship with elemental geochemistry, the potential for large spatial variability across lakes should be considered when studying biogeochemical processes involved in the cycling of carbon, nutrients and trace elements or when assessing lake budgets.

Impact of uranium (U) on the cellular glutathione pool and resultant consequences for the redox status of U.

PubMed

Viehweger, Katrin; Geipel, Gerhard; Bernhard, Gert

2011-12-01

Uranium (U) as a redox-active heavy metal can cause various redox imbalances in plant cells. Measurements of the cellular glutathione/glutathione disulfide (GSH/GSSG) by HPLC after cellular U contact revealed an interference with this essential redox couple. The GSH content remained unaffected by 10 μM U whereas the GSSG level immediately increased. In contrast, higher U concentrations (50 μM) drastically raised both forms. Using the Nernst equation, it was possible to calculate the half-cell reduction potential of 2GSH/GSSG. In case of lower U contents the cellular redox environment shifted towards more oxidizing conditions whereas the opposite effect was obtained by higher U contents. This indicates that U contact causes a consumption of reduced redox equivalents. Artificial depletion of GSH by chlorodinitrobenzene and measuring the cellular reducing capacity by tetrazolium salt reduction underlined the strong requirement of reduced redox equivalents. An additional element of cellular U detoxification mechanisms is the complex formation between the heavy metal and carboxylic functionalities of GSH. Because two GSH molecules catalyze electron transfers each with one electron forming a dimer (GSSG) two UO(2) (2+) are reduced to each UO(2) (+) by unbound redox sensitive sulfhydryl moieties. UO(2) (+) subsequently disproportionates to UO(2) (2+) and U(4+). This explains that in vitro experiments revealed a reduction to U(IV) of only around 33% of initial U(VI). Cellular U(IV) was transiently detected with the highest level after 2 h of U contact. Hence, it can be proposed that these reducing processes are an important element of defense reactions induced by this heavy metal.

The effect of aeration on the removal of wastewater-derived pharmaceutical residues from groundwater - a laboratory study.

PubMed

Burke, Victoria; Duennbier, Uwe; Massmann, Gudrun

2013-01-01

Several studies on waste- or drinking water treatment processes as well as on groundwater have recently shown that some pharmaceutical residues (PRs) are redox-sensitive. Hence, their (bio)degradation depends on the redox conditions prevalent in the aquifer. Groundwater, providing raw water for drinking water production, is often anoxic and aeration is a widespread treatment method applied mainly to eliminate unwanted iron and manganese from the water. As a side-effect, aeration may trigger the elimination of PRs. Within the present study the influence of aeration on the fate of a number of wastewater derived analgesics and their residues as well as several antimicrobial compounds was investigated. For this purpose, anoxic groundwater was transferred into stainless steel tanks, some of which were aerated while others were continuously kept anoxic. Results prove that the degradation of six phenazone type compounds is dependent on oxygen availability and compounds are efficiently removed under oxic conditions only. Concerning the antimicrobials, doxycycline and trimethoprim were better removed during aeration, whereas a slightly improved removal under anoxic conditions was observed for clindamycin, roxithromycin and clarithromycin. The study provides first laboratory proof of the redox-sensitivity of several organic trace pollutants. In addition, results demonstrate that aeration is an effective treatment for the elimination of a number of wastewater derived PRs.

Chromatographic-ICPMS methods for trace element and isotope analysis of water and biogenic calcite

NASA Astrophysics Data System (ADS)

Klinkhammer, G. P.; Haley, B. A.; McManus, J.; Palmer, M. R.

2003-04-01

ICP-MS is a powerful technique because of its sensitivity and speed of analysis. This is especially true for refractory elements that are notoriously difficult using TIMS and less energetic techniques. However, as ICP-MS instruments become more sensitive to elements of interest they also become more sensitive to interference. This becomes a pressing issue when analyzing samples with high total dissolved solids. This paper describes two trace element methods that overcome these problems by using chromatographic techniques to precondition samples prior to analysis by ICP-MS: separation of rare earth elements (REEs) from seawater using HPLC-ICPMS, and flow-through dissolution of foraminiferal calcite. Using HPLC in combination with ICP-MS it is possible to isolate the REEs from matrix, other transition elements, and each other. This method has been developed for small volume samples (5ml) making it possible to analyze sediment pore waters. As another example, subjecting foram shells to flow-through reagent addition followed by time-resolved analysis in the ICP-MS allows for systematic cleaning and dissolution of foram shells. This method provides information about the relationship between dissolution tendency and elemental composition. Flow-through is also amenable to automation thus yielding the high sample throughput required for paleoceanography, and produces a highly resolved elemental matrix that can be statistically analyzed.

Total reflection X-ray fluorescence as a convenient tool for determination of trace elements in microscale gasoline and diesel

NASA Astrophysics Data System (ADS)

Zhang, Airui; Jin, Axiang; Wang, Hai; Wang, Xiaokang; Zha, Pengfei; Wang, Meiling; Song, Xiaoping; Gao, Sitian

2018-03-01

Quantitative determination of trace elements like S, Fe, Cu, Mn and Pb in gasoline and S in diesel is of great importance due to the growing concerns over air pollution, human health and engine failure caused by utilization of gasoline and diesel with these harmful elements. A method of total reflection X-ray fluorescence (TXRF) was developed to measure these harmful trace elements in gasoline and diesel. A variety of factors to affect measurement results, including TXRF parameters, microwave-assisted digestion conditions and internal standard element and its addition, were examined to optimize these experimental procedures. The hydrophobic treatment of the surface of quartz reflectors to support the analyte with neutral silicone solutions could prepare thin films of gasoline and diesel digestion solutions for subsequent TXRF analysis. The proposed method shows good potential and reliability to determine the content of harmful trace elements in gasoline and diesel with high sensitivity and accuracy without drawing different standard calibration curves, and can be easily employed to screen gasoline and diesel in routine quality control and assurance.

Trace elements contamination and human health risk assessment in drinking water from Shenzhen, China.

PubMed

Lu, Shao-You; Zhang, Hui-Min; Sojinu, Samuel O; Liu, Gui-Hua; Zhang, Jian-Qing; Ni, Hong-Gang

2015-01-01

The levels of seven essential trace elements (Mn, Co, Ni, Cu, Zn, Se, and Mo) and six non-essential trace elements (Cr, As, Cd, Sb, Hg, and Pb) in a total of 89 drinking water samples collected in Shenzhen, China were determined using inductively coupled plasma mass spectrometry (ICP-MS) in the present study. Both the essential and non-essential trace elements were frequently detectable in the different kinds of drinking waters assessed. Remarkable temporal and spatial variations were observed among most of the trace elements in the tap water collected from two tap water treatment plants. Meanwhile, potential human health risk from these non-essential trace elements in the drinking water for local residents was also assessed. The median values of cancer risks associated with exposure to carcinogenic metals via drinking water consumption were estimated to be 6.1 × 10(-7), 2.1 × 10(-8), and 2.5 × 10(-7) for As, Cd, and Cr, respectively; the median values of incremental lifetime for non-cancer risks were estimated to be 6.1 × 10(-6), 4.4 × 10(-5), and 2.2 × 10(-5) for Hg, Pb, and Sb, respectively. The median value of total incremental lifetime health risk induced by the six non-essential trace elements for the population was 3.5 × 10(-5), indicating that the potential health risks from non-carcinogenic trace elements in drinking water also require some attention. Sensitivity analysis indicates that the most important factor for health risk assessment should be the levels of heavy metal in drinking water.

Detrital and oceanic dysoxia influence on OAE2 sediment geochemistry from Tarfaya, SW Morocco

NASA Astrophysics Data System (ADS)

Turgeon, S. C.; Kolonic, S.; Brumsack, H.-J.; Wagner, T.

2003-04-01

The Cretaceous "greenhouse" world's stratigraphic record is punctuated by several important organic-rich intervals representing quasi-global "Oceanic Anoxic Events" (OAEs). This study focuses on sediments from Tarfaya in SW Morocco deposited during the Cenomanian-Turonian Boundary Event (CTBE or OAE2 at 93.5 Ma). These sediments consist of distinctly laminated, carbonate-rich black shales alternating with lighter coloured structureless intervals and sporadic chert lenses. Sediments from three sites representing proximal to distal settings were studied. Samples were analysed for Ctot, Corg, Stot, as well as several major-, minor- and trace elements using XRF and ICP-MS. These sediments are characterised by high Corg, Stot, and CaCO3 contents and consist of a simple two component mixing system ("average shale"-CaCO3). Major element concentrations are low, except for Ca and P, owing in part to the carbonate dilution effect. Most elements plot along "average shale" lines. Elements such as Si, Ti, Fe, K, Rb, and Zr show positive relationships with Al2O3, pointing to homogeneous source area material. Several Al-normalised elements (As, Ba, Cr, Cu, Ni, Sr, U, V, Y, Zn), many of them redox-sensitive or sulphide-residing, are enriched in the sediments indicating an oxygen-depleted environment and potential availability of hydrogen sulfide in the water column at the time of deposition. High Zn concentrations suggest increased submarine volcanism and/or hydrothermal activity during this time interval. High Ba concentrations are possibly indicative of high regional paleoproductivity, which is further supported by the elevated P concentrations hinting at nutrient availability. Basinward trends in the geochemical distribution of some elements are apparent and probably reflect the decreasing influence of terrestrial sediments away from the shoreline.

Trace metal mapping by laser-induced breakdown spectroscopy

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

Kaiser, Jozef; Novotny, Dr. Karel; Hrdlicka, A

2012-01-01

Abstract: Laser-Induced Breakdown Spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of solid, gaseous and liquid samples. The potential applications of lasers for spectrochemical analysis were developed shortly after its invention; however the massive development of LIBS is connected with the availability of powerful pulsed laser sources. Since the late 80s of 20th century LIBS dominated the analytical atomic spectroscopy scene and its application are developed continuously. Here we review the utilization of LIBS for trace elements mapping in different matrices. The main emphasis is on trace metal mapping in biological samples.

Impaired redox signaling and antioxidant gene expression in endothelial cells in diabetes: a role for mitochondria and the nuclear factor-E2-related factor 2-Kelch-like ECH-associated protein 1 defense pathway.

PubMed

Cheng, Xinghua; Siow, Richard C M; Mann, Giovanni E

2011-02-01

Type 2 diabetes is an age-related disease associated with vascular pathologies, including severe blindness, renal failure, atherosclerosis, and stroke. Reactive oxygen species (ROS), especially mitochondrial ROS, play a key role in regulating the cellular redox status, and an overproduction of ROS may in part underlie the pathogenesis of diabetes and other age-related diseases. Cells have evolved endogenous defense mechanisms against sustained oxidative stress such as the redox-sensitive transcription factor nuclear factor E2-related factor 2 (Nrf2), which regulates antioxidant response element (ARE/electrophile response element)-mediated expression of detoxifying and antioxidant enzymes and the cystine/glutamate transporter involved in glutathione biosynthesis. We hypothesize that diminished Nrf2/ARE activity contributes to increased oxidative stress and mitochondrial dysfunction in the vasculature leading to endothelial dysfunction, insulin resistance, and abnormal angiogenesis observed in diabetes. Sustained hyperglycemia further exacerbates redox dysregulation, thereby providing a positive feedback loop for severe diabetic complications. This review focuses on the role that Nrf2/ARE-linked gene expression plays in regulating endothelial redox homeostasis in health and type 2 diabetes, highlighting recent evidence that Nrf2 may provide a therapeutic target for countering oxidative stress associated with vascular disease and aging.

Vertical distribution of major, minor and trace elements in sediments from mud volcanoes of the Gulf of Cadiz: evidence of Cd, As and Ba fronts in upper layers

NASA Astrophysics Data System (ADS)

Carvalho, Lina; Monteiro, Rui; Figueira, Paula; Mieiro, Cláudia; Almeida, Joana; Pereira, Eduarda; Magalhães, Vítor; Pinheiro, Luís; Vale, Carlos

2018-01-01

Mud volcanoes are feature of the coastal margins where anaerobic oxidation of methane triggers geochemical signals. Elemental composition, percentage of fine particles and loss on ignition were determined in sediment layers of eleven gravity cores retrieved from four mud volcanoes (Sagres, Bonjardim, Soloviev and Porto) and three undefined structures located on the deep Portuguese margin of the Gulf of Cadiz. Calcium was positively correlated to Sr and inversely to Al as well as to most of the trace elements. Vertical profiles of Ba, Cd and As concentrations, and their ratios to Al, in Porto and Soloviev showed pronounced enhancements in the top 50-cm depth. Sub-surface enhancements were less pronounced in other mud volcanoes and were absent in sediments from the structures. These profiles were interpreted as diagenetic enrichments related to the anaerobic oxidation of methane originated from upward methane-rich fluxes. The observed barium fronts were most likely caused by the presence of barite which precipitated at the sulphate-methane transition zone. Cd and As enrichments have probably resulted from successive dissolution/precipitation of sulphides in response to vertical shifts of redox boundaries.

The Early Toarcian oceanic anoxic event: Paleoenvironmental and paleoclimatic change across the Alpine Tethys (Switzerland)

NASA Astrophysics Data System (ADS)

Fantasia, Alicia; Föllmi, Karl B.; Adatte, Thierry; Spangenberg, Jorge E.; Montero-Serrano, Jean-Carlos

2018-03-01

Paleoenvironmental and paleoclimatic change associated with the Toarcian oceanic anoxic event (T-OAE) was evaluated in five successions located in Switzerland. They represent different paleogeographic settings across the Alpine Tethys: the northern shelf (Gipf, Riniken and Rietheim), the Sub-Briançonnais basin (Creux de l'Ours), and the Lombardian basin (Breggia). The multi-proxy approach chosen (whole-rock and clay mineralogy, phosphorus, major and trace elements) shows that local environmental conditions modulated the response to the T-OAE across the Alpine Tethys. On the northern shelf and in the Sub-Briançonnais basin, high kaolinite contents and detrital proxies (detrital index, Ti, Zr, Si) in the T-OAE interval suggest a change towards a warmer and more humid climate coupled with an increase in the chemical weathering rates. In contrast, low kaolinite content in the Lombardian basin is likely related to a more arid climate along the southern Tethys margin and/or to a deeper and more distal setting. Redox-sensitive trace-element (V, Mo, Cu, Ni) enrichments in the T-OAE intervals reveal that dysoxic to anoxic conditions developed on the northern shelf, whereas reducing conditions were less severe in the Sub-Briançonnais basin. In the Lombardian basin well-oxygenated bottom water conditions prevailed. Phosphorus (P) speciation analysis was performed at Riniken and Creux de l'Ours. This is the first report of P speciation data for T-OAE sections, clearly suggesting that high P contents during this time interval are mainly linked to the presence of an authigenic phases and fish remains. The development of oxygen-depleted conditions during the T-OAE seems to have promoted the release of the organic-bound P back into the water column, thereby further sustaining primary productivity in a positive feedback loop.

Prediction of redox-sensitive cysteines using sequential distance and other sequence-based features.

PubMed

Sun, Ming-An; Zhang, Qing; Wang, Yejun; Ge, Wei; Guo, Dianjing

2016-08-24

Reactive oxygen species can modify the structure and function of proteins and may also act as important signaling molecules in various cellular processes. Cysteine thiol groups of proteins are particularly susceptible to oxidation. Meanwhile, their reversible oxidation is of critical roles for redox regulation and signaling. Recently, several computational tools have been developed for predicting redox-sensitive cysteines; however, those methods either only focus on catalytic redox-sensitive cysteines in thiol oxidoreductases, or heavily depend on protein structural data, thus cannot be widely used. In this study, we analyzed various sequence-based features potentially related to cysteine redox-sensitivity, and identified three types of features for efficient computational prediction of redox-sensitive cysteines. These features are: sequential distance to the nearby cysteines, PSSM profile and predicted secondary structure of flanking residues. After further feature selection using SVM-RFE, we developed Redox-Sensitive Cysteine Predictor (RSCP), a SVM based classifier for redox-sensitive cysteine prediction using primary sequence only. Using 10-fold cross-validation on RSC758 dataset, the accuracy, sensitivity, specificity, MCC and AUC were estimated as 0.679, 0.602, 0.756, 0.362 and 0.727, respectively. When evaluated using 10-fold cross-validation with BALOSCTdb dataset which has structure information, the model achieved performance comparable to current structure-based method. Further validation using an independent dataset indicates it is robust and of relatively better accuracy for predicting redox-sensitive cysteines from non-enzyme proteins. In this study, we developed a sequence-based classifier for predicting redox-sensitive cysteines. The major advantage of this method is that it does not rely on protein structure data, which ensures more extensive application compared to other current implementations. Accurate prediction of redox-sensitive cysteines not only enhances our understanding about the redox sensitivity of cysteine, it may also complement the proteomics approach and facilitate further experimental investigation of important redox-sensitive cysteines.

Trace-element deposition in the Cariaco Basin, Venezuela Shelf, under sulfate-reducing conditions: a history of the local hydrography and global climate, 20 ka to the present

USGS Publications Warehouse

Piper, David Z.; Dean, Walter E.

2002-01-01

A sediment core from the Cariaco Basin on the Venezuelan continental shelf, which recovered sediment that has been dated back to 20 ka (thousand years ago), was examined for its major-element-oxide and trace-element composition. Cadmium (Cd), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), vanadium (V), and zinc (Zn) can be partitioned between a siliciclastic, terrigenous-derived fraction and two seawater-derived fractions. The two marine fractions are (1) a biogenic fraction represented by nutrient trace elements taken up mostly in the photic zone by phytoplankton, and (2) a hydrogenous fraction that has been derived from bottom water via adsorption and precipitation reactions. This suite of trace elements contrasts with a second suite of trace elements—barium (Ba), cobalt (Co), gallium (Ga), lithium (Li), the rare-earth elements, thorium (Th), yttrium (Y), and several of the major-element oxides—that has had solely a terrigenous source. The partitioning scheme, coupled with bulk sediment accumulation rates measured by others, allows us to determine the accumulation rate of trace elements in each of the three sediment fractions and of the fractions themselves. The current export of organic matter from the photic zone, redox conditions and advection of bottom water, and flux of terrigenous debris into the basin can be used to calculate independently trace-element depositional rates. The calculated rates show excellent agreement with the measured rates of the surface sediment. This agreement supports a model of trace-element accumulation rates in the subsurface sediment that gives a 20-kyr history of upwelling into the photic zone (that is, primary productivity), bottom-water advection and redox, and provenance. Correspondence of extrema in the geochemical signals with global changes in sea level and climate demonstrates the high degree to which the basin hydrography and provenance have responded to the paleoceanographic and paleoclimatic regimes of the last 20 kyr. The accumulation rate of the marine fraction of Mo increased abruptly at about 14.8 ka (calendar years), from less than 0.5 µg cm-2 yr-1 to greater than 4 µg cm-2 yr-1. Its accumulation rate remained high but variable until 8.6 ka, when it decreased sharply to 1 µg cm-2 yr-1. It continued to decrease to 4.0 ka, to its lowest value for the past 15 kyr, before gradually increasing to the present. Between 14.8 ka and 8.6 ka, its accumulation rate exhibited strong maxima at 14.4, 13.0, and 9.9 ka. The oldest maximum corresponds to melt-water pulse IA into the Gulf of Mexico. A relative minimum, centered at about 11.1 ka, corresponds to melt-water pulse IB; a strong maximum occurs in the immediately overlying sediment. The maximum at 13.0 ka corresponds to onset of the Younger Dryas cold event. This pattern to the accumulation rate of Mo (and V) can be interpreted in terms of its deposition from bottom water of the basin, the hydrogenous fraction, under SO42- -reducing conditions, during times of intense bottom-water advection 14.8 ka to 11.1 ka and significantly less intense bottom-water advection 11 ka to the present. The accumulation rate of Cd shows a pattern that is only slightly different from that of Mo, although its deposition was determined largely by the rain rate of organic matter into the bottom water, a biogenic fraction whose deposition was driven by upwelling of nutrient-enriched water into the photic zone. Its accumulation exhibits only moderately high rates, on average, during both melt-water pulses. Its highest rate, and that of upwelling, occurred during the Younger Dryas, and again following melt-water pulse IB. The marine fractions of Cu, Ni, and Zn also have a strong biogenic signal. The siliciclastic terrigenous debris, however, represents the dominant source, and host, of Cu, Ni, and Zn. All four trace elements have a consid-erably weaker hydrogenous signal than biogenic signal. Accumulation rates of the terrigenous fraction, as reflected by accumulation rates of Th and Ga, show strong maxima at 16.2 and 12.7 ka and minima at 14.1 and 11.1 ka. Co, Li, REE, and Y have a similar distribution. The minima occurred during melt-water pulses IA and IB, the maxima during the Younger Dryas and the rise in sea level following the last glacial maximum.

Ultrafast photodynamics of the indoline dye D149 adsorbed to porous ZnO in dye-sensitized solar cells.

PubMed

Rohwer, Egmont; Richter, Christoph; Heming, Nadine; Strauch, Kerstin; Litwinski, Christian; Nyokong, Tebello; Schlettwein, Derck; Schwoerer, Heinrich

2013-01-14

We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I(-)/I(3)(-) redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Determination of trace heavy metal elements in cortex Phellodendron chinense by ICP-MS after microwave-assisted digestion].

PubMed

Kou, Xing-Ming; Xu, Min; Gu, Yong-Zuo

2007-06-01

An inductively coupled plasma mass spectrometry (ICP-MS) for determination of the contents of 8 trace heavy metal elements in cortex Phellodendron chinense after microwave-assisted digestion of the sample has been developed. The accuracy of the method was evaluated by the analysis of corresponding trace heavy metal elements in standard reference materials (GBW 07604 and GBW 07605). By applying the proposed method, the contents of 8 trace heavy metal elements in cortex Phellodendron chinense cultivated in different areas (in Bazhong, Yibin and Yingjing, respectively) of Sichuan and different growth period (6, 8 and 10 years of samples from Yingjing) were determined. The relative standard deviation (RSD) is in the range of 3.2%-17.8% and the recoveries of standard addition are in the range of 70%-120%. The results of the study indicate that the proposed method has the advantages of simplicity, speediness and sensitivity. It is suitable for the determination of the contents of 8 trace heavy metal elements in cortex Phellodendron chinense. The results also show that the concentrations of 4 harmful trace heavy metal elements As, Cd, Hg and Pb in cortex Phellodendron chinense are all lower than the limits of Chinese Pharmacopoeia and Green Trade Standard for Importing and Exporting Medicinal Plant and Preparation. Therefore, the cortex Phellodendron chinense is fit for use as medicine and export.

The vanadium isotope compositions of subduction zone lavas

NASA Astrophysics Data System (ADS)

Tian, S.; Huang, F.

2017-12-01

Vanadium is a redox sensitive element with multiple oxidation states, and thus it has the potential to trace redox-related processes. With the advancement of analytical method for V isotopes, we are now able to recognize V isotope fractionation for igneous rocks. Subduction zones are critical zones on the Earth for the interaction between crust and mantle where undergo complex geological processes. However, V isotope data of subduction zone lavas are still rare except those reported in [1]. To investigate the V isotope variations of subduction zones and discuss the potential to apply V to trace mantle redox state. In this contribution, we report δ51V for three subduction zone lavas from Kamchatka, Lesser Antilles, and Aleutians which are characterized by well-documented magmatic evolutionary series. 47 arc lava samples have been analyzed and the δ51V data of them range from -0.91‰ to -0.53‰ (2sd = 0.10 ‰). Among these samples, primitive arc basalts with MgO > 6 wt. % have an average δ51V of -0.80 ± 0.15‰ (2sd, n = 20), broadly consistent with δ51V data of MORB [2, 3]. Within the single arc of Kamchatka, δ51V data of primitive basalts from the arc front to the back-arc is almost constant, suggesting limited influences of mantle melting and source heterogeneity on V isotopes. δ51V data of these samples show no correlation with Ba/Nb, suggesting that fluids have little impact on V isotopes. On the other hand, δ51V data of the more involved samples with MgO < 6 wt. % are negatively correlated with MgO contents, indicating that the 50V preferentially enters crystalline minerals, which produces heavier V isotope compositions of residual melts. Distinct to the observation showing 2‰ fractionation reported in [1], the magnitude of V isotope fractionation in arc lavas is much smaller (0.38‰) in this study. Future works are needed for better understanding the V isotope fractionation mechanisms of subduction zone lavas. [1]Prytulak et al., 2017, Geochem. Persp. Let. 3, 75-84. [2]Huang et al., 2016, Goldschmidt Abstracts. 1190. [3] Prytulak et al., 2013, EPSL. 365, 177-189.

Copper tolerance and virulence in bacteria

PubMed Central

Ladomersky, Erik; Petris, Michael J.

2015-01-01

Copper (Cu) is an essential trace element for all aerobic organisms. It functions as a cofactor in enzymes that catalyze a wide variety of redox reactions due to its ability to cycle between two oxidation states, Cu(I) and Cu(II). This same redox property of copper has the potential to cause toxicity if copper homeostasis is not maintained. Studies suggest that the toxic properties of copper are harnessed by the innate immune system of the host to kill bacteria. To counter such defenses, bacteria rely on copper tolerance genes for virulence within the host. These discoveries suggest bacterial copper intoxication is a component of host nutritional immunity, thus expanding our knowledge of the roles of copper in biology. This review summarizes our current understanding of copper tolerance in bacteria, and the extent to which these pathways contribute to bacterial virulence within the host. PMID:25652326

Trace elements and radon in groundwater across the United States, 1992-2003

USGS Publications Warehouse

Ayotte, Joseph D.; Gronberg, Jo Ann M.; Apodaca, Lori E.

2011-01-01

Trace-element concentrations in groundwater were evaluated for samples collected between 1992 and 2003 from aquifers across the United States as part of the U.S. Geological Survey National Water-Quality Assessment Program. This study describes the first comprehensive analysis of those data by assessing occurrence (concentrations above analytical reporting levels) and by comparing concentrations to human-health benchmarks (HHBs). Data from 5,183 monitoring and drinking-water wells representing more than 40 principal and other aquifers in humid and dry regions and in various land-use settings were used in the analysis. Trace elements measured include aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), uranium (U), vanadium (V), and zinc (Zn). Radon (Rn) gas also was measured and is included in the data analysis. Climate influenced the occurrence and distribution of trace elements in groundwater whereby more trace elements occurred and were found at greater concentrations in wells in drier regions of the United States than in humid regions. In particular, the concentrations of As, Ba, B, Cr, Cu, Mo, Ni, Se, Sr, U, V, and Zn were greater in the drier regions, where processes such as chemical evolution, ion complexation, evaporative concentration, and redox (oxidation-reduction) controls act to varying degrees to mobilize these elements. Al, Co, Fe, Pb, and Mn concentrations in groundwater were greater in humid regions of the United States than in dry regions, partly in response to lower groundwater pH and (or) more frequent anoxic conditions. In groundwater from humid regions, concentrations of Cu, Pb, Rn, and Zn were significantly greater in drinking-water wells than in monitoring wells. Samples from drinking-water wells in dry regions had greater concentrations of As, Ba, Pb, Li, Sr, V, and Zn, than samples from monitoring wells. In humid regions, however, concentrations of most trace elements were greater in monitoring wells than in drinking-water wells; the exceptions were Cu, Pb, Zn, and Rn. Cu, Pb, and Zn are common trace elements in pumps and pipes used in the construction of drinking-water wells, and contamination from these sources may have contributed to their concentrations. Al, Sb, Ba, B, Cr, Co, Fe, Mn, Mo, Ni, Se, Sr, and U concentrations were all greater in monitoring wells than in drinking-water wells in humid regions. Groundwater from wells in agricultural settings had greater concentrations of As, Mo, and U than groundwater from wells in urban settings, possibly owing to greater pH in the agricultural wells. Significantly greater concentrations of B, Cr, Se, Ag, Sr, and V also were found in agricultural wells in dry regions. Groundwater from dry-region urban wells had greater concentrations of Co, Fe, Pb, Li, Mn, and specific conductance than groundwater from agricultural wells. The geologic composition of aquifers and aquifer geochemistry are among the major factors affecting trace-element occurrence. Trace-element concentrations in groundwater were characterized in aquifers from eight major groups based on geologic material, including (1) unconsolidated sand and gravel; (2) glacial unconsolidated sand and gravel; (3) semiconsolidated sand; (4) sandstone; (5) sandstone and carbonate rock; (6) carbonate rock; (7) basaltic and other volcanic rock; and (8) crystalline rock. The majority of groundwater samples and the largest percentages of exceedences of HHBs were in the glacial and nonglacial unconsolidated sand and gravel aquifers; in these aquifers, As, Mn, and U are the most common trace elements exceeding HHBs. Overall, 19 percent of wells (962 of 5,097) exceeded an HHB for at least one trace element. The trace elements with HHBs included in this summary were Sb, As, Ba, Be, B, Cd, Cr,

New Developments in Hard X-ray Fluorescence Microscopy for In-situ Investigations of Trace Element Distributions in Aqueous Systems of Soil Colloids

NASA Astrophysics Data System (ADS)

Gleber, Sophie-Charlotte; Weinhausen, Britta; Köster, Sarah; Ward, Jesse; Vine, David; Finney, Lydia; Vogt, Stefan

2013-10-01

The distribution, binding and release of trace elements on soil colloids determine matter transport through the soil matrix, and necessitates an aqueous environment and short length and time scales for their study. However, not many microscopy techniques allow for that. We previously showed hard x-ray fluorescence microscopy capabilities to image aqueous colloidal soil samples [1]. As this technique provides attogram sensitivity for transition elements like Cu, Zn, and other geochemically relevant trace elements at sub micrometer spatial resolution (currently down to 150 nm at 2-ID-E [2]; below 50nm at Bionanoprobe, cf. G.Woloschak et al, this volume) combined with the capability to penetrate tens of micrometer of water, it is ideally suited for imaging the elemental content of soil colloids. To address the question of binding and release processes of trace elements on the surface of soil colloids, we developed a microfluidics based XRF flow cytometer, and expanded the applied methods of hard x-ray fluorescence microscopy towards three dimensional imaging. Here, we show (a) the 2-D imaged distributions of Si, K and Fe on soil colloids of Pseudogley samples; (b) how the trace element distribution is a dynamic, pH-dependent process; and (c) x-ray tomographic applications to render the trace elemental distributions in 3-D. We conclude that the approach presented here shows the remarkable potential to image and quantitate elemental distributions from samles within their natural aqueous microenvironment, particularly important in the environmental, medical, and biological sciences.

Accumulation, Release, and Solubility of Arsenic, Molybdenum, and Vanadium in Wetland Sediments

USGS Publications Warehouse

Fox, P.M.; Doner, H.E.

2003-01-01

This study was undertaken to determine the fate of As, Mo, and V (trace elements, TEs) in the sediments of a constructed wetland in use for the remediation of potentially toxic trace element-contaminated agricultural drainwater. After three years of wetland operation, sediment cores were collected to determine changes in TE concentrations as a function of depth and the effects of varying water column depth. All TE concentrations were highest in the top 2 to 4 cm and decreased with depth. Molybdenum accumulated in the wetland sediments, up to levels of 32.5 ?? 4.6, 30.2 ?? 8.9, and 59.3 ?? 26.1 mg kg-1 in the top 1 cm of sediment at water depths of 15, 30, and 60 cm, respectively. In the top 2 cm of sediment, As accumulated (28.2 ?? 3.0 mg kg-1) only at the 60-cm water depth. Below 2 cm, as much as 10 mg kg-1 of As was lost from the sediment at all water depths. In most cases, V concentrations decreased in the sediment. In this wetland system, the lowest redox potentials were found near the sediment surface and increased with depth. Thus, in general As, Mo, and V concentrations in the sediment were highest under more reducing conditions and lowest under more oxidizing conditions. Most of the accumulated Mo (73%) became water soluble on drying of samples. This has important implications for systems undergoing changes in redox status; for instance, if these wetland sediments are dried, potentially large amounts of Mo may be solubilized.

Olivine-hosted melt inclusions as an archive of redox heterogeneity in magmatic systems

NASA Astrophysics Data System (ADS)

Hartley, Margaret E.; Shorttle, Oliver; Maclennan, John; Moussallam, Yves; Edmonds, Marie

2017-12-01

The redox state of volcanic products determines their leverage on the oxidation of Earth's oceans and atmosphere, providing a long-term feedback on oxygen accumulation at the planet's surface. An archive of redox conditions in volcanic plumbing systems from a magma's mantle source, through crustal storage, to eruption, is carried in pockets of melt trapped within crystals. While melt inclusions have long been exploited for their capacity to retain information on a magma's history, their permeability to fast-diffusing elements such as hydrogen is now well documented and their retention of initial oxygen fugacities (fO2) could be similarly diffusion-limited. To test this, we have measured Fe3+/ΣFe by micro-XANES spectroscopy in a suite of 65 olivine-hosted melt inclusions and 9 matrix glasses from the AD 1783 Laki eruption, Iceland. This eruption experienced pre-eruptive mixing of chemically diverse magmas, syn-eruptive degassing at the vent, and post-eruptive degassing during lava flow up to 60 km over land, providing an ideal test of whether changes in the fO2 of a magma may be communicated through to its cargo of crystal-hosted melt inclusions. Melt inclusions from rapidly quenched tephra samples have Fe3+/ΣFe of 0.206 ± 0.008 (ΔQFM of +0.7 ± 0.1), with no correlation between their fO2 and degree of trace element enrichment or differentiation. These inclusions preserve the redox conditions of the mixed pre-eruptive Laki magma. When corrected for fractional crystallisation to 10 wt.% MgO, these inclusions record a parental magma [Fe3+/ΣFe](10) of 0.18 (ΔQFM of +0.4), significantly more oxidised than the Fe3+/ΣFe of 0.10 that is often assumed for Icelandic basalt magmas. Melt inclusions from quenched lava selvages are more reduced than those from the tephra, having Fe3+/ΣFe between 0.133 and 0.177 (ΔQFM from -0.4 to +0.4). These inclusions have approached equilibrium with their carrier lava, which has been reduced by sulfur degassing. The progressive re-equilibration of fO2 between inclusions and carrier melts occurs on timescales of hours to days, causing a drop in the sulfur content at sulfide saturation (SCSS) and driving the exsolution of immiscible sulfide globules in the inclusions. Our data demonstrate the roles of magma mixing, progressive re-equilibration, and degassing in redox evolution within magmatic systems, and the open-system nature of melt inclusions to fO2 during these processes. Redox heterogeneity present at the time of inclusion trapping may be overprinted by rapid re-equilibration of melt inclusion fO2 with the external environment, both in the magma chamber and during slow cooling in lava at the surface. This can decouple the melt inclusion archives of fO2, major and trace element chemistry, and mask associations between fO2, magmatic differentiation and mantle source heterogeneity unless the assembly of diverse magmas is rapidly followed by eruption. Our tools for understanding the redox conditions of magmas are thus limited; however, careful reconstruction of pre- and post-eruptive magmatic history has enabled us to confirm the relatively oxidised nature of ocean island-type mantle compared to that of mid-ocean ridge mantle.

Rare earth element geochemistry of shallow carbonate outcropping strata in Saudi Arabia: Application for depositional environments prediction

NASA Astrophysics Data System (ADS)

Eltom, Hassan A.; Abdullatif, Osman M.; Makkawi, Mohammed H.; Eltoum, Isam-Eldin A.

2017-03-01

The interpretation of depositional environments provides important information to understand facies distribution and geometry. The classical approach to interpret depositional environments principally relies on the analysis of lithofacies, biofacies and stratigraphic data, among others. An alternative method, based on geochemical data (chemical element data), is advantageous because it can simply, reproducibly and efficiently interpret and refine the interpretation of the depositional environment of carbonate strata. Here we geochemically analyze and statistically model carbonate samples (n = 156) from seven sections of the Arab-D reservoir outcrop analog of central Saudi Arabia, to determine whether the elemental signatures (major, trace and rare earth elements [REEs]) can be effectively used to predict depositional environments. We find that lithofacies associations of the studied outcrop (peritidal to open marine depositional environments) possess altered REE signatures, and that this trend increases stratigraphically from bottom-to-top, which corresponds to an upward shallowing of depositional environments. The relationship between REEs and major, minor and trace elements indicates that contamination by detrital materials is the principal source of REEs, whereas redox condition, marine and diagenetic processes have minimal impact on the relative distribution of REEs in the lithofacies. In a statistical model (factor analysis and logistic regression), REEs, major and trace elements cluster together and serve as markers to differentiate between peritidal and open marine facies and to differentiate between intertidal and subtidal lithofacies within the peritidal facies. The results indicate that statistical modelling of the elemental composition of carbonate strata can be used as a quantitative method to predict depositional environments and regional paleogeography. The significance of this study lies in offering new assessments of the relationships between lithofacies and geochemical elements by using advanced statistical analysis, a method that could be used elsewhere to interpret depositional environment and refine facies models.

BEHAVIOR OF ARSENIC AND OTHER REDOX-SENSITIVE ELEMENTS IN CROWLEY LAKE, CA: A RESERVOIR IN THE LOS ANGELES AQUEDUCT SYSTEM. (R826202)

EPA Science Inventory

Elevated arsenic concentrations in Crowley Lake derive from upstream geothermal inputs. We examined the water column of Crowley Lake under stratified and unstratified conditions, seeking evidence for algal uptake and transformation of arsenic and its deposition to and release fro...

Major and Trace Element Analysis of Natural and Experimental Igneous Systems using LA-ICP-MS

NASA Technical Reports Server (NTRS)

Jenner, Frances E.; Arevalo, Ricardo D., Jr.

2016-01-01

Major- and trace-element compositions of minerals provide valuable information on a variety of global Earth-system processes, including melting of distinct mantle reservoirs, the growth and evolution of the Earths crust and the formation of economically viable ore deposits. In the mid-1980s and early 1990s, attempts were made to couple laser ablation (LA) systems to inductively coupled plasma mass spectrometry (ICPMS) instruments (e.g. Fryer et al. 1995; Jackson et al. 1992). The goal was to develop a rapid, highly sensitive in situ analytical technique to measure abundances and spatial distributions of trace elements in minerals and other geological samples. Elemental analysis using LAICPMS was envisaged as a quicker and less destructive means of chemical analysis (requiring only g quantities) than labour-intensive sample digestion and solution analysis (requiring mg-levels of material); and it would be a more cost-effective method than secondary ion mass spectrometry (SIMS) for the routine analysis of trace elements from solid samples. Furthermore, it would have lower limits-of-detection than electron probe microanalysis (EPMA) (e.g. Jackson et al. 1992; Eggins 2003).

Nuclear microanalysis of platinum and trace elements in cisplatin-resistant human ovarian adenocarcinoma cells

NASA Astrophysics Data System (ADS)

Moretto, P.; Ortega, R.; Llabador, Y.; Simonoff, M.; Bénard, J.; Moretto, Ph.

1995-09-01

Macro-and Micro-PIXE analysis were applied to study the mechanisms of cellular resistance to cisplatin, a chemotherapeutic agent, widely used nowadays for the treatment of ovarian cancer. Two cultured cell lines, a cisplatin-sensitive and a resistant one, were compared for their trace elements content and platinum accumulation following in vitro exposure to the drug. Bulk analysis revealed significant differences in copper and iron content between the two lines. Subsequent individual cell microanalysis permitted us to characterize the response of the different morphological cell types of the resistant line. This study showed that the metabolism of some trace metals in cisplatin-resistant cells could be affected but the exact relationship with the resistant phenotype remains to be determined. From a technical point of view, this experiment demonstrated that an accurate measurement of trace elements could be derived from nuclear microprobe analysis of individual cell.

Physiological Effects of Trace Elements and Chemicals in Water

ERIC Educational Resources Information Center

Varma, M. M.; And Others

1976-01-01

The physiological effects on humans and animals of trace amounts of organic and unorganic pollutants in natural and waste waters are examined. The sensitivity of particular organs and species is emphasized. Substances reviewed include mercury, arsenic, cadmium, lead, chromium, fluorides, nitrates and organics, including polychlounated biphenyls.…

[Study on the determination of 28 inorganic elements in sunflower seeds by ICP-OES/ICP-MS].

PubMed

Liu, Hong-Wei; Qin, Zong-Hui; Xie, Hua-Lin; Cao, Shu

2013-01-01

The present paper describes a simple method for the determination of trace elements in sunflower seeds by using inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma spectrometry (ICP-MS). HNO3 + H2O2 were used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The contents of 10 trace elements (Al, B, Ca, Fe, K, Mg, Na, Si, P and S) in sunflower seeds were determined by ICP-OES while 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sr, Sn, Sb, Ti, V and Zn) were determined by ICP-MS. The rice reference material (GBW10045) was used as standard reference materials. The results showed a good agreement between measured and certified values for all analytes. The concentrations of necessary micro elements Ca, K, Mg, P and S were higher. This method was simple, sensitive and precise and can perform simultaneous multi-elements determination of sunflower seeds.

Brain imaging in methamphetamine-treated mice using a nitroxide contrast agent for EPR imaging of the redox status and a gadolinium contrast agent for MRI observation of blood-brain barrier function.

PubMed

Emoto, M C; Yamato, M; Sato-Akaba, H; Yamada, K; Matsuoka, Y; Fujii, H G

2015-01-01

Methamphetamine (METH)-induced neurotoxicity is associated with mitochondrial dysfunction and enhanced oxidative stress. The aims of the present study conducted in the mouse brain repetitively treated with METH were to (1) examine the redox status using the redox-sensitive imaging probe 3-methoxycarbonyl-2,2,5,5-tetramethylpiperidine-1-oxyl (MCP) and (2) non-invasively visualize the brain redox status with electron paramagnetic resonance (EPR) imaging. The rate of reduction of MCP was measured from a series of temporal EPR images of mouse heads, and this rate was used to construct a two-dimensional map of rate constants called a "redox map." The obtained redox map clearly illustrated the change in redox balance in the METH-treated mouse brain that is a known result of oxidative damage. Biochemical assays also showed that the level of thiobarbituric acid-reactive substance, an index of lipid peroxidation, was increased in mouse brains by METH. The enhanced reduction in MCP observed in mouse brains was remarkably suppressed by treatment with the dopamine synthase inhibitor, α-methyl-p-tyrosine, suggesting that enhancement of the reduction reaction of MCP resulted from enzymatic reduction in the mitochondrial respiratory chain. Furthermore, magnetic resonance imaging (MRI) of METH-treated mice using a blood-brain barrier (BBB)-impermeable paramagnetic contrast agent revealed BBB dysfunction after treatment with METH for 7 days. MRI also indicated that the impaired BBB recovered after withdrawal of METH. EPR imaging and MRI are useful tools not only for following changes in the redox status and BBB dysfunction in mouse brains repeatedly administered METH, but also for tracing the drug effect after withdrawal of METH.

Rapid screening of heavy metals and trace elements in environmental samples using portable X-ray fluorescence spectrometer, A comparative study

PubMed Central

McComb, Jacqueline Q.; Rogers, Christian; Han, Fengxiang X.; Tchounwou, Paul B.

2014-01-01

With industrialization, great amounts of trace elements and heavy metals have been excavated and released on the surface of the earth and dissipated into the environments. Rapid screening technology for detecting major and trace elements as well as heavy metals in variety of environmental samples is most desired. The objectives of this study were to determine the detection limits, accuracy, repeatability and efficiency of a X-ray fluorescence spectrometer (Niton XRF analyzer) in comparison with the traditional analytical methods, inductively coupled plasma optical emission spectrometer (ICP-OES) and inductively coupled plasma optical emission spectrometer (ICP-MS) in screening of major and trace elements of environmental samples including estuary soils and sediments, contaminated soils, and biological samples. XRF is a fast and non-destructive method in measuring the total concentration of multi--elements simultaneously. Contrary to ICP-OES and ICP-MS, XRF analyzer is characterized by the limited preparation required for solid samples, non-destructive analysis, increased total speed and high throughout, the decreased production of hazardous waste and the low running costs as well as multi-elemental determination and portability in the fields. The current comparative study demonstrates that XRF is a good rapid non-destructive method for contaminated soils, sediments and biological samples containing higher concentrations of major and trace elements. Unfortunately, XRF does not have sensitive detection limits of most major and trace elements as ICP-OES or ICP-MS but it may serve as a rapid screening tool for locating hot spots of uncontaminated field soils and sediments. PMID:25861136

Optimizing detector geometry for trace element mapping by X-ray fluorescence.

PubMed

Sun, Yue; Gleber, Sophie-Charlotte; Jacobsen, Chris; Kirz, Janos; Vogt, Stefan

2015-05-01

Trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral response of energy dispersive detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. We conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples. Copyright © 2015. Published by Elsevier B.V.

Optimizing detector geometry for trace element mapping by X-ray fluorescence

PubMed Central

Sun, Yue; Gleber, Sophie-Charlotte; Jacobsen, Chris; Kirz, Janos; Vogt, Stefan

2016-01-01

Trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral response of energy dispersive detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. We conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples. PMID:25600825

Optimizing detector geometry for trace element mapping by X-ray fluorescence

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

Sun, Yue; Gleber, Sophie-Charlotte; Jacobsen, Chris

Trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral response of energy dispersivemore » detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. We conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples.« less

Chemostratigraphy of the Sudbury impact basin fill: Volatile metal loss and post-impact evolution of a submarine impact basin

NASA Astrophysics Data System (ADS)

O'Sullivan, Edel M.; Goodhue, Robbie; Ames, Doreen E.; Kamber, Balz S.

2016-06-01

The 1.85 Ga Sudbury structure provides a unique opportunity to study the sequence of events that occurred within a hydrothermally active subaqueous impact crater during the late stages of an impact and in its aftermath. Here we provide the first comprehensive chemostratigraphic study for the lower crater fill, represented by the ca. 1.4 km thick Onaping Formation. Carefully hand-picked ash-sized matrix of 81 samples was analysed for major elements, full trace elements and C isotopes. In most general terms, the composition of the clast-free matrix resembles that of the underlying melt sheet. However, many elements show interesting chemostratigraphies. The high field strength element evolution clearly indicates that the crater rim remained intact during the deposition of the entire Onaping Formation, collapsing only at the transition to the overlying Onwatin Formation. An interesting feature is that several volatile metals (e.g., Pb, Sb) are depleted by >90% in the lower Onaping Formation, suggesting that the impact resulted in a net loss of at least some volatile species, supporting the idea of ;impact erosion,; whereby volatile elements were vaporised and lost to space during impact. Reduced C contents in the lower Onaping Formation are low (<0.1 wt%) but increase to 0.5-1 wt% up stratigraphy, where δ13C becomes constant at -31‰, indicating a biogenic origin. Elevated Y/Ho and U/Th require that the ash interacted with saline water, most likely seawater. Redox-sensitive trace metal chemostratigraphies (e.g., V and Mo) suggest that the basin was anoxic and possibly euxinic and became inhabited by plankton, whose rain-down led to a reservoir effect in certain elements (e.g., Mo). This lasted until the crater rim was breached, the influx of fresh seawater promoting renewed productivity. If the Sudbury basin is used as an analogue for the Hadean and Eoarchaean Earth, our findings suggest that hydrothermal systems, capable of producing volcanogenic massive sulphides, could develop within the rims of large to giant impact structures. These hydrothermal systems did not require mid-ocean ridges and implicitly, the operation of plate tectonics. Regardless of hydrothermal input, enclosed submarine impact basins also provided diverse isolated environments (potential future oases) for the establishment of life.

A new method for automated discontinuity trace mapping on rock mass 3D surface model

NASA Astrophysics Data System (ADS)

Li, Xiaojun; Chen, Jianqin; Zhu, Hehua

2016-04-01

This paper presents an automated discontinuity trace mapping method on a 3D surface model of rock mass. Feature points of discontinuity traces are first detected using the Normal Tensor Voting Theory, which is robust to noisy point cloud data. Discontinuity traces are then extracted from feature points in four steps: (1) trace feature point grouping, (2) trace segment growth, (3) trace segment connection, and (4) redundant trace segment removal. A sensitivity analysis is conducted to identify optimal values for the parameters used in the proposed method. The optimal triangular mesh element size is between 5 cm and 6 cm; the angle threshold in the trace segment growth step is between 70° and 90°; the angle threshold in the trace segment connection step is between 50° and 70°, and the distance threshold should be at least 15 times the mean triangular mesh element size. The method is applied to the excavation face trace mapping of a drill-and-blast tunnel. The results show that the proposed discontinuity trace mapping method is fast and effective and could be used as a supplement to traditional direct measurement of discontinuity traces.

An FeIII Azamacrocyclic Complex as a pH-Tunable Catholyte and Anolyte for Redox-Flow Battery Applications.

PubMed

Tsitovich, Pavel B; Kosswattaarachchi, Anjula M; Crawley, Matthew R; Tittiris, Timothy Y; Cook, Timothy R; Morrow, Janet R

2017-11-02

A reversible Fe 3+ /Fe 2+ redox couple of an azamacrocyclic complex is evaluated as an electrolyte with a pH-tunable potential range for aqueous redox-flow batteries (RFBs). The Fe III complex is formed by 1,4,7-triazacyclononane (TACN) appended with three 2-methyl-imidazole donors, denoted as Fe(Tim). This complex exhibits pH-sensitive redox couples that span E 1/2 (Fe 3+ /Fe 2+ )=317 to -270 mV vs. NHE at pH 3.3 and pH 12.8, respectively. The 590 mV shift in potential and kinetic inertness are driven by ionization of the imidazoles at various pH values. The Fe 3+ /Fe 2+ redox is proton-coupled at alkaline conditions, and bulk electrolysis is non-destructive. The electrolyte demonstrates high charge/discharge capacities at both acidic and alkaline conditions throughout 100 cycles. Given its tunable redox, fast electrochemical kinetics, exceptional stability/cyclability, this complex is promising for the design of aqueous RFB catholytes and anolytes that utilize the earth-abundant element iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vegetarian diets and public health: biomarker and redox connections.

PubMed

Benzie, Iris F F; Wachtel-Galor, Sissi

2010-11-15

Vegetarian diets are rich in antioxidant phytochemicals. However, they may not act as antioxidants in vivo, and yet still have important signaling and regulatory functions. Some may act as pro-oxidants, modulating cellular redox tone and oxidizing redox sensitive sites. In this review, evidence for health benefits of vegetarian diets is presented from different perspectives: epidemiological, biomarker, evolutionary, and public health, as well as antioxidant. From the perspective of molecular connections between diet and health, evidence of a role for plasma ascorbic acid as a biomarker for future disease risk is presented. Basic concepts of redox-based cell signaling are presented, and effects of antioxidant phytochemicals on signaling, especially via redox tone, sulfur switches and the Antioxidant Response Element (ARE), are explored. Sufficient scientific evidence exists for public health policy to promote a plant-rich diet for health promotion. This does not need to wait for science to provide all the answers as to why and how. However, action and interplay of dietary antioxidants in the nonequilibrium systems that control redox balance, cell signaling, and cell function provide rich ground for research to advance understanding of orthomolecular nutrition and provide science-based evidence to advance public health in our aging population.

In situ phytoremediation of arsenic- and metal-polluted pyrite waste with field crops: effects of soil management.

PubMed

Vamerali, Teofilo; Bandiera, Marianna; Mosca, Giuliano

2011-05-01

Sunflower, alfalfa, fodder radish and Italian ryegrass were cultivated in severely As-Cd-Co-Cu-Pb-Zn-contaminated pyrite waste discharged in the past and capped with 0.15m of unpolluted soil at Torviscosa (Italy). Plant growth and trace element uptake were compared under ploughing and subsoiling tillages (0.3m depth), the former yielding higher contamination (∼30%) in top soil. Tillage choice was not critical for phytoextraction, but subsoiling enhanced above-ground productivity, whereas ploughing increased trace element concentrations in plants. Fodder radish and sunflower had the greatest aerial biomass, and fodder radish the best trace element uptake, perhaps due to its lower root sensitivity to pollution. Above-ground removals were generally poor (maximum of 33mgm(-2) of various trace elements), with Zn (62%) and Cu (18%) as main harvested contaminants. The most significant finding was of fine roots proliferation in shallow layers that represented a huge sink for trace element phytostabilisation. It is concluded that phytoextraction is generally far from being an efficient management option in pyrite waste. Sustainable remediation requires significant improvements of the vegetation cover to stabilise the site mechanically and chemically, and provide precise quantification of root turnover. Copyright © 2011 Elsevier Ltd. All rights reserved.

Trace elements content in the selected medicinal plants traditionally used for curing skin diseases by the natives of Mizoram, India.

PubMed

Rajan, Jay Prakash; Singh, Kshetrimayum Birla; Kumar, Sanjiv; Mishra, Raj Kumar

2014-09-01

To determine the trace elements content in the selected medicinal plants, namely, Eryngium foetidum L., Mimosa pudica L., Polygonum plebeium, and Prunus cerasoides D. Don traditionally used by the natives of the Mizoram, one of the north eastern states in India as their folklore medicines for curing skin diseases like eczema, leg and fingers infection, swelling and wound. A 3 MeV proton beam of proton induced X-ray emission technique, one of the most powerful techniques for its quick multi elemental trace analysis capability and high sensitivity was used to detect and characterized for trace elements. The studies revealed that six trace elements, namely, Fe, Zn, Cu, Mn, V, and Co detected in mg/L unit were present in varying concentrations in the selected medicinal plants with high and notable concentration of Fe, Zn, Mn and appreciable amount of the Cu, Co and V in all the plants. The results of the present study support the therapeutic usage of these medicinal plants in the traditional practices for curing skin diseases since they are found to contain appreciable amount of the Fe, Zn, Cu, Mn, V and Co. Copyright © 2014 Hainan Medical College. Published by Elsevier B.V. All rights reserved.

LA-ICP-MS trace element mapping: insights into the crystallisation history of a metamorphic garnet population

NASA Astrophysics Data System (ADS)

George, Freya; Gaidies, Fred

2017-04-01

In comparison to our understanding of major element zoning, relatively little is known about the incorporation of trace elements into metamorphic garnet. Given their extremely slow diffusivities and sensitivity to changing mineral assemblages, the analysis of the distribution of trace elements in garnet has the potential to yield a wealth of information pertaining to interfacial attachment mechanisms during garnet crystallisation, the mobility of trace elements in both garnet and the matrix, and trace element geochronology. Due to advances in the spatial resolution and analytical precision of modern microbeam techniques, small-scale trace element variations can increasingly be documented and used to inform models of metamorphic crystallisation. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in particular, can be used to rapidly quantify a wide range of elemental masses as a series of laser rasters, producing large volumes of spatially constrained trace element data. In this study, we present LA-ICP-MS maps of trace element concentrations from numerous centrally-sectioned garnets representative of the crystal size-distribution of a single sample's population. The study sample originates from the garnet-grade Barrovian zone of the Lesser Himalayan Sequence in Sikkim, northeast India, and has been shown to have crystallised garnet within a single assemblage between 515 ˚C and 565˚C, with no evidence for accessory phase reaction over the duration of garnet growth. Previous models have indicated that the duration of garnet crystallisation was extremely rapid (<1 Myr), with negligible diffusional homogenisation of major divalent cations. Consequently, the trace element record likely documents the primary zonation generated during garnet growth. In spite of straightforward (i.e. concentrically-zoned) major element garnet zonation, trace elements maps are characterised by significant complexity and variability. Y and the heavy rare earth elements are strongly enriched in crystal cores, where there is overprinting of the observed internal fabric, and exhibit numerous concentric annuli towards crystal rims. Conversely, the medium rare earth elements (e.g. Gd, Eu and Sm) exhibit bowl-shaped zoning from core to rim, with no annuli, and core and rim compositions of the medium rare earth elements are the same throughout the population within crystals of differing size. Cr exhibits pronounced spiral zoning, and the average Cr content increases towards garnet rims. In all cases, spirals are centered on the geometric core of the crystals. These LA-ICP-MS maps highlight the complexity of garnet growth over a single prograde event, and indicate that there is still much to be learnt from the analysis of garnet using ever-improving analytical methods. We explore the potential causes of the variations in the distribution of trace elements in garnet, and assess how these zoning patterns may be used to refine our understanding of the intricacies of garnet crystallisation and the spatial and temporal degree of trace element equilibration during metamorphism.

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

Gong, Ke; Xu, Fei; Grunewald, Jonathan B.

The rapid growth of intermittent renewable energy (e.g., wind and solar) demands low-cost and large-scale energy storage systems for smooth and reliable power output, where redox-flow batteries (RFBs) could find their niche. In this work, we introduce the first all-soluble all-iron RFB based on iron as the same redox-active element but with different coordination chemistries in alkaline aqueous system. The adoption of the same redox-active element largely alleviates the challenging problem of cross-contamination of metal ions in RFBs that use two redox-active elements. An all-soluble all-iron RFB is constructed by combining an iron–triethanolamine redox pair (i.e., [Fe(TEOA)OH] –/[Fe(TEOA)(OH)] 2–) andmore » an iron–cyanide redox pair (i.e., Fe(CN) 6 3–/Fe(CN) 6 4–), creating 1.34 V of formal cell voltage. Furthermore, good performance and stability have been demonstrated, after addressing some challenges, including the crossover of the ligand agent. As exemplified by the all-soluble all-iron flow battery, combining redox pairs of the same redox-active element with different coordination chemistries could extend the spectrum of RFBs.« less

All-soluble all-iron aqueous redox-flow battery

DOE PAGES

Gong, Ke; Xu, Fei; Grunewald, Jonathan B.; ...

2016-05-03

The rapid growth of intermittent renewable energy (e.g., wind and solar) demands low-cost and large-scale energy storage systems for smooth and reliable power output, where redox-flow batteries (RFBs) could find their niche. In this work, we introduce the first all-soluble all-iron RFB based on iron as the same redox-active element but with different coordination chemistries in alkaline aqueous system. The adoption of the same redox-active element largely alleviates the challenging problem of cross-contamination of metal ions in RFBs that use two redox-active elements. An all-soluble all-iron RFB is constructed by combining an iron–triethanolamine redox pair (i.e., [Fe(TEOA)OH] –/[Fe(TEOA)(OH)] 2–) andmore » an iron–cyanide redox pair (i.e., Fe(CN) 6 3–/Fe(CN) 6 4–), creating 1.34 V of formal cell voltage. Furthermore, good performance and stability have been demonstrated, after addressing some challenges, including the crossover of the ligand agent. As exemplified by the all-soluble all-iron flow battery, combining redox pairs of the same redox-active element with different coordination chemistries could extend the spectrum of RFBs.« less

Marine Biogeochemistry of Particulate Trace Elements in the Exclusive Economic Zone (eez) of the State of Qatar

NASA Astrophysics Data System (ADS)

Yigiterhan, O.; Al-Ansari, I. S.; Abdel-Moati, M.; Murray, J. W.; Al-Ansi, M.

2016-02-01

We focus on the trace element geochemistry of particulate matter in the Exclusive Economic Zone (EEZ) of Qatar. A main goal of this research was to analyze a complete suite of trace elements on particulate matter samples from the water column from different oceanographic biogeochemical zones of the EEZ around Qatar. The sample set also includes plankton samples which are the main source of biogenic particles, dust samples which are a source of abiological particles to surface seawater and surface sediments which can be a source of resuspended particles and a sink for settling particles. The 15 metals and 2 non-metals analyzed in this study will be Al, Ti, V, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn, Mo, Ag, Ba, U and P, N. Many factors control the composition of trace elements in marine particles. Most of these are important in the EEZ of Qatar, including:1. Natural sources: These are rivers, atmospheric dust, sediment resuspension and leaks from oil beds. However, due to very limited rainfall rivers play no major role in Qatar but resuspension of shallow carbonate rich sediments and input of atmospheric dust are important due to strong currents and surrounding deserts.2. Adsorption/desorption: These chemical processes occur everywhere in the ocean and transfer metals between particles and the solution phase.3. Biological uptake: This process is likewise a universal ocean process and results in transport of metals from the solution phase to biological particles.4. Redox conditions: These are important chemical reactions in the oxic, suboxic and anoxic zones. This can be the dominant controlling mechanism in the northeastern hypoxic deeper waters of the Qatar EEZ.5. Anthropogenic sources: The eastern part of the Qatar contains numerous industrial sites, petroleum/gas platforms and refineries. There are numerous industrial sources but the main hot spots are the port of Doha and the industrial cities of Mesaieed, Khor Al-Odaid, and Ras Laffan. We aimed to determine the influence of the different current systems, water masses, and terrestrial inputs on the distribution, fractionation, and fate of trace metal contaminants and elemental pollutants. We have also observed the level of anthropogenic enrichments for some of the elements which have not been previously documented. This research should be viewed as the first stage of a complete study.

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry.

PubMed

Becker, J S; Breuer, U; Westheide, J; Saprykin, A I; Holzbrecher, H; Nickel, H; Dietze, H J

1996-06-01

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.

Geochemistry of host rocks in the Howards Pass district, Yukon-Northwest Territories, Canada: implications for sedimentary environments of Zn-Pb and phosphate mineralization

USGS Publications Warehouse

Slack, John F.; Falck, Hendrik; Kelley, Karen D.; Xue, Gabriel G.

2017-01-01

Detailed lithogeochemical data are reported here on early Paleozoic sedimentary rocks that host the large Howards Pass stratiform Zn-Pb deposits in Yukon-Northwest Territories. Redox-sensitive trace elements (Mo, Re, V, U) and Ce anomalies in members of the Duo Lake Formation record significant environmental changes. During the deposition of lower footwall units (Pyritic siliceous and Calcareous mudstone members), bottom waters were anoxic and sulphidic, respectively; these members formed in a marginal basin that may have become increasingly restricted with time. Relative to lower members, a major environmental change is proposed for deposition of the overlying Lower cherty mudstone member, which contains phosphorite beds up to ∼0.8 m thick in the upper part, near the base of the Zn-Pb deposits. The presence of these beds, together with models for modern phosphorite formation, suggests P input from an upwelling system and phosphorite deposition in an upper slope or outer shelf setting. The overlying Active mudstone member contains stratabound to stratiform Zn-Pb deposits within black mudstone and gray calcareous mudstone. Data for unmineralized black mudstone in this member indicate deposition under diverse redox conditions from suboxic to sulphidic. Especially distinctive in this member are uniformly low ratios of light to heavy rare earth elements that are unique within the Duo Lake Formation, attributed here to the dissolution of sedimentary apatite by downward-percolating acidic metalliferous brines. Strata that overlie the Active member (Upper siliceous mudstone member) consist mainly of black mudstone with thin (0.5–1.5 cm) laminae of fine-grained apatite, recording continued deposition on an upper slope or outer shelf under predominantly suboxic bottom waters. Results of this study suggest that exploration for similar stratiform sediment-hosted Zn-Pb deposits should include the outer parts of ancient continental margins, especially at and near stratigraphic transitions from marginal basin facies to overlying slope or shelf facies.

Plants as indicators of urban air pollution (ozone and trace elements) in Pisa, Italy.

PubMed

Nali, Cristina; Crocicchi, Lara; Lorenzini, Giacomo

2004-07-01

A biennial integrated survey, based on the use of vascular plants for the bioindication of the effects of tropospheric ozone, was performed in the area of Pisa (Tuscany, Central Italy). It also investigated the distribution of selected trace elements in plants and the data were compared with those obtained from the use of passive samplers, automatic analysers of ozone and lichen biodiversity. Photochemically produced ozone proved to be present during the warm season, with maximum hourly means surpassing 100 ppb: the use of supersensitive tobacco Bel-W3 confirmed the value of detailed, cost-effective, monitoring surveys. Trials with clover clones demonstrate that sensitive plants undergo severe biomass reduction in the current ozone regime. The mean NC-S (clover clone sensitive to ozone):NC-R (resistant) biomass ratio ranged from 0.7 (in 1999) to 0.5 (in 2000). The economic impact of these reductions deserves attention. The data obtained using passive ozone samplers exceeded those obtained using an automatic analyser. The mapping of epiphytic lichen biodiversity was not related to the geographical ozone distribution as can be seen from the tobacco's response. Lettuce plants grown under standardized conditions were used positively as bioaccumulators of trace elements: Pb was abundantly recovered, but a large portion of this element was removed by washing.

Trace elements as paradigms of developmental neurotoxicants: lead, methylmercury and arsenic

PubMed Central

Grandjean, Philippe; Herz, Katherine T.

2014-01-01

Trace elements have contributed unique insights into developmental neurotoxicity and serve as paradigms for such adverse effects. Many trace elements are retained in the body for long periods and can be easily measured to assess exposure by inexpensive analytical methods that became available several decades ago so that past and cumulated exposures could be easily characterized through analysis of biological samples, e.g. blood and urine. The first compelling evidence resulted from unfortunate poisoning events that allowed scrutiny of long-term outcomes of acute exposures that occurred during early development. Pursuant to this documentation, prospective studies of children's cohorts that applied sensitive neurobehavioral methods supported the notion that the brain is uniquely vulnerable to toxic damage during early development. Lead, methylmercury, and arsenic thereby serve as paradigm neurotoxicants that provide a reference for other substances that may have similar adverse effects. Less evidence is available on manganese, fluoride, and cadmium, but experience from the former trace elements suggest that, with time, adverse effects are likely to be documented at exposures previously thought to be low and safe. PMID:25175507

Trace elements as paradigms of developmental neurotoxicants: Lead, methylmercury and arsenic.

PubMed

Grandjean, Philippe; Herz, Katherine T

2015-01-01

Trace elements have contributed unique insights into developmental neurotoxicity and serve as paradigms for such adverse effects. Many trace elements are retained in the body for long periods and can be easily measured to assess exposure by inexpensive analytical methods that became available several decades ago so that past and cumulated exposures could be easily characterized through analysis of biological samples, e.g. blood and urine. The first compelling evidence resulted from unfortunate poisoning events that allowed scrutiny of long-term outcomes of acute exposures that occurred during early development. Pursuant to this documentation, prospective studies of children's cohorts that applied sensitive neurobehavioral methods supported the notion that the brain is uniquely vulnerable to toxic damage during early development. Lead, methylmercury, and arsenic thereby serve as paradigm neurotoxicants that provide a reference for other substances that may have similar adverse effects. Less evidence is available on manganese, fluoride, and cadmium, but experience from the former trace elements suggest that, with time, adverse effects are likely to be documented at exposures previously thought to be low and safe. Copyright © 2014 Elsevier GmbH. All rights reserved.

The Effects of Supplementary Mulberry Leaf (Morus alba) Extracts on the Trace Element Status (Fe, Zn and Cu) in Relation to Diabetes Management and Antioxidant Indices in Diabetic Rats.

PubMed

Król, Ewelina; Jeszka-Skowron, Magdalena; Krejpcio, Zbigniew; Flaczyk, Ewa; Wójciak, Rafał W

2016-11-01

Mulberry leaves (Morus alba) have been used in folk medicine to mitigate symptoms of diabetes. The mulberry plant contains phenolic compounds that are able to decrease blood glucose concentration. Since various phenolics have antioxidant and metal binding properties, they can be used to alleviate oxidative stress and chelate trace elements involved in redox reactions. The aim of this study was to evaluate the effects of dietary supplementation with mulberry leaf extracts (acetone-water (AE) and ethanol-water (EE)) on the trace element status (Fe, Zn and Cu) in relation to diabetes management and antioxidant indices in high-fat diet-fed/STZ diabetic rats. The experiment was performed on 38 male Wistar rats with diabetes (induced by high-fat diet (HF) and streptozotocin injection) or the control fed with AIN-93M or high-fat diet. As a result, five experimental groups were used: (1) a healthy control group fed with AIN-93M; (2) an HF control group; (3) a diabetic HF group; (4) a diabetic HF + AE group (6 g/kg diet); (5) a diabetic HF + EE group (6 g/kg diet). The rats were fed with appropriate diets for 4 weeks. The content of trace elements (Fe, Zn and Cu) in the serum and tissues was measured by means of atomic absorption spectrometry (AAS). Biochemical analyses (glucose, TBARS, FRAP) were performed on the blood serum. It was shown that the AE decreased hepatic and renal Fe stores, while the EE increased hepatic Cu levels in diabetic rats and confirmed their ability to regulate the Fe and Cu status in diabetes. The results confirmed a significant hypoglycaemic and antioxidant potential of both mulberry leaf extracts in diabetic rats.

Trace Elements in River Waters

NASA Astrophysics Data System (ADS)

Gaillardet, J.; Viers, J.; Dupré, B.

2003-12-01

Trace elements are characterized by concentrations lower than 1 mg L-1 in natural waters. This means that trace elements are not considered when "total dissolved solids" are calculated in rivers, lakes, or groundwaters, because their combined mass is not significant compared to the sum of Na+, K+, Ca2+, Mg2+, H4SiO4, HCO3-, CO32-, SO42-, Cl-, and NO3-. Therefore, most of the elements, except about ten of them, occur at trace levels in natural waters. Being trace elements in natural waters does not necessarily qualify them as trace elements in rocks. For example, aluminum, iron, and titanium are major elements in rocks, but they occur as trace elements in waters, due to their low mobility at the Earth's surface. Conversely, trace elements in rocks such as chlorine and carbon are major elements in waters.The geochemistry of trace elements in river waters, like that of groundwater and seawater, is receiving increasing attention. This growing interest is clearly triggered by the technical advances made in the determination of concentrations at lower levels in water. In particular, the development of inductively coupled plasma mass spectrometry (ICP-MS) has considerably improved our knowledge of trace-element levels in waters since the early 1990s. ICP-MS provides the capability of determining trace elements having isotopes of interest for geochemical dating or tracing, even where their dissolved concentrations are extremely low.The determination of trace elements in natural waters is motivated by a number of issues. Although rare, trace elements in natural systems can play a major role in hydrosystems. This is particularly evident for toxic elements such as aluminum, whose concentrations are related to the abundance of fish in rivers. Many trace elements have been exploited from natural accumulation sites and used over thousands of years by human activities. Trace elements are therefore highly sensitive indexes of human impact from local to global scale. Pollution impact studies require knowledge of the natural background concentrations and knowledge of pollutant behavior. For example, it is generally accepted that rare earth elements (REEs) in waters behave as good analogues for the actinides, whose natural levels are quite low and rarely measured. Water quality investigations have clearly been a stimulus for measurement of toxic heavy metals in order to understand their behavior in natural systems.From a more fundamental point of view, it is crucial to understand the behavior of trace elements in geological processes, in particular during chemical weathering and transport by waters. Trace elements are much more fractionated by weathering and transport processes than major elements, and these fractionations give clues for understanding the nature and intensity of the weathering+transport processes. This has not only applications for weathering studies or for the past mobilization and transport of elements to the ocean (potentially recorded in the sediments), but also for the possibility of better utilization of trace elements in the aqueous environment as an exploration tool.In this chapter, we have tried to review the recent literature on trace elements in rivers, in particular by incorporating the results derived from recent ICP-MS measurements. We have favored a "field approach" by focusing on studies of natural hydrosystems. The basic questions which we want to address are the following: What are the trace element levels in river waters? What controls their abundance in rivers and fractionation in the weathering+transport system? Are trace elements, like major elements in rivers, essentially controlled by source-rock abundances? What do we know about the chemical speciation of trace elements in water? To what extent do colloids and interaction with solids regulate processes of trace elements in river waters? Can we relate the geochemistry of trace elements in aquatic systems to the periodic table? And finally, are we able to satisfactorily model and predict the behavior of most of the trace elements in hydrosystems?An impressive literature has dealt with experimental works on aqueous complexation, uptake of trace elements by surface complexation (inorganic and organic), uptake by living organisms (bioaccumulation) that we have not reported here, except when the results of such studies directly explain natural data. As continental waters encompass a greater range of physical and chemical conditions, we focus on river waters and do not discuss trace elements in groundwaters, lakes, and the ocean. In lakes and in the ocean, the great importance of life processes in regulating trace elements is probably the major difference from rivers.Section 5.09.2 of this chapter reports data. We will review the present-day literature on trace elements in rivers to show that our knowledge is still poor. By comparing with the continental abundances, a global mobility index is calculated for each trace element. The spatial and temporal variability of trace-element concentrations in rivers will be shown to be important. In Section 5.09.3, sources of trace elements in river waters are indicated. We will point out the great diversity of sources and the importance of global anthropogenic contamination for a number of elements. The question of inorganic and organic speciation of trace elements in river water will then be addressed in Section 5.09.4, considering some general relationships between speciation and placement in the periodic table. In Section 5.09.5, we will show that studies on organic-rich rivers have led to an exploration of the "colloidal world" in rivers. Colloids are small particles, passing through the conventional filters used to separate dissolved and suspended loads in rivers. They appear as major carriers of trace elements in rivers and considerably complicate aqueous-speciation calculation. Finally, in Section 5.09.6, the significance of interactions between solutes and solid surfaces in river waters will be reviewed. Regulation by surfaces is of major importance for a great range of elements. Although for both colloids and surface interactions, some progress has been made, we are still far from a unified model that can accurately predict trace-element concentrations in natural water systems. This is mainly due to our poor physical description of natural colloids, surface site complexation, and their interaction with solutes.

Geomicrobiological redox cycling of the transuranic element neptunium.

PubMed

Law, Gareth T W; Geissler, Andrea; Lloyd, Jonathan R; Livens, Francis R; Boothman, Christopher; Begg, James D C; Denecke, Melissa A; Rothe, Jörg; Dardenne, Kathy; Burke, Ian T; Charnock, John M; Morris, Katherine

2010-12-01

Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

Simultaneous trace multielement determination by ICP-OES after solid phase extraction with modified octadecyl silica gel.

PubMed

Karbasi, Mohamad-Hadi; Jahanparast, Babak; Shamsipur, Mojtaba; Hassan, Jalal

2009-10-15

Multielement simultaneous determination of 35 trace elements in environmental samples was carried out by inductively coupled plasma emission spectrometry (ICP-OES) after preconcentration with octadecyl silicagel, modified with aurin tricarboxylic acid (Aluminon). Optimal experimental conditions including pH of sample solution, sample volume, sample and eluent flow rate, type, concentration and volume of eluent and foreign ions effect were investigated and established. Trace element ions in aqueous solution were quantitatively adsorbed onto octadecyl silicagel modified with aurin tricarboxylic acid at pH 8.0 with a flow rate of 11.0 mL min(-1). The adsorbed element ions were eluted with 3-5 mL of 0.5 mol L(-1) HNO(3) at a flow rate of 10.0 mL min(-1) and analyzed by ICP-OES simultaneously. The proposed method has at least preconcentration factor of 100 in water samples, which results high sensitive detection of ultra-trace and trace analysis. The present methodology gave recoveries better than 70% and RSD less than 16%.

Contrasting Granite Metallogeny through the Zircon Record: A Case Study from Myanmar.

PubMed

Gardiner, Nicholas J; Hawkesworth, Chris J; Robb, Laurence J; Whitehouse, Martin J; Roberts, Nick M W; Kirkland, Christopher L; Evans, Noreen J

2017-04-07

Granitoid-hosted mineral deposits are major global sources of a number of economically important metals. The fundamental controls on magma metal fertility are tectonic setting, the nature of source rocks, and magma differentiation. A clearer understanding of these petrogenetic processes has been forged through the accessory mineral zircon, which has considerable potential in metallogenic studies. We present an integrated zircon isotope (U-Pb, Lu-Hf, O) and trace element dataset from the paired Cu-Au (copper) and Sn-W (tin) magmatic belts in Myanmar. Copper arc zircons have juvenile εHf (+7.6 to +11.5) and mantle-like δ 18 O (5.2-5.5‰), whereas tin belt zircons have low εHf (-7 to -13) and heavier δ 18 O (6.2-7.7‰). Variations in zircon Hf and U/Yb reaffirm that tin belt magmas contain greater crustal contributions than copper arc rocks. Links between whole-rock Rb/Sr and zircon Eu/Eu* highlight that the latter can monitor magma fractionation in these systems. Zircon Ce/Ce* and Eu/Eu* are sensitive to redox and fractionation respectively, and here are used to evaluate zircon sensitivity to the metallogenic affinity of their host rock. Critical contents of Sn in granitic magmas, which may be required for the development of economic tin deposits, are marked by zircon Eu/Eu* values of ca. ≤0.08.

Chemostratigraphy of the Gohan Formation in the eastern central Korea : implications for the Capitanian environmental change

NASA Astrophysics Data System (ADS)

Kwon, Hyosang; Lee, Yong Il; Lim, Hyoun Soo

2017-04-01

The Gohan Formation in the Pyeongan Supergroup in central eastern Korea was deposited in a marginal marine to terrestrial setting in the Capitanian. It is 450 m thick and comprises alternation of gray-greenish medium-grained sandstone and mudrock. A detailed carbon isotope profile along with some paleoenvironmental proxies are presented for the Gohan Formation at Danyang site. CN ratios of organic matters reveal the presence of both vascular and non vascular plants. Excursion of carbon isotope ratios represents disturbance of carbon cycle. Carbon isotope values indicated a 3‰ negative excursion in the lower part of the studied section. This can be interpreted carbon cycle disturbance from the Capitanian extinction event. Mercury concentration is a proxy of volcanic activity. The horizon of a mercury peak near the bottom of the section is consistent with that of negative carbon isotope excursion and the coincidence between negative carbon isotope excursion and high mercury concentration may represent the influence from Emeishan volcanism, which has been regarded as a possible cause of the Capitanian extiction. Two more mercury peaks are noted in the upper part of the section but they are not related to carbon cycle disturbance which suggests effect of local volcanic eruptions as supported by the presence of volcanic rock fragments in coarse-grained sediment. Trace metal redox proxies indicate that the depositional basin was ventillated. TOC values tend to increase when the concentration of redox elements rise. However, the TOC and trace metal redox proxies trends are observed to behave independently of changes in carbon isotope and mercury concentrations suggesting transitions in local paleoenvironmental conditions.

Mix or un-mix? Trace element segregation from a heterogeneous mantle, simulated.

NASA Astrophysics Data System (ADS)

Katz, R. F.; Keller, T.; Warren, J. M.; Manley, G.

2016-12-01

Incompatible trace-element concentrations vary in mid-ocean ridge lavas and melt inclusions by an order of magnitude or more, even in samples from the same location. This variability has been attributed to channelised melt flow [Spiegelman & Kelemen, 2003], which brings enriched, low-degree melts to the surface in relative isolation from depleted inter-channel melts. We re-examine this hypothesis using a new melting-column model that incorporates mantle volatiles [Keller & Katz 2016]. Volatiles cause a deeper onset of channelisation: their corrosivity is maximum at the base of the silicate melting regime. We consider how source heterogeneity and melt transport shape trace-element concentrations in basaltic lavas. We use both equilibrium and non-equilibrium formulations [Spiegelman 1996]. In particular, we evaluate the effect of melt transport on probability distributions of trace element concentration, comparing the inflow distribution in the mantle with the outflow distribution in the magma. Which features of melt transport preserve, erase or overprint input correlations between elements? To address this we consider various hypotheses about mantle heterogeneity, allowing for spatial structure in major components, volatiles and trace elements. Of interest are the roles of wavelength, amplitude, and correlation of heterogeneity fields. To investigate how different modes of melt transport affect input distributions, we compare melting models that produce either shallow or deep channelisation, or none at all.References:Keller & Katz (2016). The Role of Volatiles in Reactive Melt Transport in the Asthenosphere. Journal of Petrology, http://doi.org/10.1093/petrology/egw030. Spiegelman (1996). Geochemical consequences of melt transport in 2-D: The sensitivity of trace elements to mantle dynamics. Earth and Planetary Science Letters, 139, 115-132. Spiegelman & Kelemen (2003). Extreme chemical variability as a consequence of channelized melt transport. Geochemistry Geophysics Geosystems, http://doi.org/10.1029/2002GC000336

Feasibility of the detection of trace elements in particulate matter using online High-Resolution Aerosol Mass Spectrometry

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

Salcedo, D.; Laskin, Alexander; Shutthanandan, V.

The feasibility of using an online thermal-desorption electron-ionization high-resolution aerosol mass spectrometer (AMS) for the detection of particulate trace elements was investigated analyzing data from Mexico City obtained during the MILAGRO 2006 field campaign, where relatively high concentrations of trace elements have been reported. This potential application is of interest due to the real-time data provided by the AMS, its high sensitivity and time resolution, and the widespread availability and use of this instrument. High resolution mass spectral analysis, isotopic ratios, and ratios of different ions containing the same elements are used to constrain the chemical identity of the measuredmore » ions. The detection of Cu, Zn, As, Se, Sn, and Sb is reported. There was no convincing evidence for the detection of other trace elements commonly reported in PM. The elements detected tend to be those with lower melting and boiling points, as expected given the use of a vaporizer at 600oC in this instrument. Operation of the AMS vaporizer at higher temperatures is likely to improve trace element detection. The detection limit is estimated at approximately 0.3 ng m-3 for 5-min of data averaging. Concentration time series obtained from the AMS data were compared to concentration records determined from offline analysis of particle samples from the same times and locations by ICP (PM2.5) and PIXE (PM1.1 and PM0.3). The degree of correlation and agreement between the three instruments (AMS, ICP, and PIXE) varied depending on the element. The AMS shows promise for real-time detection of some trace elements, although additional work including laboratory calibrations with different chemical forms of these elements are needed to further develop this technique and to understand the differences with the ambient data from the other techniques. The trace elements peaked in the morning as expected for primary sources, and the many detected plumes suggest the presence of multiple point sources, probably industrial, in Mexico City which are variable in time and space, in agreement with previous studies.« less

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

USGS Publications Warehouse

Odigie, Kingsley; Cohen, A.D.; Swarzenski, Peter W.; Flegal, R

2014-01-01

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815–1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements – likely caused by changes in land use – over that period. For example, the flux of Pb increased by ∼300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77–0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82–0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake’s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Trace Metal Variations Detected by Using Continuous XRF Core Scanning: Preliminary Results on Redox-sensitive Elements in East Sea, Korea

NASA Astrophysics Data System (ADS)

Cho, J. H.; Shin, D. H.; Kim, J. K.; Hyun, S.; Jang, S.; Kum, B. C.; Yoo, K. C.; Moh, T. J.

2017-12-01

The cruise of R/V ISABU focused on the detailed geological, geochemical and paleoceanographical investigations in the East Sea. The purpose of this cruise was the use of technically sophisticated Giant Piston Corer (GPC, OSIL) as well as the recovery of the longest piston core (20.7 m, ISA-16ESUB-2B) ever recorded in KIOST with a high resolution of stratigraphic sedimentary layer. The Late Pleistocene to the Holocene sediments in the Ulleung Basin are characterized by several volcanic tephra layers with alternations of fine light and dark clayey layers, reflecting variability in the paleoenvironment. Based on the previous researches and AMS results, we determine the ages of sedimentary layers from three tephra layers, 1.86 mbsf (U-Oki, 10.7 ka), 3.31 mbsf (AT, 29.4 ka), 11.67 mbsf (Aso-4, 88.0 ka) and 17.09 mbsf (Aso-3, 133.0 ka) respectively. Sediment textures are identified as hemipelagic mud, bioturbated mud and laminated mud with tephra layers. The sedimentation rates of each intervals are 0.174 m/kyr (present to U-Oki), 0.078 m/kyr (U-Oki to AT), 0.143 m/kyr (AT to Aso-4) and 0.120 m/kyr (Aso-4 to Aso-3) respectively. Sensitivity of XRF core scanner was obtained by establishing equivalences between peak areas. Element concentrations are analyzed by traditional techniques such as ICP-MS, ICP-OES. The Ca/Fe ratio reflects carbonate content and ISA-16ESUB-2B core shows strong correlation to sedimentary horizons. Sr/Ca ratio has good correlation with sedimentary units. Enhanced Sr contents indicates strong surface ocean production. Br/Cl ratio are high peak during MIS 5.5. Br content implies generally high organic rich sediments.

Redox Regulation of Mitochondrial Function

PubMed Central

Handy, Diane E.

2012-01-01

Abstract Redox-dependent processes influence most cellular functions, such as differentiation, proliferation, and apoptosis. Mitochondria are at the center of these processes, as mitochondria both generate reactive oxygen species (ROS) that drive redox-sensitive events and respond to ROS-mediated changes in the cellular redox state. In this review, we examine the regulation of cellular ROS, their modes of production and removal, and the redox-sensitive targets that are modified by their flux. In particular, we focus on the actions of redox-sensitive targets that alter mitochondrial function and the role of these redox modifications on metabolism, mitochondrial biogenesis, receptor-mediated signaling, and apoptotic pathways. We also consider the role of mitochondria in modulating these pathways, and discuss how redox-dependent events may contribute to pathobiology by altering mitochondrial function. Antioxid. Redox Signal. 16, 1323–1367. PMID:22146081

Impact of Redox Reactions on Colloid Transport in Saturated Porous Media: An Example of Ferrihydrite Colloids Transport in the Presence of Sulfide.

PubMed

Liao, Peng; Yuan, Songhu; Wang, Dengjun

2016-10-18

Transport of colloids in the subsurface is an important environmental process with most research interests centered on the transport in chemically stable conditions. While colloids can be formed under dynamic redox conditions, the impact of redox reactions on their transport is largely overlooked. Taking the redox reactions between ferrihydrite colloids and sulfide as an example, we investigated how and to what extent the redox reactions modulated the transport of ferrihydrite colloids in anoxic sand columns over a range of environmentally relevant conditions. Our results reveal that the presence of sulfide (7.8-46.9 μM) significantly decreased the breakthrough of ferrihydrite colloids in the sand column. The estimated travel distance of ferrihydrite colloids in the absence of sulfide was nearly 7-fold larger than that in the presence of 46.9 μM sulfide. The reduced breakthrough was primarily attributed to the reductive dissolution of ferrihydrite colloids by sulfide in parallel with formation of elemental sulfur (S(0)) particles from sulfide oxidation. Reductive dissolution decreased the total mass of ferrihydrite colloids, while the negatively charged S(0) decreased the overall zeta potential of ferrihydrite colloids by attaching onto their surfaces and thus enhanced their retention in the sand. Our findings provide novel insights into the critical role of redox reactions on the transport of redox-sensitive colloids in saturated porous media.

Dietary exposure estimates of 14 trace elements in Xuanwei and Fuyuan, two high lung cancer incidence areas in China.

PubMed

Zhang, Linlin; Lv, Jungang; Liao, Chunyang

2012-06-01

Xuanwei and Fuyuan, located in the Yunnan province in southwest of China, are known to have a strikingly high incidence of lung cancer. Among the many factors that have been explored, the association between lung cancer and trace elements has not received enough attention. In this study, dietary samples were collected from 60 families of the lung cancer and control groups and abundances of 14 trace elements were determined using inductively coupled-plasma mass spectroscopy. Accuracy and sensitivity of the method were demonstrated by analyzing national standard reference materials. The results showed that the dietary intake of the trace elements contributed 96.6% of total intake. Among the 14 elements tested, cadmium and titanium were found to be present at a significantly higher level in the food consumed by the cancer group than by the control group. The intake of selenium by the population living in the areas is much lower than what it should be, with the people in the cancer group experiencing even more severe selenium deficiency. In addition, in both groups, the intakes of several essential elements (iron, copper, and zinc) from food and the drinking water were found to be significantly lower than required according to the Chinese Dietary Reference Intakes. The present study of the relationship between trace element intakes of lung cancer cases and controls provides important information urgently needed for the assessment of lung cancer risk of healthy subjects. The study also gives rational dietary suggestions to local residents which is important to the early diagnosis and pretreatment of lung cancer.

The effect of acidified sample storage time on the determination of trace element concentration in ice cores by ICP-SFMS

NASA Astrophysics Data System (ADS)

Uglietti, C.; Gabrielli, P.; Lutton, A.; Olesik, J.; Thompson, L. G.

2012-12-01

Trace elements in micro-particles entrapped in ice cores are a valuable proxy of past climate and environmental variations. Inductively coupled plasma sector field mass spectrometry (ICP-SFMS) is generally recognized as a sensitive and accurate technique for the quantification of ultra-trace element concentrations in ice cores. Usually, ICP-SFMS analyses of ice core samples are performed by melting and acidifying aliquots. Acidification is important to transfer trace elements from particles into solution by partial and/or complete dissolution. Only elements in solution and in sufficiently small particles will be vaporized and converted to elemental ions in the plasma for detection by ICP-SFMS. However, experimental results indicate that differences in acidified sample storage time at room temperature may lead to the recovery of different trace element fractions. Moreover, different lithologies of the relatively abundant crustal material entrapped in the ice matrix could also influence the fraction of trace elements that are converted into elemental ions in the plasma. These factors might affect the determination of trace elements concentrations in ice core samples and hamper the comparison of results obtained from ice cores from different locations and/or epochs. In order to monitor the transfer of elements from particles into solution in acidified melted ice core samples during storage, a test was performed on sections from nine ice cores retrieved from low latitude drilling sites around the world. When compared to ice cores from polar regions, these samples are characterized by a relative high content of micro-particles that may leach trace elements into solution differently. Of the nine ice cores, five are from the Tibetan Plateau (Dasuopu, Guliya, Naimonanyi, Puruogangri and Dunde), two from the Andes (Quelccaya and Huascaran), one from Africa (Kilimanjaro) and one from the Eastern Alps (Ortles). These samples were decontaminated by triple rinsing, melted and stored in pre-cleaned low-density polyethylene bottles, and kept frozen until acidification (2% v/v ultra-pure HNO3). Determination of twenty trace elements (Ag, Al, As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Rb, Sb, Sn, Ti, Tl, U, V, and Zn) was repeated at different times after acidification using the same aliquot. Analyses show a mean increase of 40-50% in trace element concentration in all the samples during the first 15 days of storage after acidification, except Al, Fe, V and Cr, which show a larger increase (90-100%). After 15 days the trace element concentrations reach generally stable values (with small increases within measurement uncertainty), except for the Naimonanyi and Kilimanjaro samples which continue to increase. In contrast, Ag concentration decreases after one week, likely due to its low stability in the acidified solution that may depend on the Cl- concentration. We froze the samples 43 days after the acidification. After two weeks the samples were melted and re-analyzed by ICP-SFMS in two different laboratories as an inter-calibration exercise. The results show a good correspondence between the measured concentrations determined by the two instruments and a consistent additional increase of 20-30% of measured trace element concentrations in almost all samples.

Optimizing detector geometry for trace element mapping by X-ray fluorescence

DOE PAGES

Sun, Yue; Gleber, Sophie -Charlotte; Jacobsen, Chris; ...

2015-01-01

We report that trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral responsemore » of energy dispersive detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. In conclusion, we conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples.« less

Optimizing detector geometry for trace element mapping by X-ray fluorescence

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

Sun, Yue; Gleber, Sophie -Charlotte; Jacobsen, Chris

We report that trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral responsemore » of energy dispersive detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. In conclusion, we conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples.« less

The Neoproterozoic oxygenation event: Environmental perturbations and biogeochemical cycling

NASA Astrophysics Data System (ADS)

Och, Lawrence M.; Shields-Zhou, Graham A.

2012-01-01

The oxygen content of the Earth's surface environment is thought to have increased in two broad steps: the Great Oxygenation Event (GOE) around the Archean-Proterozoic boundary and the Neoproterozoic Oxygenation Event (NOE), during which oxygen possibly accumulated to the levels required to support animal life and ventilate the deep oceans. Although the concept of the GOE is widely accepted, the NOE is less well constrained and its timing and extent remain the subjects of debate. We review available evidence for the NOE against the background of major climatic perturbations, tectonic upheaval related to the break-up of the supercontinent Rodinia and reassembly into Gondwana, and, most importantly, major biological innovations exemplified by the Ediacarian Biota and the Cambrian 'Explosion'. Geochemical lines of evidence for the NOE include perturbations to the biogeochemical cycling of carbon. Generally high δ 13C values are possibly indicative of increased organic carbon burial and the release of oxidative power to the Earth's surface environment after c. 800 Ma. A demonstrably global and primary record of extremely negative δ 13C values after about 580 Ma strongly suggests the oxidation of a large dissolved organic carbon pool (DOC), the culmination of which around c. 550 Ma coincided with an abrupt diversification of Ediacaran macrobiota. Increasing 87Sr/ 86Sr ratios toward the Neoproterozoic-Cambrian transition indicates enhanced continental weathering which may have fuelled higher organic production and burial during the later Neoproterozoic. Evidence for enhanced oxidative recycling is given by the increase in sulfur isotope fractionation between sulfide and sulfate, exceeding the range usually attained by sulfate reduction alone, reflecting an increasing importance of the oxidative part in the sulfur cycle. S/C ratios attained a maximum during the Precambrian-Cambrian transition, further indicating higher sulfate concentrations in the ocean and a transition from dominantly pyrite burial to sulfate burial after the Neoproterozoic. Strong evidence for the oxygenation of the deep marine environment has emerged through elemental approaches over the past few years which were able to show significant increases in redox-sensitive trace-metal (notably Mo) enrichment in marine sediments not only during the GOE but even more pronounced during the inferred NOE. In addition to past studies involving Mo enrichment, which has been extended and further substantiated in the current review, we present new compilations of V and U concentrations in black shales throughout Earth history that confirm such a rise and further support the NOE. With regard to ocean ventilation, we also review other sedimentary redox indicators, such as iron speciation, molybdenum isotopes and the more ambiguous REE patterns. Although the timing and extent of the NOE remain the subjects of debate and speculation, we consider the record of redox-sensitive trace-metals and C and S contents in black shales to indicate delayed ocean ventilation later in the Cambrian on a global scale with regard to rising oxygen levels in the atmosphere which likely rose during the Late Neoproterozoic.

Kinetic determinations of trace element bioaccumulation in the mussel Mytilus edulis

USGS Publications Warehouse

Wang, W.-X.; Fisher, N.S.; Luoma, S.N.

1996-01-01

Laboratory experiments employing radiotracer methodology were conducted to determine the assimilation efficiencies from ingested natural seston, the influx rates from the dissolved phase and the efflux rates of 6 trace elements (Ag, Am, Cd, Co, Se and Zn) in the mussel Mytilus edulis. A kinetic model was then employed to predict trace element concentration in mussel tissues in 2 locations for which mussel and environmental data are well described: South San Francisco Bay (California, USA) and Long Island Sound (New York, USA). Assimilation efficiencies from natural seston ranged from 5 to 18% for Ag, 0.6 to 1% for Am, 8 to 20% for Cd, 12 to 16% for Co, 28 to 34% for Se, and 32 to 41% for Zn. Differences in chlorophyll a concentration in ingested natural seston did not have significant impact on the assimilation of Am, Co, Se and Zn. The influx rate of elements from the dissolved phase increased with the dissolved concentration, conforming to Freundlich adsorption isotherms. The calculated dissolved uptake rate constant was greatest for Ag, followed by Zn > Am = Cd > Co > Se. The estimated absorption efficiency from the dissolved phase was 1.53% for Ag, 0.34% for Am, 0.31% for Cd, 0.11% for Co, 0.03% for Se and 0.89% for Zn. Salinity had an inverse effect on the influx rate from the dissolved phase and dissolved organic carbon concentration had no significant effect on trace element uptake. The calculated efflux rate constants for all elements ranged from 1.0 to 3.0% d-1. The route of trace element uptake (food vs dissolved) and the duration of exposure to dissolved trace elements (12 h vs 6 d) did not significantly influence trace element efflux rates. A model which used the experimentally determined influx and efflux rates for each of the trace elements, following exposure from ingested food and from water, predicted concentrations of Ag, Cd, Se and Zn in mussels that were directly comparable to actual tissue concentrations independently measured in the 2 reference sites in national monitoring programs. Sensitivity analysis indicated that the total suspended solids load, which can affect mussel feeding activity, assimilation, and trace element concentration in the dissolved and particulate phases, can significantly influence metal bioaccumulation for particle-reactive elements such as Ag and Am. For all metals, concentrations in mussels are proportionately related to total metal load in the water column and their assimilation efficiency from ingested particles. Further, the model predicted that over 96% of Se in mussels is obtained from ingested food, under conditions typical of coastal waters. For Ag, Am, Cd, Co and Zn, the relative contribution from the dissolved phase decreases significantly with increasing trace element partition coefficients for suspended particles and the assimilation efficiency in mussels of ingested trace elements; values range between 33 and 67% for Ag, 5 and 17% for Am, 47 and 82% for Cd, 4 and 30% for Co, and 17 and 51% for Zn.

Recent Advances in the Measurement of Arsenic, Cadmium, and Mercury in Rice and Other Foods

PubMed Central

Punshon, Tracy

2015-01-01

Trace element analysis of foods is of increasing importance because of raised consumer awareness and the need to evaluate and establish regulatory guidelines for toxic trace metals and metalloids. This paper reviews recent advances in the analysis of trace elements in food, including challenges, state-of-the art methods, and use of spatially resolved techniques for localizing the distribution of As and Hg within rice grains. Total elemental analysis of foods is relatively well-established but the push for ever lower detection limits requires that methods be robust from potential matrix interferences which can be particularly severe for food. Inductively coupled plasma mass spectrometry (ICP-MS) is the method of choice, allowing for multi-element and highly sensitive analyses. For arsenic, speciation analysis is necessary because the inorganic forms are more likely to be subject to regulatory limits. Chromatographic techniques coupled to ICP-MS are most often used for arsenic speciation and a range of methods now exist for a variety of different arsenic species in different food matrices. Speciation and spatial analysis of foods, especially rice, can also be achieved with synchrotron techniques. Sensitive analytical techniques and methodological advances provide robust methods for the assessment of several metals in animal and plant-based foods, in particular for arsenic, cadmium and mercury in rice and arsenic speciation in foodstuffs. PMID:25938012

Trace element study in scallop shells by laser ablation ICP-MS: the example of Ba/Ca ratios

NASA Astrophysics Data System (ADS)

Lorrain, A.; Pécheyran, C.; Paulet, Y.-M.; Chauvaud, L.; Amouroux, D.; Krupp, E.; Donard, O.

2003-04-01

As scallop shells grow incrementally at a rate of one line per day, environmental changes could then be evidenced on a daily basis. As an example for trace element incorporation studies, barium is a geochemical tracer that can be directly related to oceanic primary productivity. Hence, monitoring Ba/Ca variations in a scallop shell should give information about phytoplanktonic events encountered day by day during its life. The very high spatial resolution (typically 40 - 200 µm) and the high elemental sensitivity required can only be achieved by the combination of laser ablation coupled to inductively coupled plasma mass spectrometry. This study demonstrates that Laser ablation coupled to ICP-MS determination is a relevant tool for high resolution distribution measurement of trace elements in calcite matrix. The ablation strategy related to single line rastering and calcium normalisation were found to be the best analytical conditions in terms of reproducibility and sensitivity. The knowledge of P. maximus growth rings periodicity (daily), combined with LA-ICP-MS micro analysis allows the acquisition of time dated profiles with high spatial and thus temporal resolution. This resolution makes P. maximus a potential tool for environmental reconstruction and especially for accurate calibration of proxies. However, the relations among Ba/Ca peaks and phytoplanktonic events differed according to the animals and some inter-annual discrepancies complexify the interpretation.

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

Sun, Yue; Gleber, Sophie-Charlotte; Jacobsen, Chris

Trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral response of energy dispersivemore » detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. We conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples.« less

Investigation of the behavior of potentially hazardous trace elements in Kentucky coals and combustion byproducts

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

Robertson, J.D.; Blanchard, L.J.; Srikantapura, S.

1996-12-31

The minor- and trace-element content of coal is of great interest because of the potentially hazardous impact on human health and the environment resulting from their release during coal combustion. Of the one billion tons of coal mined annually in the United States, 85-90% is consumed by coal-fired power plants. Potentially toxic elements present at concentrations as low as a few egg can be released in large quantities from combustion of this magnitude. Of special concern are those trace elements that occur naturally in coal which have been designated as potential hazardous air pollutants (HAPs) in the 1990 Amendments tomore » the Clean Air Act. The principle objective of this work was to investigate a combination of physical and chemical coal cleaning techniques to remove 90 percent of HAP trace elements at 90 percent combustibles recovery from Kentucky No. 9 coal. Samples of this coal were first subjected to physical separation by flotation in a Denver cell. The float fraction from the Denver cell was then used as feed material for hydrothermal leaching tests in which the efficacy of dilute alkali (NaOH) and acid (HNO{sub 3}) solutions at various temperatures and pressures was investigated. The combined column flotation and mild chemical cleaning strategy removed 60-80% of trace elements with greater than 85, recovery of combustibles from very finely ground (-325 mesh) coal. The elemental composition of the samples generated at each stage was determined using particle induced X-ray emission (PIXE) analysis. PIXE is a rapid, instrumental technique that, in principle, is capable of analyzing all elements from sodium through uranium with sensitivities as low as 1 {mu}g/g.« less

Physicochemical and redox characteristics of particulate matter (PM) emitted from gasoline and diesel passenger cars

NASA Astrophysics Data System (ADS)

Geller, Michael D.; Ntziachristos, Leonidas; Mamakos, Athanasios; Samaras, Zissis; Schmitz, Debra A.; Froines, John R.; Sioutas, Constantinos

Particulate matter (PM) originating from mobile sources has been linked to a myriad of adverse health outcomes, ranging from cancer to cardiopulmonary disease, and an array of environmental problems, including global warming and acid rain. Till date, however, it is not clear which physical characteristics or chemical constituents of PM are significant contributors to the magnitude of the health risk. This study sought to determine the relationship between physical and chemical characteristics of PM while quantitatively measuring samples for redox activity of diesel and gasoline particulate emissions from passenger vehicles typically in use in Europe. The main objective was to relate PM chemistry to the redox activity in relation to vehicle type and driving cycle. Our results showed a high degree of correlation between several PM species, including elemental and organic carbon, low molecular weight polycyclic aromatic hydrocarbons, and trace metals such as lithium, beryllium, nickel and zinc, and the redox activity of PM, as measured by a quantitative chemical assay, the dithiothreitol (DTT) assay. The reduction in PM mass or number emission factors resulting from the various engine configurations, fuel types and/or after-treatment technologies, however, was non-linearly related to the decrease in overall PM redox activity. While the PM mass emission rate from the diesel particle filter (DPF)-equipped vehicle was on average approximately 25 times lower than that of the conventional diesel, the redox potential was only eight times lower, which makes the per mass PM redox potential of the DPF vehicle about three times higher. Thus, a strategy aimed at protecting public health and welfare by reducing total vehicle mass and number emissions may not fully achieve the desired goal of preventing the health consequences of PM exposure. Further, study of the chemical composition and interactions between various chemical species may yield greater insights into the toxicity of the PM content of vehicle exhaust.

Iron chemistry of Hawaiian rainforest soil solution: Biogeochemical implications of multiple Fe redox cycles

NASA Astrophysics Data System (ADS)

Thompson, A.; Chorover, J.; Chadwick, O.

2003-12-01

Iron (Fe)-oxides are important sorbents for nutrients, pollutants and natural organic matter (NOM). When flucutations in soil oxygen status exist, Fe can cycle through reduced and oxidized forms and thus greatly affect the aqueous conc. of nutrients and metals. We are examining the influence of oscillating oxic/anoxic conditions on Fe-oxide formation and biogeochemical processes (microbial community composition, and carbon, nutrient and trace metal availability). Our work makes use of a natural rainfall gradient ranging from 2.2 to 4.2 m mean annual precipitation (MAP) on the island of Maui, Hawaii, USA. All sites developed on a 400ky basaltic lava flow and comprise soils under similar vegetation. Solid phase Fe concentration and oxidation state vary systematically across this rainfall gradient with a sharp decrease in pedogenic Fe between 2.8 m and 3.5 m MAP that corresponds with an Eh of 330 mV (1-yr ave.). Fe isotopic composition and Fe-oxide associated rare earth elements (REE) also suggest a shift from ligand-promoted to redutive Fe dissolution with increasing rainfall. To examine the effects of multiple Fe oxidation/reduction cycles, we constructed a set of redox-stat reactors that maintain Eh values within a set range by small Eh-triggered additions of oxygen. Triplicate soil slurry reactors are subjected to redox (Eh) oscillations such that Fe is repeatedly cycled from oxidized to reduced forms. During our current experiment, we measure pH and Eh dynamics and monitor the distribution of Fe(II) and Fe(III), major ion and anion concentrations, a range of trace metals including the REE, and total organic carbon (TOC) in three Stokes-effective particle size fractions (<0.45 mm, <0.1 mm, and <0.02 mm) by cascade centrifugation and a <3000 MW fraction isolated via ultra-filtration. Each sample is then sequentially extracted in dilute (0.5 M) HCl and acid-ammonium oxalate. Concurrently, CO2 release is measured and DNA fingerprinting is used to track changes in the microbial community. Prior to implementing the rigorous sampling procedure above, we completed two preliminary reactor experiments focusing only on Fe distribution between aqueous, HCl, and oxalate extractions. These experiments illustrated (1) a distinct threshold for Fe oxidation at ~ 350 mV in the soils (pH 5) and (2) multiple redox cycles increased the HCl-extractable Fe(III) fraction relative to initial conditions. Unexpectedly, this increase occurred predominantly during reducing cycles-perhaps indicating a weakening of Fe-oxide structures during initiation of reducing conditions or oxidation of Fe(II) by NO3. By integrating Fe analysis with trace metal and microbial characterization in triplicate reactors, we will verify this increase in HCl-extractable Fe(III), and assess the impacts of Fe redox oscillation on biogeochemical processes.

Inorganic trace analysis by mass spectrometry

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine; Dietze, Hans-Joachim

1998-10-01

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g -1 concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.

Mapping the diatom redox-sensitive proteome provides insight into response to nitrogen stress in the marine environment.

PubMed

Rosenwasser, Shilo; Graff van Creveld, Shiri; Schatz, Daniella; Malitsky, Sergey; Tzfadia, Oren; Aharoni, Asaph; Levin, Yishai; Gabashvili, Alexandra; Feldmesser, Ester; Vardi, Assaf

2014-02-18

Diatoms are ubiquitous marine photosynthetic eukaryotes responsible for approximately 20% of global photosynthesis. Little is known about the redox-based mechanisms that mediate diatom sensing and acclimation to environmental stress. Here we used a quantitative mass spectrometry-based approach to elucidate the redox-sensitive signaling network (redoxome) mediating the response of diatoms to oxidative stress. We quantified the degree of oxidation of 3,845 cysteines in the Phaeodactylum tricornutum proteome and identified approximately 300 redox-sensitive proteins. Intriguingly, we found redox-sensitive thiols in numerous enzymes composing the nitrogen assimilation pathway and the recently discovered diatom urea cycle. In agreement with this finding, the flux from nitrate into glutamine and glutamate, measured by the incorporation of (15)N, was strongly inhibited under oxidative stress conditions. Furthermore, by targeting the redox-sensitive GFP sensor to various subcellular localizations, we mapped organelle-specific oxidation patterns in response to variations in nitrogen quota and quality. We propose that redox regulation of nitrogen metabolism allows rapid metabolic plasticity to ensure cellular homeostasis, and thus is essential for the ecological success of diatoms in the marine ecosystem.

Physiological and hydrological controls on mineral redox cycling by long-range electron transport by bacteria in anaerobic sediments

NASA Astrophysics Data System (ADS)

Michelson, K.; Werth, C. J.; Sanford, R. A.; Valocchi, A. J.

2016-12-01

The cycling of iron and manganese oxides plays a critical role in the bioavailability of trace elements and macronutrients, the flux of carbon across terrestrial and atmospheric ecosystems, and the remediation of groundwater contaminated by toxic metals and radionuclides. Bacteria control one half of the redox cycle as the primary drivers of iron and manganese reduction in anaerobic soils and sediments. However, Fe(III) and Mn(IV) are almost exclusively present under anaerobic conditions as insoluble oxides, the reduction of which are facilitated by extracellular electron transport via conductive `nanowires', electron shuttling, and direct contact with outer membrane cytochromes. Our research focus is on the relative contribution of nanowires and electron shuttles under different physiological and hydrological conditions, which remains unexplored. We present a novel microfluidic platform that allows us to directly observe these phenomena under a controlled environment representative of groundwater conditions, monitor the metabolic activity and redox state of bacteria, and determine the presence of reduced products in-situ using Raman spectroscopy. Using Geobacter sulfurreducens and Shewanella oneidensis as model metal-reducing bacteria, and insoluble manganese dioxide (i.e. birnessite) as an electron acceptor, we show that 1) electron shuttling is more effective under static conditions 2) the presence of exogenous shuttles allows efficient electron transport under all flow regimes 3) redox potential of the bulk medium exerts significant control over reduction by both nanowires and electron shuttles 4) shuttling is amplified by orders of magnitude in nanopores.

Experimental study of trace element partitioning between enstatite and melt in enstatite chondrites at low oxygen fugacities and 5 GPa

NASA Astrophysics Data System (ADS)

Cartier, Camille; Hammouda, Tahar; Doucelance, Régis; Boyet, Maud; Devidal, Jean-Luc; Moine, Bertrand

2014-04-01

In order to investigate the influence of very reducing conditions, we report enstatite-melt trace element partition coefficients (D) obtained on enstatite chondrite material at 5 GPa and under oxygen fugacities (fO2) ranging between 0.8 and 8.2 log units below the iron-wustite (IW) buffer. Experiments were conducted in a multianvil apparatus between 1580 and 1850 °C, using doped (Sc, V, REE, HFSE, U, Th) starting materials. We used a two-site lattice strain model and a Monte-Carlo-type approach to model experimentally determined partition coefficient data. The model can fit our partitioning data, i.e. trace elements repartition in enstatite, which provides evidence for the attainment of equilibrium in our experiments. The precision on the lattice strain model parameters obtained from modelling does not enable determination of the influence of intensive parameters on crystal chemical partitioning, within our range of conditions (fO2, P, T, composition). We document the effect of variable oxygen fugacity on the partitioning of multivalent elements. Cr and V, which are trivalent in the pyroxene at around IW - 1 are reduced to 2+ state with increasingly reducing conditions, thus affecting their partition coefficients. In our range of redox conditions Ti is always present as a mixture between 4+ and 3+ states. However the Ti3+-Ti4+ ratio increases strongly with increasingly reducing conditions. Moreover in highly reducing conditions, Nb and Ta, that usually are pentavalent in magmatic systems, appear to be reduced to lower valence species, which may be Nb2+ and Ta3+. We propose a new proxy for fO2 based on D(Cr)/D(V). Our new data extend the redox range covered by previous studies and allows this proxy to be used in the whole range of redox conditions of the solar system objects. We selected trace-element literature data of six chondrules on the criterion of their equilibrium. Applying the proxy to opx-matrix systems, we estimated that three type I chondrules have equilibrated at IW - 7 ± 1, one type I chondrule at IW - 4 ± 1, and two type II chondrules at IW + 3 ± 1. This first accurate estimation of enstatite-melt fO2 for type I chondrules is very close to CAI values. Find the best-fit for trivalent elements. We set the r0M1 (3+) range to 0.55-0.75 Å, based on visual observations of the datapoints. For the other variables we have set boundary values beyond which the solutions would be unacceptable. For example, r0M2 (3+) has to be larger than r0M1 (3+). Finally we restricted the D0 range as follow: 0.2 r0(3+) > r0(4+) (see van Westrenen et al., 2000, for explanation), together with visual observation of our experimental data. D0 ranges: 1 < D0M1(2+) < 100; D0M2 (3+) < D0M2(2+) < 100 ; 0.01 < D0M1(4+) < 0.1 ; 0.0001 < D0M2(4+) < 0.01. These ranges are based on visual observation of our experimental data.

Dysoxia in the Gulf of Alaska evinced by benthic foraminiferal assemblages and redox-sensitive trace elements during deglacial and glacial intervals

NASA Astrophysics Data System (ADS)

Sharon, S.; Belanger, C. L.; Du, J.; Mix, A. C.; Asahi, H.

2016-12-01

During the last ice age, millennial-scale episodes of expanded low-oxygen conditions occurred around the margins of the North Pacific, however the drivers of these events are not well understood. Differences in the timing of dysoxic events in the shallow and deep Pacific have been proposed, which imply changes in ocean circulation may play a role. Here we combine faunal and geochemical analyses to investigate the timing and severity of low-oxygen events in the North Pacific at a slope (682 m) and a deeper-water (3680 m) site from a transect cored by IODP Expedition 341 in the Gulf of Alaska. At the slope site, multivariate faunal analyses based on the relative abundances of benthic foraminiferal species reveal a distinct fauna characterized by high abundances of taxa associated with dysoxic to suboxic conditions including Buliminella tenuata, Bolivia pacifica, and Epistominella pacifica. These assemblages occur during the most recent deglacial ( 12,000 kyr) and during MIS 3 from 45,000-55,000 years ago. These fossil assemblages have no faunal analog within the modern Gulf of Alaska, although they are most similar to faunas from the modern oxygen minimum zone (OMZ). Thus, these faunas may represent a more intense OMZ. Sedimentary trace element analyses show enrichment in Re, Mo, and U where these faunas are found, supporting them as low-oxygen indicators. Similarly, a distinct fauna occurs at the deeper site, which has high relative abundances of Nonionella sp., Stainforthia fusiformis, and small-bodied taxa common in suboxic settings with high phytodetritus. Ongoing age-model improvements and increased sampling resolution will allow us to better test whether faunal changes are offset at the two sites and assess the abruptness of the onset of extreme low-oxygen events in the North Pacific.

Analysis of Trace Siderophile Elements at High Spatial Resolution Using Laser Ablation ICP-MS

NASA Astrophysics Data System (ADS)

Campbell, A. J.; Humayun, M.

2006-05-01

Laser ablation inductively coupled plasma mass spectometry is an increasingly important method of performing spatially resolved trace element analyses. Over the last several years we have applied this technique to measure siderophile element distributions at the ppm level in a variety of natural and synthetic samples, especially metallic phases in meteorites and experimental run products intended for trace element partitioning studies. These samples frequently require trace element analyses to be made at a finer spatial resolution (25 microns or better) than is frequently attained using LA-ICP-MS. In this presentation we review analytical protocols that were developed to optimize the LA-ICP-MS measurements for high spatial resolution. Particular attention is paid to the trade-offs involving sensitivity, ablation pit depth and diameter, background levels, and number of elements measured. To maximize signal/background ratios and avoid difficulties associated with ablating to depths greater than the ablation pit diameter, measurement involved integration of rapidly varying, transient but well-behaved signals. The abundances of platinum group elements and other siderophile elements in ferrous metals were calibrated against well-characterized standards, including iron meteorites and NIST certified steels. The calibrations can be set against the known abundance of an independently determined element, but normalization to 100 percent can also be employed, and was more useful in many circumstances. Evaluation of uncertainties incorporated counting statistics as well as a measure of instrumental uncertainty, determined by replicate analyses of the standards. These methods have led to a number of insights into the formation and chemical processing of metal in the early solar system.

Enhanced identification of trace element fingerprint of prehistoric pigments by PIXE mapping

NASA Astrophysics Data System (ADS)

Lebon, M.; Pichon, L.; Beck, L.

2018-02-01

The elemental composition of Fe rich rocks used as pigment during prehistoric periods can provide valuable information about the type of material used and their geological origin. However, these materials present several analytical constraints since their patrimonial value involve using non-invasive techniques maintaining a high sensitivity of the detection and the quantification of trace elements. Micro-beam techniques also require to take into account the heterogeneity of these geomaterials from the macroscopic to microscopic scales. Several previous studies have demonstrated that PIXE analysis satisfies these analytical conditions. However, application of micro-PIXE analysis is still complex when thin and discontinuous layer of pigment is deposed on the surface of other materials such as rocks or bones. In such case, PIXE imaging could improve the ability to take into account the high heterogeneity of such archaeological objects. In study, we used PIXE imaging system developed at the NewAGLAE facility in order to visualize distribution of elements associated with iron-rich pigment phase. The results obtained show that PIXE maps can improve the identification of the main trace elements specific to the iron mineral phase. By grouping pixels of iron-rich areas and performing quantitative treatment, it was possible to reveal additional trace elements associated to pigment. This study highlights the contribution of PIXE imaging to the identification of elements associated with mineral phases of interest and to use them as proxies to discriminate different geological materials used in archaeological context.

Trace elements quantified by the APXS on Mars

NASA Astrophysics Data System (ADS)

Gellert, R.; Berger, J. A.; Boyd, N.; O'Connell-Cooper, C.; Desouza, E.; Thompson, L. M.; VanBommel, S.; Yen, A.

2017-12-01

The APXS accurately quantifies many trace elements within the dime-sized sample: Ni, Cu, Zn, Ga, Ge, Pb, Br, Se, As, and Y with 20 ppm detection limit (DL) and Rb, Sr, Zr, Co, Cr, and Mn with 200 ppm DL. Together with the major and minor elements, this gives important constraints for a variety of formation processes of the investigated soils, floats or extensive bedrock on Mars. The global soil, found at all rover landing sites, was used to define an average Mars value for Ni, Zn, Cr and Mn, with a consistent value of Fe/Mn 50 for soils and igneous rocks. All other APXS trace elements are below DL. Strong enrichments or depletions can both give evidence for the formation processes and link together groups of rocks and indicate their common diagenetic origin. Felsic rocks at Gale and Gusev have Cr, Ni and Zn far below soil, indicating their likely igneous origin. Further, similarly low values are found in elevated silica samples in the Murray Fm. at Gale where these elements have been mobilized and leached by fluids. High Sr and Ga was found in the host rock surrounding the Garden City vein system, which contains also high Ge, Mn and Cu, indicating mobilization in high temperature and/or acidic fluids after the Murray was lithified. The fracture fill sample Stephen at Windjana is high in Zn, Co and Cu. Germanium is enriched in the Murray Fm with very consistent values of about 100 ppm over many kilometers and 200 meters elevation, similar to perviously found bedrock at Yellowknife Bay and Windjana in Gale. Zinc is highly elevated but changes significantly with elevation in Murray, often correlated with Fe/Mn, possibly indicating changing redox conditions. Pb and Se are highly enriched at Pahrump (150, 75 ppm, resp.), drop first to low values and increase again uphill towards HematiteRidge. Nodules found at Pahrump show striking evidence for (Mg, Ni)-sulfates with Nickel up to 4% in the sulfates. All together these trends might indicate hydrothermal activity. The MER APXS instruments with somewhat higher DL found similar patterns. Elevated Ge was found at Home plate, Gusev crater, and at the rim of Endeavour crater at Meridiani Planum. Together with detailed investigations of SNC meteorites, the APXS detected trace elements supplement the bulk chemistry significantly and allow new insights into the formation processes encountered on Mars

Investigation of a redox-sensitive predictive model of mouse embryonic stem cells differentiation using quantitative nuclease protection assays and glutathione redox status

EPA Science Inventory

Investigation of a redox-sensitive predictive model of mouse embryonic stem cell differentiation via quantitative nuclease protection assays and glutathione redox status Chandler KJ,Hansen JM, Knudsen T,and Hunter ES 1. U.S. Environmental Protection Agency, Research Triangl...

Persistent millennial-scale link between Greenland climate and northern Pacific Oxygen Minimum Zone under interglacial conditions

NASA Astrophysics Data System (ADS)

Cartapanis, O.; Tachikawa, K.; Romero, O. E.; Bard, E.

2014-02-01

The intensity and/or extent of the northeastern Pacific Oxygen Minimum Zone (OMZ) varied in-phase with the Northern Hemisphere high latitude climate on millennial timescales during the last glacial period, indicating the occurrence of atmospheric and oceanic connections under glacial conditions. While millennial variability was reported for both the Greenland and the northern Atlantic Ocean during the last interglacial period, the climatic connections with the northeastern Pacific OMZ has not yet been observed under warm interglacial conditions. Here we present a new geochemical dataset, spanning the past 120 ka, for major components (terrigenous fraction, marine organic matter, biogenic opal, and carbonates) generated by X-ray fluorescence scanning alongside with biological productivity and redox sensitive trace element content (Mo, Ni, Cd) of sediment core MD02-2508 at 23° N, retrieved from the northern limit of the modern OMZ. Based on elemental ratios Si / Ti (proxy for opal), Cd / Al and Ni / Al, we suggest that biological productivity was high during the last interglacial (MIS5). Highly resolved opal reconstruction presents millennial variability corresponding to all the Dansgaard-Oeschger interstadial events over the last interglacial, while the Mo / Al ratio indicates reduced oxygenation during these events. Extremely high opal content during warm interstadials suggests high diatom productivity. Despite the different climatic and oceanic background between glacial and interglacial periods, rapid variability in the northeastern Pacific OMZ seems to be tightly related to Northern Hemisphere high latitude climate via atmospheric and possibly oceanic processes.

Studies of LA-ICP-MS on quartz glasses at different wavelengths of a Nd:YAG laser.

PubMed

Becker, J S; Tenzler, D

2001-07-01

The capability of LA-ICP-MS for determination of trace impurities in transparent quartz glasses was investigated. Due to low or completely lacking absorption of laser radiation, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) proves difficult on transparent solids, and in particular the quantification of measurement results is problematic in these circumstances. Quartz glass reference materials of various compositions were studied by using a Nd:YAG laser system with focused laser radiation of wavelengths of 1064 nm, 532 nm and 266 nm, and an ICP-QMS (Elan 6000, Perkin Elmer). The influence of ICP and laser ablation conditions in the analysis of quartz glasses of different compositions was investigated, with the laser power density in the region of interaction between laser radiation and solid surface determining the ablation process. The trace element concentration was determined via calibration curves recorded with the aid of quartz glass reference materials. Under optimized measuring conditions the correlation coefficients of the calibration curves are in the range of 0.9-1. The relative sensitivity factors of the trace elements determined in the quartz glass matrix are 0.1-10 for most of the trace elements studied by LA-ICP-MS. The detection limits of the trace elements in quartz glass are in the low ng/g to pg/g range.

Geochemistry of a marine phosphate deposit: A signpost to phosphogenesis

USGS Publications Warehouse

Piper, David Z.; Perkins, R.B.

2014-01-01

The Permian age Phosphoria Formation in southeastern Idaho and adjoining states represents possibly the largest marine phosphate deposit in the world. The Meade Peak Member, which contains the highest concentrations and amount of carbonate fluorapatite in the formation, was not significantly altered by mechanical reworking during deposition or subsequently by chemical weathering. Thus, its present composition reflects properties of the Phosphoria Sea that were critical to its accumulation and possibly to the accumulation of most major marine phosphate deposits. These properties included the chemistry of the water column, the hydrography, and the level of primary productivity. Calculated accumulation rates of the PO43− and trace nutrients – Cd, Cu, Ni, and Zn – recorded a dynamic upwelling rate of c.30 m year−1 that supported primary productivity of 2g C m−2day−1. High accumulation rates of the hydrogenous redox-sensitive trace metals – Cr, Mo, U, and V – reflect bottom-water redox conditions that were dominantly suboxic, maintained by a balance between the oxidation of ~ 8% of the organic detritus that settled out of the photic zone and advection of bottom water with a residence time of c.10 years. A limited flux into the basin of siliciclastic lithogenous debris contributed further to elevated concentrations of the seawater-derived sediment fractions.

Concise Access to 2-Aroylbenzothiazoles by Redox Condensation Reaction between o-Halonitrobenzenes, Acetophenones, and Elemental Sulfur.

PubMed

Nguyen, Thanh Binh; Pasturaud, Karine; Ermolenko, Ludmila; Al-Mourabit, Ali

2015-05-15

A wide range of 2-aroylbenzothiazoles 3 including some pharmacologically relevant derivatives can be obtained in high yields by simply heating o-halonitrobenzenes 1, acetophenones 2, elemental sulfur, and N-methylmorpholine. This three-component nitro methyl coupling was found to occur in an excellent atom-, step-, and redox-efficient manner in which elemental sulfur played the role of nucleophile building block and redox moderating agent to fulfill electronic requirements of the global reaction.

Redox flow batteries having multiple electroactive elements

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

Wang, Wei; Li, Liyu; Yang, Zhenguo

Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

Paclitaxel-loaded redox-sensitive nanoparticles based on hyaluronic acid-vitamin E succinate conjugates for improved lung cancer treatment.

PubMed

Song, Yu; Cai, Han; Yin, Tingjie; Huo, Meirong; Ma, Ping; Zhou, Jianping; Lai, Wenfang

2018-01-01

Lung cancer is the primary cause of cancer-related death worldwide. A redox-sensitive nanocarrier system was developed for tumor-targeted drug delivery and sufficient drug release of the chemotherapeutic agent paclitaxel (PTX) for improved lung cancer treatment. The redox-sensitive nanocarrier system constructed from a hyaluronic acid-disulfide-vitamin E succinate (HA-SS-VES, HSV) conjugate was synthesized and PTX was loaded in the delivery system. The physicochemical properties of the HSV nanoparticles were characterized. The redox-sensitivity, tumor-targeting and intracellular drug release capability of the HSV nanoparticles were evaluated. Furthermore, in vitro and in vivo antitumor activity of the PTX-loaded HSV nanoparticles was investigated in a CD44 over-expressed A549 tumor model. This HSV conjugate was successfully synthesized and self-assembled to form nanoparticles in aqueous condition with a low critical micelle concentration of 36.3 μg mL -1 . Free PTX was successfully entrapped into the HSV nanoparticles with a high drug loading of 33.5% (w/w) and an entrapment efficiency of 90.6%. Moreover, the redox-sensitivity of the HSV nanoparticles was confirmed by particle size change of the nanoparticles along with in vitro release profiles in different reducing environment. In addition, the HA-receptor mediated endocytosis and the potency of redox-sensitivity for intracellular drug delivery were further verified by flow cytometry and confocal laser scanning microscopic analysis. The antitumor activity results showed that compared to redox-insensitive nanoparticles and Taxol ® , PTX-loaded redox-sensitive nanoparticles exhibited much greater in vitro cytotoxicity and apoptosis-inducing ability against CD44 over-expressed A549 tumor cells. In vivo, the PTX-loaded HSV nanoparticles possessed much higher antitumor efficacy in an A549 mouse xenograft model and demonstrated improved safety profile. In summary, our PTX-loaded redox-sensitive HSV nanoparticles demonstrated enhanced antitumor efficacy and improved safety of PTX. The results of our study indicated the redox-sensitive HSV nanoparticle was a promising nanocarrier for lung cancer therapy.

A redox-stratified ocean 3.2 billion years ago

NASA Astrophysics Data System (ADS)

Satkoski, Aaron M.; Beukes, Nicolas J.; Li, Weiqiang; Beard, Brian L.; Johnson, Clark M.

2015-11-01

Before the Great Oxidation Event (GOE) 2.4-2.2 billion years ago it has been traditionally thought that oceanic water columns were uniformly anoxic due to a lack of oxygen-producing microorganisms. Recently, however, it has been proposed that transient oxygenation of shallow seawater occurred between 2.8 and 3.0 billion years ago. Here, we present a novel combination of stable Fe and radiogenic U-Th-Pb isotope data that demonstrate significant oxygen contents in the shallow oceans at 3.2 Ga, based on analysis of the Manzimnyama Banded Iron Formation (BIF), Fig Tree Group, South Africa. This unit is exceptional in that proximal, shallow-water and distal, deep-water facies are preserved. When compared to the distal, deep-water facies, the proximal samples show elevated U concentrations and moderately positive δ56Fe values, indicating vertical stratification in dissolved oxygen contents. Confirmation of oxidizing conditions using U abundances is robustly constrained using samples that have been closed to U and Pb mobility using U-Th-Pb geochronology. Although redox-sensitive elements have been commonly used in ancient rocks to infer redox conditions, post-depositional element mobility has been rarely tested, and U-Th-Pb geochronology can constrain open- or closed-system behavior. The U abundances and δ56Fe values of the Manzimnyama BIF suggest the proximal, shallow-water samples record precipitation under stronger oxidizing conditions compared to the distal deeper-water facies, which in turn indicates the existence of a discrete redox boundary between deep and shallow ocean waters at this time; this work, therefore, documents the oldest known preserved marine redox gradient in the rock record. The relative enrichment of O2 in the upper water column is likely due to the existence of oxygen-producing microorganisms such as cyanobacteria. These results provide a new approach for identifying free oxygen in Earth's ancient oceans, including confirming the age of redox proxies, and indicate that cyanobacteria evolved prior to 3.2 Ga.

Biogeochemical zonation of sulfur during the discharge of groundwater to lake in desert plateau (Dakebo Lake, NW China).

PubMed

Su, Xiaosi; Cui, Geng; Wang, Huang; Dai, Zhenxue; Woo, Nam-Chil; Yuan, Wenzhen

2018-06-01

As one of the important elements of controlling the redox system within the hyporheic and hypolentic zone, sulfur is involved in a series of complex biogeochemical processes such as carbon cycle, water acidification, formation of iron and manganese minerals, redox processes of trace metal elements and a series of important ecological processes. Previous studies on biogeochemistry of the hyporheic and hypolentic zones mostly concentrated on nutrients of nitrogen and phosphorus, heavy metals and other pollutants. Systematic study of biogeochemical behavior of sulfur and its main controlling factors within the lake hypolentic zone is very urgent and important. In this paper, a typical desert plateau lake, Dakebo Lake in northwestern China, was taken for example within which redox zonation and biogeochemical characteristics of sulfur affected by hydrodynamic conditions were studied based on not only traditional hydrochemical analysis, but also environmental isotope evidence. In the lake hypolentic zone of the study area, due to the different hydrodynamic conditions, vertical profile of sulfur species and environmental parameters differ at the two sites of the lake (western side and center). Reduction of sulfate, deposition and oxidation of sulfide, dissolution and precipitation of sulfur-bearing minerals occurred are responded well to Eh, dissolved oxygen, pH, organic carbon and microorganism according to which the lake hypolentic zone can be divided into reduced zone containing H 2 S, reduced zone containing no H 2 S, transition zone and oxidized zone. The results of this study provide valuable insights for understanding sulfur conversion processes and sulfur biogeochemical zonation within a lake hypolentic zone in an extreme plateau arid environment and for protecting the lake-wetland ecosystem in arid and semiarid regions.

Temporal variability in trace metal solubility in a paddy soil not reflected in uptake by rice (Oryza sativa L.).

PubMed

Pan, Yunyu; Koopmans, Gerwin F; Bonten, Luc T C; Song, Jing; Luo, Yongming; Temminghoff, Erwin J M; Comans, Rob N J

2016-12-01

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.

Occurrence and health risk assessment of selected metals in drinking water from two typical remote areas in China.

PubMed

Geng, Menghan; Qi, Hongjuan; Liu, Xuelin; Gao, Bo; Yang, Zhan; Lu, Wei; Sun, Rubao

2016-05-01

The potential contaminations of 16 trace elements (Cr, Mn, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, Co, Be, V, Ti, Tl, Al) in drinking water collected in two remote areas in China were analyzed. The average levels of the trace elements were lower than the allowable concentrations set by national agencies, except for several elements (As, Sb, Mn, and Be) in individual samples. A health risk assessment model was conducted and carcinogenic and non-carcinogenic risks were evaluated separately. The results indicated that the total carcinogenic risks were higher than the maximum allowed risk level set by most organizations (1 × 10(-6)). Residents in both study areas were at risk of carcinogenic effects from exposure to Cr, which accounted for 80-90 % of the total carcinogenic risks. The non-carcinogenic risks (Cu, Zn, Ni) were lower than the maximum allowance levels. Among the four population groups, infants incurred the highest health risks and required special attention. Correlation analysis revealed significant positive associations among most trace elements, indicating the likelihood of a common source. The results of probabilistic health risk assessment of Cr based on Monte-Carlo simulation revealed that the uncertainty of system parameters does not affect the decision making of pollution prevention and control. Sensitivity analysis revealed that ingestion rate of water and concentration of Cr showed relatively high sensitivity to the health risks.

Constraining Gas Diffusivity-Soil Water Content Relationships in Forest Soils Using Surface Chamber Fluxes and Depth Profiles of Multiple Trace Gases

NASA Astrophysics Data System (ADS)

Dore, J. E.; Kaiser, K.; Seybold, E. C.; McGlynn, B. L.

2012-12-01

Forest soils are sources of carbon dioxide (CO2) to the atmosphere and can act as either sources or sinks of methane (CH4) and nitrous oxide (N2O), depending on redox conditions and other factors. Soil moisture is an important control on microbial activity, redox conditions and gas diffusivity. Direct chamber measurements of soil-air CO2 fluxes are facilitated by the availability of sensitive, portable infrared sensors; however, corresponding CH4 and N2O fluxes typically require the collection of time-course physical samples from the chamber with subsequent analyses by gas chromatography (GC). Vertical profiles of soil gas concentrations may also be used to derive CH4 and N2O fluxes by the gradient method; this method requires much less time and many fewer GC samples than the direct chamber method, but requires that effective soil gas diffusivities are known. In practice, soil gas diffusivity is often difficult to accurately estimate using a modeling approach. In our study, we apply both the chamber and gradient methods to estimate soil trace gas fluxes across a complex Rocky Mountain forested watershed in central Montana. We combine chamber flux measurements of CO2 (by infrared sensor) and CH4 and N2O (by GC) with co-located soil gas profiles to determine effective diffusivity in soil for each gas simultaneously, over-determining the diffusion equations and providing constraints on both the chamber and gradient methodologies. We then relate these soil gas diffusivities to soil type and volumetric water content in an effort to arrive at empirical parameterizations that may be used to estimate gas diffusivities across the watershed, thereby facilitating more accurate, frequent and widespread gradient-based measurements of trace gas fluxes across our study system. Our empirical approach to constraining soil gas diffusivity is well suited for trace gas flux studies over complex landscapes in general.

Application of relativistic electrons for the quantitative analysis of trace elements

NASA Astrophysics Data System (ADS)

Hoffmann, D. H. H.; Brendel, C.; Genz, H.; Löw, W.; Richter, A.

1984-04-01

Particle induced X-ray emission methods (PIXE) have been extended to relativistic electrons to induce X-ray emission (REIXE) for quantitative trace-element analysis. The electron beam (20 ≤ E0≤ 70 MeV) was supplied by the Darmstadt electron linear accelerator DALINAC. Systematic measurements of absolute K-, L- and M-shell ionization cross sections revealed a scaling behaviour of inner-shell ionization cross sections from which X-ray production cross sections can be deduced for any element of interest for a quantitative sample investigation. Using a multielemental mineral monazite sample from Malaysia the sensitivity of REIXE is compared to well established methods of trace-element analysis like proton- and X-ray-induced X-ray fluorescence analysis. The achievable detection limit for very heavy elements amounts to about 100 ppm for the REIXE method. As an example of an application the investigation of a sample prepared from manganese nodules — picked up from the Pacific deep sea — is discussed, which showed the expected high mineral content of Fe, Ni, Cu and Ti, although the search for aliquots of Pt did not show any measurable content within an upper limit of 250 ppm.

Albumin-bound fatty acids but not albumin itself alter redox balance in tubular epithelial cells and induce a peroxide-mediated redox-sensitive apoptosis

PubMed Central

Ruggiero, Christine; Elks, Carrie M.; Kruger, Claudia; Cleland, Ellen; Addison, Kaity; Noland, Robert C.

2014-01-01

Albuminuria is associated with metabolic syndrome and diabetes. It correlates with the progression of chronic kidney disease, particularly with tubular atrophy. The fatty acid load on albumin significantly increases in obesity, presenting a proinflammatory environment to the proximal tubules. However, little is known about changes in the redox milieu during fatty acid overload and how redox-sensitive mechanisms mediate cell death. Here, we show that albumin with fatty acid impurities or conjugated with palmitate but not albumin itself compromised mitochondrial and cell viability, membrane potential and respiration. Fatty acid overload led to a redox imbalance which deactivated the antioxidant protein peroxiredoxin 2 and caused a peroxide-mediated apoptosis through the redox-sensitive pJNK/caspase-3 pathway. Transfection of tubular cells with peroxiredoxin 2 was protective and mitigated apoptosis. Mitochondrial fatty acid entry and ceramide synthesis modulators suggested that mitochondrial β oxidation but not ceramide synthesis may modulate lipotoxic effects on tubular cell survival. These results suggest that albumin overloaded with fatty acids but not albumin itself changes the redox environment in the tubules, inducing a peroxide-mediated redox-sensitive apoptosis. Thus, mitigating circulating fatty acid levels may be an important factor in both preserving redox balance and preventing tubular cell damage in proteinuric diseases. PMID:24500687

Benthic foraminifera and trace element distribution: a case-study from the heavily polluted lagoon of Venice (Italy).

PubMed

Coccioni, Rodolfo; Frontalini, Fabrizio; Marsili, Andrea; Mana, Davide

2009-01-01

Living benthic foraminiferal assemblages were studied in surface samples collected from the lagoon of Venice (Italy) in order to investigate the relationship between these sensitive microorganisms and trace element pollution. Geochemical analysis of sediments shows that the lagoon is affected by trace element pollution (Cd, Cu, Ni, Pb, Zn and Hg) with the highest concentrations in its inner part, which corresponds to the Porto Marghera industrial area. The biocenosis are largely dominated by Ammonia tepida, Haynesina germanica and Cribroelphidium oceanensis and, subordinately, by Aubignyna perlucida, Ammonia parkinsoniana and Bolivina striatula. Biotic and abiotic factors were statistically analyzed with multivariate technique of cluster analysis and principal component analysis. The statistical analysis reveals a strong relationship between trace elements (in particular Mn, Pb and Hg) and the occurrence of abnormalities in foraminiferal tests. Remarkably, greater proportions of abnormal specimens are usually found at stations located close to the heaviest polluted industrial zone of Porto Marghera. This paper shows that benthic foraminifera can be used as useful and relatively speedy and inexpensive bio-indicators in monitoring the health quality of the lagoon of Venice. It also provides a basis for future investigations aimed at unraveling the benthic foraminiferal response to human-induced pollution in marine and transitional marine environments.

The Boring Billion, a slingshot for Complex Life on Earth.

PubMed

Mukherjee, Indrani; Large, Ross R; Corkrey, Ross; Danyushevsky, Leonid V

2018-03-13

The period 1800 to 800 Ma ("Boring Billion") is believed to mark a delay in the evolution of complex life, primarily due to low levels of oxygen in the atmosphere. Earlier studies highlight the remarkably flat C, Cr isotopes and low trace element trends during the so-called stasis, caused by prolonged nutrient, climatic, atmospheric and tectonic stability. In contrast, we suggest a first-order variability of bio-essential trace element availability in the oceans by combining systematic sampling of the Proterozoic rock record with sensitive geochemical analyses of marine pyrite by LA-ICP-MS technique. We also recall that several critical biological evolutionary events, such as the appearance of eukaryotes, origin of multicellularity & sexual reproduction, and the first major diversification of eukaryotes (crown group) occurred during this period. Therefore, it appears possible that the period of low nutrient trace elements (1800-1400 Ma) caused evolutionary pressures which became an essential trigger for promoting biological innovations in the eukaryotic domain. Later periods of stress-free conditions, with relatively high nutrient trace element concentration, facilitated diversification. We propose that the "Boring Billion" was a period of sequential stepwise evolution and diversification of complex eukaryotes, triggering evolutionary pathways that made possible the later rise of micro-metazoans and their macroscopic counterparts.

Groundwater-saline lakes interaction - The contribution of saline groundwater circulation to solute budget of saline lakes: a lesson from the Dead Sea

NASA Astrophysics Data System (ADS)

Kiro, Yael; Weinstein, Yishai; Starinsky, Abraham; Yechieli, Yoseph

2013-04-01

Saline lakes act as base level for both surface water and groundwater. Thus, a change in lake levels is expected to result in changes in the hydrogeological system in its vicinity, exhibited in groundwater levels, location of the fresh-saline water interface, sub-lacustrine groundwater discharge (SGD) and saline water circulation. All these processes were observed in the declining Dead Sea system, whose water level dropped by ~35 meters in the last 50 years. This work focuses mainly on the effect of circulation of Dead Sea water in the aquifer, which continues even in this very rapid base level drop. In general, seawater circulation in coastal aquifers is now recognized as a major process affecting trace element mass balances in coastal areas. Estimates of submarine groundwater discharge (SGD) vary over several orders of magnitude (1-1000000 m3/yr per meter shoreline). These estimates are sensitive to fresh-saline SGD ratios and to the temporal and spatial scales of the circulation. The Dead Sea system is an excellent natural field lab for studying seawater-groundwater interaction and large-scale circulation due to the absence of tides and to the minor role played by waves. During Dead Sea water circulation in the aquifer several geochemical reactions occur, ranging from short-term adsorption-desorption reactions and up to long-term precipitation and dissolution reactions. These processes affect the trace element distribution in the saline groundwater. Barite and celestine, which are supersaturated in the lake water, precipitate during circulation in the aquifer, reducing barium (from 5 to 1.5 mg/L), strontium (from 350 to 300 mg/L) and the long-lived 226Ra (from 145 to 60 dpm/L) in the saline groundwater. Redox-controlled reactions cause a decrease in uranium from 2.4 to 0.1 μg/L, and an increase in iron from 1 to 13 mg/L. 228Ra (t1/2=5.75 yr) activity in the Dead Sea is ~1 dpm/L and increase gradually as the saline water flows further inland until reaching steady-state activities (~27 dpm/L) with the aquifer sediments. The decrease in 226Ra and increase in 228Ra in the circulation process provide a robust method for calculating the amount of Dead Sea water circulating in the aquifer. This process can affect trace element concentrations in the Dead Sea and emphasize the potential of long-term seawater circulation in mass balances of saline water bodies.

PIXE analysis of caries related trace elements in tooth enamel

NASA Astrophysics Data System (ADS)

Annegarn, H. J.; Jodaikin, A.; Cleaton-Jones, P. E.; Sellschop, J. P. F.; Madiba, C. C. P.; Bibby, D.

1981-03-01

PIXE analysis has been applied to a set of twenty human teeth to determine trace element concentration in enamel from areas susceptible to dental caries (mesial and distal contact points) and in areas less susceptible to the disease (buccal surfaces), with the aim of determining the possible roles of trace elements in the curious process. The samples were caries-free anterior incisors extracted for periodontal reasons from subjects 10-30 years of age. Prior to extraction of the sample teeth, a detailed dental history and examination was carried out in each individual. PIXE analysis, using a 3 MeV proton beam of 1 mm diameter, allowed the determination of Ca, Mn, Fe, Cu, Zn, Sr and Pb above detection limits. As demonstrated in this work, the enhanced sensitivity of PIXE analysis over electron microprobe analysis, and the capability of localised surface analysis compared with the pooled samples required for neutron activation analysis, makes it a powerful and useful technique in dental analysis.

Modeling Trace Element Concentrations in the San Francisco Bay Estuary from Remote Measurement of Suspended Solids

NASA Astrophysics Data System (ADS)

Press, J.; Broughton, J.; Kudela, R. M.

2014-12-01

Suspended and dissolved trace elements are key determinants of water quality in estuarine and coastal waters. High concentrations of trace element pollutants in the San Francisco Bay estuary necessitate consistent and thorough monitoring to mitigate adverse effects on biological systems and the contamination of water and food resources. Although existing monitoring programs collect annual in situ samples from fixed locations, models proposed by Benoit, Kudela, & Flegal (2010) enable calculation of the water column total concentration (WCT) and the water column dissolved concentration (WCD) of 14 trace elements in the San Francisco Bay from a more frequently sampled metric—suspended solids concentration (SSC). This study tests the application of these models with SSC calculated from remote sensing data, with the aim of validating a tool for continuous synoptic monitoring of trace elements in the San Francisco Bay. Using HICO imagery, semi-analytical and empirical SSC algorithms were tested against a USGS dataset. A single-band method with statistically significant linear fit (p < 0.001) was chosen as the proxy for SSC values. The numerical models for WCT and the distribution ratio D were applied in MATLAB with terms to account for regional and seasonal effects, and results were used to calculate WCD. The modeled results were assessed against in situ data from the San Francisco Estuary Regional Monitoring Program. Quantile regression was used to evaluate model sensitivity to the distribution of regions, and outliers displaying regional aberrations were removed before robust regression was applied. Statistically significant and highly correlated results for WCT were found for 10 elements, with goodness of fit greater than or equal to that of the original models of seven elements. WCD was successfully modeled for six elements, with goodness of fit for each exceeding that of the original models. Concentrations of Arsenic, Iron, and Lead in the southern region of the Bay were found to exceed EPA water quality criteria for human health and aquatic life. The results of this study demonstrate the potential of monitoring programs using remote observation of trace element concentrations, and provide the foundation for investigation of pollutant sources and pathways over time.

Inductively coupled plasma optical emission spectrometry for trace multi-element determination in vegetable oils, margarine and butter after stabilization with propan-1-ol and water

NASA Astrophysics Data System (ADS)

de Souza, Roseli M.; Mathias, Bárbara M.; da Silveira, Carmem Lúcia P.; Aucélio, Ricardo Q.

2005-06-01

The quantitative evaluation of trace elements in foodstuffs is of considerable interest due to the potential toxicity of many elements, and because the presence of some metallic species might affect the overall quality (flavor and stability) of these products. In the present work, an inductively coupled plasma optical emission spectrometric method has been developed for the determination of six elements (Cd, Co, Cr, Cu, Ni and Mn) in olive oil, soy oil, margarine and butter. Organic samples (oils and fats) were stabilized using propan-1-ol and water, which enabled long-time sample dispersion in the solution. This simple sample preparation procedure, together with an efficient sample introduction strategy (using a Meinhard K3 nebulizer and a twister cyclonic spray chamber), facilitated the overall analytical procedure, allowing quantification using calibration curves prepared with inorganic standards. Internal standardization (Sc) was used for correction of matrix effects and signal fluctuations. Good sensitivities with limits of detection in the ng g -1 range were achieved for all six elements. These sensitivities were appropriate for the intended application. The method was tested through the analysis of laboratory-fortified samples with good recoveries (between 91.3% and 105.5%).

Trace organic chemical attenuation during managed aquifer recharge: Insights from a variably saturated 2D tank experiment

NASA Astrophysics Data System (ADS)

Regnery, Julia; Lee, Jonghyun; Drumheller, Zachary W.; Drewes, Jörg E.; Illangasekare, Tissa H.; Kitanidis, Peter K.; McCray, John E.; Smits, Kathleen M.

2017-05-01

Meaningful model-based predictions of water quality and quantity are imperative for the designed footprint of managed aquifer recharge installations. A two-dimensional (2D) synthetic MAR system equipped with automated sensors (temperature, water pressure, conductivity, soil moisture, oxidation-reduction potential) and embedded water sampling ports was used to test and model fundamental subsurface processes during surface spreading managed aquifer recharge operations under controlled flow and redox conditions at the meso-scale. The fate and transport of contaminants in the variably saturated synthetic aquifer were simulated using the finite element analysis model, FEFLOW. In general, the model concurred with travel times derived from contaminant breakthrough curves at individual sensor locations throughout the 2D tank. However, discrepancies between measured and simulated trace organic chemical concentrations (i.e., carbamazepine, sulfamethoxazole, tris (2-chloroethyl) phosphate, trimethoprim) were observed. While the FEFLOW simulation of breakthrough curves captured overall shapes of trace organic chemical concentrations well, the model struggled with matching individual data points, although compound-specific attenuation parameters were used. Interestingly, despite steady-state operation, oxidation-reduction potential measurements indicated temporal disturbances in hydraulic properties in the saturated zone of the 2D tank that affected water quality.

Hydrologic and biogeochemical controls of river subsurface solutes under agriculturally enhanced ground water flow

USGS Publications Warehouse

Wildman, R.A.; Domagalski, Joseph L.; Hering, J.G.

2009-01-01

The relative influences of hydrologic processes and biogeochemistry on the transport and retention of minor solutes were compared in the riverbed of the lower Merced River (California, USA). The subsurface of this reach receives ground water discharge and surface water infiltration due to an altered hydraulic setting resulting from agricultural irrigation. Filtered ground water samples were collected from 30 drive point locations in March, June, and October 2004. Hydrologic processes, described previously, were verified by observations of bromine concentrations; manganese was used to indicate redox conditions. The separate responses of the minor solutes strontium, barium, uranium, and phosphorus to these influences were examined. Correlation and principal component analyses indicate that hydrologic processes dominate the distribution of trace elements in the ground water. Redox conditions appear to be independent of hydrologic processes and account for most of the remaining data variability. With some variability, major processes are consistent in two sampling transects separated by 100 m. Copyright ?? 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Potential Aquifer Vulnerability in Regions Down-Gradient from ...

EPA Pesticide Factsheets

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of these uranium ores is a process of contacting the uranium mineral deposit with leaching (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality impacts from: 1) potential excursions of leaching solutions away from the injection zone into down-dip, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies

The measurement of trace elements in interplanetary dust and cometary particles by ultra-high sensitivity INAA

NASA Technical Reports Server (NTRS)

Zolensky, M. E.; Lindstrom, David J.; Lindstrom, Richard M.; Lindstrom, M. M.

1989-01-01

Today the major elemental composition of interplanetary dust particles (IDPs) is routinely determined in many laboratories. These and mineralogical studies have revealed the presence of at least two major types of IDPs, chondritic and refractory. Preliminary results of a successful attempt to determine abundances of a large suite of trace elements from both chondritic and refractory IDPs are reported. The analytical procedure can be used in the grain-by-grain analysis of returned cometary samples. Chondritic and refractory IDPs are characterized by standard scanning electron microscopy and energy dispersive x ray spectroscopy (SEM-EDX) techniques. With this system, detection limits for many elements are well below picogram levels, and some approach femtogram levels. This technique is non-destructive, although some sample handling is required, so particles can be analyzed by other techniques after instrument neutron activation analysis (INAA) is completed. Data is presently being reduced from the analyses of 7 IDPs. These are U2015E10, U2015F1, W7029-A2, W7029-A3, W7013A8, LACl (all chondritic) and 705 (refractory). So far, 17 different major and trace elements were detected and measured in these particles, including rare earths and some very volatile elements (Br and Zn).

Air pollution source identification

NASA Technical Reports Server (NTRS)

Fordyce, J. S.

1975-01-01

The techniques available for source identification are reviewed: remote sensing, injected tracers, and pollutants themselves as tracers. The use of the large number of trace elements in the ambient airborne particulate matter as a practical means of identifying sources is discussed. Trace constituents are determined by sensitive, inexpensive, nondestructive, multielement analytical methods such as instrumental neutron activation and charged particle X-ray fluorescence. The application to a large data set of pairwise correlation, the more advanced pattern recognition-cluster analysis approach with and without training sets, enrichment factors, and pollutant concentration rose displays for each element is described. It is shown that elemental constituents are related to specific source types: earth crustal, automotive, metallurgical, and more specific industries. A field-ready source identification system based on time and wind direction resolved sampling is described.

Proteomic identification of early salicylate- and flg22-responsive redox-sensitive proteins in Arabidopsis

PubMed Central

Liu, Pei; Zhang, Huoming; Yu, Boying; Xiong, Liming; Xia, Yiji

2015-01-01

Accumulation of reactive oxygen species (ROS) is one of the early defense responses against pathogen infection in plants. The mechanism about the initial and direct regulation of the defense signaling pathway by ROS remains elusive. Perturbation of cellular redox homeostasis by ROS is believed to alter functions of redox-sensitive proteins through their oxidative modifications. Here we report an OxiTRAQ-based proteomic study in identifying proteins whose cysteines underwent oxidative modifications in Arabidopsis cells during the early response to salicylate or flg22, two defense pathway elicitors that are known to disturb cellular redox homeostasis. Among the salicylate- and/or flg22-responsive redox-sensitive proteins are those involved in transcriptional regulation, chromatin remodeling, RNA processing, post-translational modifications, and nucleocytoplasmic shuttling. The identification of the salicylate-/flg22-responsive redox-sensitive proteins provides a foundation from which further study can be conducted toward understanding biological significance of their oxidative modifications during the plant defense response. PMID:25720653

Distribution of Major and Trace Elements in a Tropical Hydroelectric Reservoir in Sarawak, Malaysia.

PubMed

Sim, Siong Fong; Ling, Teck Yee; Nyanti, Lee; Ean Lee, Terri Zhuan; Mohd Irwan Lu, Nurul Aida Lu; Bakeh, Tomy

2014-01-01

This paper reports the metals content in water, sediment, macroalgae, aquatic plant, and fish of Batang Ai Hydroelectric Reservoir in Sarawak, Malaysia. The samples were acid digested and subjected to atomic absorption spectrometry analysis for Na, K, Mn, Cr, Ni, Zn, Mg, Fe, Sn, Al, Ca, As, Se, and Hg. The total Hg content was analysed on the mercury analyser. Results showed that metals in water, sediment, macroalgae, aquatic plant, and fish are distinguishable, with sediment and biota samples more susceptible to metal accumulation. The distributions of heavy metals in water specifically Se, Sn, and As could have associated with the input of fish feed, boating, and construction activities. The accumulation of heavy metals in sediment, macroalgae, and aquatic plant on the other hand might be largely influenced by the redox conditions in the aquatic environment. According to the contamination factor and the geoaccumulation index, sediment in Batang Ai Reservoir possesses low risk of contamination. The average metal contents in sediment and river water are consistently lower than the literature values reported and well below the limit of various guidelines. For fishes, trace element Hg was detected; however, the concentration was below the permissible level suggested by the Food and Agriculture Organization.

Distribution of Major and Trace Elements in a Tropical Hydroelectric Reservoir in Sarawak, Malaysia

PubMed Central

Nyanti, Lee; Ean Lee, Terri Zhuan; Mohd Irwan Lu, Nurul Aida Lu

2014-01-01

This paper reports the metals content in water, sediment, macroalgae, aquatic plant, and fish of Batang Ai Hydroelectric Reservoir in Sarawak, Malaysia. The samples were acid digested and subjected to atomic absorption spectrometry analysis for Na, K, Mn, Cr, Ni, Zn, Mg, Fe, Sn, Al, Ca, As, Se, and Hg. The total Hg content was analysed on the mercury analyser. Results showed that metals in water, sediment, macroalgae, aquatic plant, and fish are distinguishable, with sediment and biota samples more susceptible to metal accumulation. The distributions of heavy metals in water specifically Se, Sn, and As could have associated with the input of fish feed, boating, and construction activities. The accumulation of heavy metals in sediment, macroalgae, and aquatic plant on the other hand might be largely influenced by the redox conditions in the aquatic environment. According to the contamination factor and the geoaccumulation index, sediment in Batang Ai Reservoir possesses low risk of contamination. The average metal contents in sediment and river water are consistently lower than the literature values reported and well below the limit of various guidelines. For fishes, trace element Hg was detected; however, the concentration was below the permissible level suggested by the Food and Agriculture Organization. PMID:27437493

PROTON MICROPROBE ANALYSIS OF TRACE-ELEMENT VARIATIONS IN VITRINITES IN THE SAME AND DIFFERENT COAL BEDS.

USGS Publications Warehouse

Minkin, J.A.; Chao, E.C.T.; Blank, Herma; Dulong, F.T.

1987-01-01

The PIXE (proton-induced X-ray emission) microprobe can be used for nondestructive, in-situ analyses of areas as small as those analyzed by the electron microprobe, and has a sensitivity of detection as much as two orders of magnitude better than the electron microprobe. Preliminary studies demonstrated that PIXE provides a capability for quantitative determination of elemental concentrations in individual coal maceral grains with a detection limit of 1-10 ppm for most elements analyzed. Encouraged by the earlier results, we carried out the analyses reported below to examine trace element variations laterally (over a km range) as well as vertically (cm to m) in the I and J coal beds in the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in central Utah, and to compare the data with the data from two samples of eastern coals of Pennsylvanian age.

Redox regulation of stress signals: possible roles of dendritic stellate TRX producer cells (DST cell types).

PubMed

Yodoi, Junji; Nakamura, Hajime; Masutani, Hiroshi

2002-01-01

Thioredoxin (TRX) is a 12 kDa protein with redox-active dithiol (Cys-Gly-Pro-Cys) in the active site. TRX is induced by a variety of stresses including viral infection and inflammation. The promoter sequences of the TRX gene contain a series of stress-responsive elements including ORE, ARE, XRE, CRE and SP-1. TRX promotes DNA binding of transcription factors such as NF-kappaB, AP-1 and p53. TRX interacts with target proteins modulating the activity of those proteins. We have identified TRX binding protein-2 (TBP-2), which was identical to vitamin D3 up-regulated protein 1 (VDUP1). Potential action of TBP-2/VDUP1 as a redox-sensitive tumor suppressor will be discussed. There is accumulating evidence for the involvement of TRX in the protection against infectious and inflammatory disorders. We will discuss the role of TRX-dependent redox regulation of the host defense mechanism, in particular its relation to the emerging concept of constitutive and/or inducible TRX on special cell types with dendritic and stellate morphology in the immune, endocrine and nervous systems, which we provisionally designate as dendritic stellate TRX producer cells (DST cell types).

Trace metal concentrations in single specimens of the intestinal broad flatworm ( Diphyllobothrium latum), compared to their fish host ( Oncorhynchus mykiss) measured by total reflection X-ray fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Woelfl, Stefan; Mages, Margarete; Torres, Patricio

2008-12-01

The aim of this study was to investigate (1) whether intestine endoparasites ( Diphyllobothrium latum) accumulate trace elements related to its body size and (2) whether parasites bioconcentrate more trace elements than their host. Freshwater fish (rainbow trout Oncorhynchus mykiss) were sampled in the deep, oligotrophic and uncontaminated Lake Riñihue in Southern Chile. The element concentration of different organs (intestine, muscle, liver) and of the intestine endoparasites were analyzed using total reflection X-ray fluorescence spectrometry. The results showed that the mass fraction for Mn, Fe, Ni, Cu, and Pb decreased significantly with the body size (dry weight) of the endoparasite. Only Zn did not reveal such a relationship. Small parasites accumulated up to 80 times more Fe, Ni, Mn, Pb, and Cu than large parasites. Compared to the fish organs, small parasites accumulated in maximum 35 to 307 times more Mn, 5 to 255 times more Fe, 98 to 220 times more Ni, 3 to 175 times more Cu, and 0.4 to 12 times more Zn than the fish. Lead was only found in the endoparasite, but not in the fish organs. We conclude that (1) D. latum is a good indicator for trace element accumulation in fishes and that (2) small endoparasites are more sensitive as bioindicators because they showed higher bioconcentrations of trace metals than larger parasites.

Benthic foraminiferal trace metal uptake: a field calibration from the Arabia Sea Oxygen Minimum Zone

NASA Astrophysics Data System (ADS)

Koho, K. A.; Reichart, G.-J.

2012-04-01

The Arabian Sea Oxygen Minimum Zone (OMZ) is sustained by high surface water productivity and relatively weak mid-depth water column ventilation. High primary productivity drives high respiration rates in the water column, causing severe oxygen depletion between ±150-1400 m water depths, with the oxygen concentrations falling below 2 μM in the core of the OMZ. Living (rose Bengal stained) benthic foraminifera were collected at 10-stations, covering a large bottom water oxygen concentration gradient from the Murray Ridge. This sub-marine ridge is located in the open marine environment of the Arabian Sea and thus not affected by large gradients in surface water productivity such as encountered at the continental margins. Since these sites thus receive similar organic fluxes, but are bathed in bottom waters with contrasting oxygen concentrations, pore water profiles mainly reflect bottom water oxygenation. The study sites represent a natural laboratory to investigate the impact of bottom water chemistry on trace metal incorporation in benthic foraminifera. Trace metal analyses by laser ablation ICP-MS allows detailed single chamber measurements of trace metal content, which can be related to in situ pore water geochemistry. Focus of this study is on redox sensitive trace metal (e.g. Mn, U) incorporation into foraminiferal test calcite in relation to pore water oxygen and carbonate chemistry.

Deletion of Selenoprotein M Leads to Obesity without Cognitive Deficits*

PubMed Central

Pitts, Matthew W.; Reeves, Mariclair A.; Hashimoto, Ann C.; Ogawa, Ashley; Kremer, Penny; Seale, Lucia A.; Berry, Marla J.

2013-01-01

Selenium is an essential trace element that is co-translationally incorporated into selenoproteins in the form of the 21st amino acid, selenocysteine. This class of proteins largely functions in oxidation-reduction reactions and is critically involved in maintaining proper redox balance essential to health. Selenoprotein M (SelM) is a thioredoxin-like endoplasmic reticulum-resident protein that is highly expressed in the brain and possesses neuroprotective properties. In this study, we first assessed the regional pattern of SelM expression in the mouse brain to provide insights into the potential functional implications of this protein in physiology and behavior. Next, we generated transgenic mice with a targeted deletion of the SelM gene and subjected them to a battery of neurobehavioral tests to evaluate motor coordination, locomotion, and cognitive function in comparison with wild-type controls. Finally, these mice were tested for several measures of metabolic function and body composition. Our results show that SelM knock-out (KO) mice display no deficits in measures of motor coordination and cognitive function but exhibit increased weight gain, elevated white adipose tissue deposition, and diminished hypothalamic leptin sensitivity. These findings suggest that SelM plays an important role in the regulation of body weight and energy metabolism. PMID:23880772

Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2015-12-01

The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at <10-5 present atmospheric O2).2 As a result, it is difficult to quantify O2 concentrations implied by observed trace metal variations. As a first step toward providing more quantitative constraints on late Archean pO2, we conducted laboratory studies of pyrite and molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our results provide new empirical data that should allow for more precise quantitative constraints on atmospheric pO2 based on the sedimentary rock record. 1Anbar, A.D. et al., 2007. Science, 317, i. 5846: 1903-1906. 2Williamson & Rimstidt, 1994. Geochim. et Cosmochim. Acta, 58, n. 24: 5443-5454. 3Lehner et al., 2015. PLoS ONE, 10, n. 6: 1-15.

In search of the dead zone: Use of otoliths for tracking fish exposure to hypoxia

DOE PAGES

Limburg, Karin E.; Walther, Benjamin D.; Lu, Zunli; ...

2015-01-01

Otolith chemistry is often useful for tracking provenance of fishes, as well as examining migration histories. Whereas elements such as strontium and barium correlate well with salinity and temperature, experiments that examine manganese uptake as a function of these parameters have found no such correlation. Instead, dissolved manganese is available as a redox product, and as such, is indicative of low-oxygen conditions. Here we present evidence for that mechanism in a range of habitats from marine to freshwater, across species, and also present ancillary proxies that support the mechanism as well. For example, iodine is redox-sensitive and varies inversely withmore » Mn; and sulfur stable isotope ratios provide evidence of anoxic sulfate reduction in some circumstances.« less

The Bacterial Response Regulator ArcA Uses a Diverse Binding Site Architecture to Regulate Carbon Oxidation Globally

PubMed Central

Park, Dan M.; Akhtar, Md. Sohail; Ansari, Aseem Z.; Landick, Robert; Kiley, Patricia J.

2013-01-01

Despite the importance of maintaining redox homeostasis for cellular viability, how cells control redox balance globally is poorly understood. Here we provide new mechanistic insight into how the balance between reduced and oxidized electron carriers is regulated at the level of gene expression by mapping the regulon of the response regulator ArcA from Escherichia coli, which responds to the quinone/quinol redox couple via its membrane-bound sensor kinase, ArcB. Our genome-wide analysis reveals that ArcA reprograms metabolism under anaerobic conditions such that carbon oxidation pathways that recycle redox carriers via respiration are transcriptionally repressed by ArcA. We propose that this strategy favors use of catabolic pathways that recycle redox carriers via fermentation akin to lactate production in mammalian cells. Unexpectedly, bioinformatic analysis of the sequences bound by ArcA in ChIP-seq revealed that most ArcA binding sites contain additional direct repeat elements beyond the two required for binding an ArcA dimer. DNase I footprinting assays suggest that non-canonical arrangements of cis-regulatory modules dictate both the length and concentration-sensitive occupancy of DNA sites. We propose that this plasticity in ArcA binding site architecture provides both an efficient means of encoding binding sites for ArcA, σ70-RNAP and perhaps other transcription factors within the same narrow sequence space and an effective mechanism for global control of carbon metabolism to maintain redox homeostasis. PMID:24146625

Design of organic dyes and cobalt polypyridine redox mediators for high-efficiency dye-sensitized solar cells.

PubMed

Feldt, Sandra M; Gibson, Elizabeth A; Gabrielsson, Erik; Sun, Licheng; Boschloo, Gerrit; Hagfeldt, Anders

2010-11-24

Dye-sensitized solar cells (DSCs) with cobalt-based mediators with efficiencies surpassing the record for DSCs with iodide-free electrolytes were developed by selecting a suitable combination of a cobalt polypyridine complex and an organic sensitizer. The effect of the steric properties of two triphenylamine-based organic sensitizers and a series of cobalt polypyridine redox mediators on the overall device performance in DSCs as well as on transport and recombination processes in these devices was compared. The recombination and mass-transport limitations that, previously, have been found to limit the performance of these mediators were avoided by matching the properties of the dye and the cobalt redox mediator. Organic dyes with higher extinction coefficients than the standard ruthenium sensitizers were employed in DSCs in combination with outer-sphere redox mediators, enabling thinner TiO(2) films to be used. Recombination was reduced further by introducing insulating butoxyl chains on the dye rather than on the cobalt redox mediator, enabling redox couples with higher diffusion coefficients and more suitable redox potential to be used, simultaneously improving the photocurrent and photovoltage of the device. Optimization of DSCs sensitized with a triphenylamine-based organic dye in combination with tris(2,2'-bipyridyl)cobalt(II/III) yielded solar cells with overall conversion efficiencies of 6.7% and open-circuit potentials of more than 0.9 V under 1000 W m(-2) AM1.5 G illumination. Excellent performance was also found under low light intensity indoor conditions.

Cause of the chalcophile trace element enrichments marking the Holocene to Anthropocene transition in northern Chesapeake Bay sediments

NASA Astrophysics Data System (ADS)

Dolor, Marvourneen K.; Helz, George R.; McDonough, William F.

2012-04-01

In Chesapeake Bay sediments, concentrations of 15 chalcophile trace elements, half rarely determined in estuaries, display historical profiles having remarkably similar features. All element concentrations rose more or less simultaneously in the 1920-1940 interval, creating a chemostratigraphic marker of the Holocene to Anthropocene transition. Subsequently, concentration maxima occurred at ˜20-year intervals, suggesting a link to a documented climate cycle of similar period. These elements' correlated profiles suggest that sediments approximate binary mixtures of one lithogenic and one multi-element anthropogenic component. The latter component is characterized by these mass ratios (±standard error): Co/Zn 0.071 ± 0.003 Cu/Zn 0.147 ± 0.007 Ag/Zn 0.0030 ± 0.0002 Cd/Zn 0.0050 ± 0.0004 In/Zn 0.00031 ± 0.00004 Sn/Zn 0.019 ± 0.002 Sb/Zn 0.0040 ± 0.0002 Te/Zn 0.00059 ± 0.00003 Tl/Zn 0.0016 ± 0.0002 Pb/Zn 0.242 ± 0.013 Bi/Zn 0.00087 ± 0.00005 Where comparisons are possible, these ratios differ from those of contaminants in the harbor of the region's principal industrial city, Baltimore, but are surprisingly similar to those in sediment contaminants from the Susquehanna River, the Bay's chief tributary. Thus both the anthropogenic and the lithogenic components in the Bay's central channel appear to originate in the river basin. Many chalcophile element ratios in the anthropogenic component are similar to those in regional aerosols. If cumulative aerosol deposition on soils in the river basin is the source of the anthropogenic component, then the above ratios could be a regional anthropogenic signature that should be looked for more widely. Unlike Mo, the enrichment of these chalcophile elements in the Bay's sediments is not controlled by seasonal anoxia; Mo apparently possesses a unique capacity to record past redox information about estuaries owing to its high seawater concentration.

Development of redox-sensitive red fluorescent proteins for imaging redox dynamics in cellular compartments.

PubMed

Fan, Yichong; Ai, Hui-wang

2016-04-01

We recently reported a redox-sensitive red fluorescent protein, rxRFP1, which is one of the first genetically encoded red-fluorescent probes for general redox states in living cells. As individual cellular compartments have different basal redox potentials, we hereby describe a group of rxRFP1 mutants, showing different midpoint redox potentials for detection of redox dynamics in various subcellular domains, such as mitochondria, the cell nucleus, and endoplasmic reticulum (ER). When these redox probes were expressed and subcellularly localized in human embryonic kidney (HEK) 293 T cells, they responded to membrane-permeable oxidants and reductants. In addition, a mitochondrially localized rxRFP1 mutant, Mito-rxRFP1.1, was used to detect mitochondrial oxidative stress induced by doxorubicin-a widely used cancer chemotherapy drug. Our work has expanded the fluorescent protein toolkit with new research tools for studying compartmentalized redox dynamics and oxidative stress under various pathophysiological conditions.

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; McCleskey, R. Blaine; Schoonen, Martin A.A.; Xu, Yong

2001-01-01

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

Highly Sensitive Aluminium(III) Ion Sensor Based on a Self-assembled Monolayer on a Gold Nanoparticles Modified Screen-printed Carbon Electrode.

PubMed

See, Wong Pooi; Heng, Lee Yook; Nathan, Sheila

2015-01-01

A new approach for the development of a highly sensitive aluminium(III) ion sensor via the preconcentration of aluminium(III) ion with a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode and current mediation by potassium ferricyanide redox behavior during aluminium(III) ion binding has been attempted. A monolayer of mercaptosuccinic acid served as an effective complexation ligand for the preconcentration of trace aluminium; this led to an enhancement of aluminium(III) ion capture and thus improved the sensitivity of the sensor with a detection limit of down to the ppb level. Under the optimum experimental conditions, the sensor exhibited a wide linear dynamic range from 0.041 to 12.4 μM. The lower detection limit of the developed sensor was 0.037 μM (8.90 ppb) using a 10 min preconcentration time. The sensor showed excellent selectivity towards aluminium(III) ion over other interference ions.

Geochemical characterization of Neogene sediments from onshore West Baram Delta Province, Sarawak: paleoenvironment, source input and thermal maturity

NASA Astrophysics Data System (ADS)

Togunwa, Olayinka S.; Abdullah, Wan H.

2017-08-01

The Neogene strata of the onshore West Baram Province of NW Borneo contain organic rich rock formations particularly within the Sarawak basin. This basin is a proven prolific oil and gas province, thus has been a subject of great interest to characterise the nature of the organic source input and depositional environment conditions as well as thermal maturation. This study is performed on outcrop samples of Lambir, Miri and Tukau formations, which are of stratigraphic equivalence to the petroleum bearing cycles of the offshore West Baram delta province in Sarawak. The investigated mudstone samples are organic rich with a total organic carbon (TOC) content of more than 1.0 wt.%. The integration of elemental and molecular analyses indicates that there is no significant variation in the source input between these formations. The investigated biomarkers parameters achieved from acyclic isoprenoids, terpanes and steranes biomarkers of a saturated hydrocarbon biomarkers revealed that these sediments contain high contribution of land plants with minor marine organic matter input that was deposited and preserved under relatively oxic to suboxic conditions. This is further supported by low total sulphur (TS), high TOC/TN ratios, source and redox sensitive trace elements (V, Ni, Cr, Co and Mo) concentrations and their ratios, which suggest terrigenous source input deposited under oxic to suboxic conditions. Based on the analysed biomarker thermal maturity indicators, it may be deduced that the studied sediments are yet to enter the maturity stage for hydrocarbon generation, which is also supported by measured vitrinite reflectance values of 0.39-0.48% Ro.

Landslide-induced iron mobilisation shapes benthic accumulation of nutrients, trace metals and REE fractionation in an oligotrophic alpine stream

NASA Astrophysics Data System (ADS)

Johnston, Scott G.; Rose, Andrew L.; Burton, Edward D.; Webster-Brown, Jenny

2015-01-01

Large alpine landslides that entrain substantial organic material below the water table and create suspended floodplains may have long-term consequences for the mobilisation of redox sensitive elements, such as Fe, into streamwaters. In turn, the cycling of iron in aquatic systems can influence the fate of nutrients, alter primary productivity, enhance accumulation of trace metals and induce fractionation of rare earth elements (REE). In this study we examine a reach of a pristine oligotrophic alpine stream bracketing a 30 year-old landslide and explore the consequences of landslide-induced Fe mobilisation for aqueous geochemistry and the composition of benthic stream cobble biofilm. Elevated Fe2+ and Mn in landslide zone stream waters reflect inputs of circumneutral groundwater from the landslide debris-zone floodplain. Geochemical characteristics are consistent with reductive dissolution being a primary mechanism of Fe2+ and Mn mobilisation. Stream cobble biofilm in the landslide zone is significantly (P < 0.01) enriched in poorly crystalline Fe(III) (∼10-400 times background) and Mn (∼15-150 times background) (1 M HCl extractable; Fe(III)Ab). While the landslide zone accounts for less than ∼9% of the total stream length, we estimate it is responsible for approximately 60-80% of the stream's benthic biofilm load of poorly crystalline Fe(III) and Mn. Biofilm Fe(III) precipitates are comprised mainly of ferrihydrite, lepidocrocite and an organic-Fe species, while precipitate samples collected proximal to hyporheic seeps contain abundant sheath structures characteristic of the neutrophilic Fe(II)-oxidising bacteria Leptothrix spp. Stream-cobble Fe(III)-rich biofilm is accumulating PO43- (∼3-30 times background) and behaving as a preferential substrate for photosynthetic periphyton, with benthic PO43-, chlorophyll a, organic carbonHCl and total N all significantly positively correlated with Fe(III)Ab and significantly elevated within the landslide zone (P < 0.01). P K-edge XANES indicates P is associated with both ferric and Ca-phosphate minerals, while SEM-EDX elemental mapping of Fe(III) precipitates reveal strong spatial associations between P, Ca and Fe. Cobble Fe(III)-rich biofilm is also sorbing and accumulating multiple trace metals and REE. Within the landslide zone there are significant (P < 0.01) enrichments (up to ∼10-100 times background) for most trace metals examined here and metals display significant positive linear correlations with Fe(III)Ab on a log transformed basis. Stream cobble biofilm also exhibits distinct REE fractionation along the flow path, with light REE (La, Ce, Nd, Pr) preferentially partitioning to the Fe(III) and Mn-rich biofilm within the landslide zone. Accumulation of PO43- and trace metals in this relatively environmentally labile form may have implications for their bioavailability and downstream transport, but further research is required to assess possible ecological consequences. This study demonstrates the potential for large alpine landslides to encourage reach-scale circumneutral Fe mobilisation in adjacent streams, thereby shaping multiple aspects of benthic stream geochemistry for many years after the landslide event itself.

Recent developments in the analysis of toxic elements.

PubMed

Lisk, D J

1974-06-14

One may conclude that it is impractical to confine oneself to any one analytical method since ever more sensitive instrumentation continues to be produced. However, in certain methods such as anodic stripping voltammetry and flameless atomic absorption it may be background contamination from reagent impurities and surroundings rather than instrument sensitivity which controls the limits of element detection. The problem of contamination from dust or glassware is greatly magnified when the sample size becomes ever smaller. Air entering laboratories near highways may contain trace quantities of lead, cadmium, barium, antimony, and other elements from engine exhaust. Even plastic materials contacting the sample may be suspect as a source of contamination since specific metals may be used as catalysts in the synthesis of the plastic and traces may be retained in it. Certain elements may even be deliberately added to plastics during manufacture for identification purposes. Nondestructive methods such as neutron activation and x-ray techniques thus offer great advantages not only in time but in the elimination of impurities introduced during sample ashing. Future improvements in attainable limits of detection may arise largely from progress in the ultrapurification of reagents and "clean-room" techniques. Finally, the competence of the analyst is also vitally important in the skillful operation of modern complex analytical instrumentation and in the experienced evaluation of data.

Evaluation of methods for trace-element determination with emphasis on their usability in the clinical routine laboratory.

PubMed

Bolann, B J; Rahil-Khazen, R; Henriksen, H; Isrenn, R; Ulvik, R J

2007-01-01

Commonly used techniques for trace-element analysis in human biological material are flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Elements that form volatile hydrides, first of all mercury, are analysed by hydride generation techniques. In the absorption techniques the samples are vaporized into free, neutral atoms and illuminated by a light source that emits the atomic spectrum of the element under analysis. The absorbance gives a quantitative measure of the concentration of the element. ICP-AES and ICP-MS are multi-element techniques. In ICP-AES the atoms of the sample are excited by, for example, argon plasma at very high temperatures. The emitted light is directed to a detector, and the optical signals are processed to values for the concentrations of the elements. In ICP-MS a mass spectrometer separates and detects ions produced by the ICP, according to their mass-to-charge ratio. Dilution of biological fluids is commonly needed to reduce the effect of the matrix. Digestion using acids and microwave energy in closed vessels at elevated pressure is often used. Matrix and spectral interferences may cause problems. Precautions should be taken against trace-element contamination during collection, storage and processing of samples. For clinical problems requiring the analysis of only one or a few elements, the use of FAAS may be sufficient, unless the higher sensitivity of GFAAS is required. For screening of multiple elements, however, the ICP techniques are preferable.

Utilizing rare earth elements as tracers in high TDS reservoir brines in CCS applications

DOE PAGES

McLing, Travis; Smith, William; Smith, Robert

2014-12-31

In this paper we report the result of research associated with the testing of a procedures necessary for utilizing natural occurring trace elements, specifically the Rare Earth Elements (REE) as geochemical tracers in Carbon Capture and Storage (CCS) applications. Trace elements, particularly REE may be well suited to serve as in situ tracers for monitoring geochemical conditions and the migration of CO₂-charged waters within CCS storage systems. We have been conducting studies to determine the efficacy of using REE as a tracer and characterization tool in the laboratory, at a CCS analogue site in Soda Springs, Idaho, and at amore » proposed CCS reservoir at the Rock Springs Uplift, Wyoming. Results from field and laboratory studies have been encouraging and show that REE may be an effective tracer in CCS systems and overlying aquifers. In recent years, a series of studies using REE as a natural groundwater tracer have been conducted successfully at various locations around the globe. Additionally, REE and other trace elements have been successfully used as in situ tracers to describe the evolution of deep sedimentary Basins. Our goal has been to establish naturally occurring REE as a useful monitoring measuring and verification (MMV) tool in CCS research because formation brine chemistry will be particularly sensitive to changes in local equilibrium caused by the addition of large volumes of CO₂. Because brine within CCS target formations will have been in chemical equilibrium with the host rocks for millions of years, the addition of large volumes of CO₂ will cause reactions in the formation that will drive changes to the brine chemistry due to the pH change caused by the formation of carbonic acid. This CO₂ driven change in formation fluid chemistry will have a major impact on water rock reaction equilibrium in the formation, which will impart a change in the REE fingerprint of the brine that can measured and be used to monitor in situ reservoir conditions. Our research has shown that the REE signature imparted to the formation fluid by the introduction of CO₂ to the formation, can be measured and tracked as part of an MMV program. Additionally, this REE fingerprint may serve as an ideal tracer for fluid migration, both within the CCS target formation, and should formation fluids migrate into overlying aquifers. However application of REE and other trace elements to CCS system is complicated by the high salt content of the brines contained within the target formations. In the United States by regulation, in order for a geologic reservoir to be considered suitable for carbon storage, it must contain formation brine with total dissolved solids (TDS) > 10,000 ppm, and in most cases formation brines have TDS well in excess of that threshold. The high salinity of these brines creates analytical problems for elemental analysis, including element interference with trace metals in Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) (i.e. element mass overlap due to oxide or plasma phenomenon). Additionally, instruments like the ICP-MS that are sensitive enough to measure trace elements down to the parts per trillion level are quickly oversaturated when water TDS exceeds much more than 1,000 ppm. Normally this problem is dealt with through dilution of the sample, bringing the water chemistry into the instruments working range. However, dilution is not an option when analyzing these formation brines for trace metals, because trace elements, specifically the REE, which occur in aqueous solutions at the parts per trillion levels. Any dilution of the sample would make REE detection impossible. Therefore, the ability to use trace metals as in situ natural tracers in high TDS brines environments requires the development of methods for pre-concentrating trace elements, while reducing the salinity and associated elemental interference such that the brines can be routinely analyzed by standard ICP-MS methods. As part of the Big Sky Carbon Sequestration Project the INL-CAES has developed a rapid, easy to use process that pre-concentrates trace metals, including REE, up to 100x while eliminating interfering ions (e.g. Ba, Cl). The process is straightforward, inexpensive, and requires little infrastructure, using only a single chromatography column with inexpensive, reusable, commercially available resins and wash chemicals. The procedure has been tested with synthetic brines (215,000 ppm or less TDS) and field water samples (up to 5,000 ppm TDS). Testing has produced data of high quality with REE capture efficiency exceeding 95%, while reducing interfering elements by > 99%.« less

Thiolate/disulfide organic redox couples for efficient organic dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Li, Wen-Yan; Zheng, Hai-Kuo; Wang, Jian-Wen; Zhang, Le-Le; Han, Hui-Min; Wu, Ming-Xing

2017-08-01

A series of organic thiolate/disulfide redox couples based on benz-imidazole/othiazole/oxazole have been synthesized and applied to dye-sensitized solar cells (DSCs). Platinum (Pt) and carbon material are introduced as counter electrode (CE) catalysts towards this kind of organic redox couples regeneration and the photovoltaic performance of the DSCs using this organic redox couples has been investigated. The carbon CE shows high catalytic activity than Pt for the organic redox couples and the DSCs using carbon CE exhibit much higher efficiencies than those of the Pt CE-based devices.

Determination of low concentrations of iron, arsenic, selenium, cadmium, and other trace elements in natural samples using an octopole collision/reaction cell equipped quadrupole-inductively coupled plasma mass spectrometer.

PubMed

Dial, Angela R; Misra, Sambuddha; Landing, William M

2015-04-30

Accurate determination of trace metals has many applications in environmental and life sciences, such as constraining the cycling of essential micronutrients in biological production and employing trace metals as tracers for anthropogenic pollution. Analysis of elements such as Fe, As, Se, and Cd is challenged by the formation of polyatomic mass spectrometric interferences, which are overcome in this study. We utilized an Octopole Collision/Reaction Cell (CRC)-equipped Quadrupole-Inductively Coupled Plasma Mass Spectrometer for the rapid analysis of small volume samples (~250 μL) in a variety of matrices containing HNO3 and/or HCl. Efficient elimination of polyatomic interferences was demonstrated by the use of the CRC in Reaction Mode (RM; H2 gas) and in Collision-Reaction Mode (CRM; H2 and He gas), in addition to hot plasma (RF power 1500 W) and cool plasma (600 W) conditions. It was found that cool plasma conditions with RM achieved the greatest signal sensitivity while maintaining low detection limits (i.e. (56) Fe in 0.44 M HNO3 has a sensitivity of 160,000 counts per second (cps)-per-1 µg L(-1) and a limit of detection (LoD) of 0.86 ng L(-1) ). The average external precision was ≤ ~10% for minor (≤10 µg L(-1) ) elements measured in a 1:100 dilution of NIST 1643e and for iron in rainwater samples under all instrumental operating conditions. An improved method has been demonstrated for the rapid multi-element analysis of trace metals that are challenged by polyatomic mass spectrometric interferences, with a focus on (56) Fe, (75) As, (78) Se and (111) Cd. This method can contribute to aqueous environmental geochemistry and chemical oceanography, as well as other fields such as forensic chemistry, agriculture, food chemistry, and pharmaceutical sciences. Copyright © 2015 John Wiley & Sons, Ltd.

Fully 3D-Printed Preconcentrator for Selective Extraction of Trace Elements in Seawater.

PubMed

Su, Cheng-Kuan; Peng, Pei-Jin; Sun, Yuh-Chang

2015-07-07

In this study, we used a stereolithographic 3D printing technique and polyacrylate polymers to manufacture a solid phase extraction preconcentrator for the selective extraction of trace elements and the removal of unwanted salt matrices, enabling accurate and rapid analyses of trace elements in seawater samples when combined with a quadrupole-based inductively coupled plasma mass spectrometer. To maximize the extraction efficiency, we evaluated the effect of filling the extraction channel with ordered cuboids to improve liquid mixing. Upon automation of the system and optimization of the method, the device allowed highly sensitive and interference-free determination of Mn, Ni, Zn, Cu, Cd, and Pb, with detection limits comparable with those of most conventional methods. The system's analytical reliability was further confirmed through analyses of reference materials and spike analyses of real seawater samples. This study suggests that 3D printing can be a powerful tool for building multilayer fluidic manipulation devices, simplifying the construction of complex experimental components, and facilitating the operation of sophisticated analytical procedures for most sample pretreatment applications.

Redox-Responsive Biomimetic Polymeric Micelle for Simultaneous Anticancer Drug Delivery and Aggregation-Induced Emission Active Imaging.

PubMed

Hu, Jun; Zhuang, Weihua; Ma, Boxuan; Su, Xin; Yu, Tao; Li, Gaocan; Hu, Yanfei; Wang, Yunbing

2018-05-10

Intelligent polymeric micelles have been developed as potential nanoplatforms for efficient drug delivery and diagnosis. Herein, we successfully prepared redox-sensitive polymeric micelles combined aggregation-induced emission (AIE) imaging as an outstanding anticancer drug carrier system for simultaneous chemotherapy and bioimaging. The amphiphilic copolymer TPE-SS-PLAsp- b-PMPC could self-assemble into spherical micelles, and these biomimetic micelles exhibited great biocompatibility and remarkable ability in antiprotein adsorption, showing great potential for biomedical application. Anticancer drug doxorubicin (DOX) could be encapsulated during the self-assembly process, and these drug-loaded micelles showed intelligent drug release and improved antitumor efficacy due to the quick disassembly in response to high levels of glutathione (GSH) in the environment. Moreover, the intracellular DOX release could be traced through the fluorescent imaging of these AIE micelles. As expected, the in vivo antitumor study exhibited that these DOX-carried micelles showed better antitumor efficacy and less adverse effects than that of free DOX. These results strongly indicated that this smart biomimetic micelle system would be a prominent candidate for chemotherapy and bioimaging.

Effects of boundary conditions on the cleaning efficiency of riverbank filtration and artificial groundwater recharge systems regarding bulk parameters and trace pollutants.

PubMed

Storck, Florian R; Schmidt, Carsten K; Wülser, Richard; Brauch, Heinz-Jürgen

2012-01-01

Drinking water is often produced from surface water by riverbank filtration (RBF) or artificial groundwater recharge (AGR). In this study, an AGR system was exemplarily investigated and results were compared with those of RBF systems, in which the effects of redox milieu, temperature and surface water discharge on the cleaning efficiency were evaluated. Besides bulk parameters such as DOC (dissolved organic carbon), organic trace pollutants including iodinated X-ray contrast media, personal care products, complexing agents, and pharmaceuticals were investigated. At all studied sites, levels of TOC (total organic carbon), DOC, AOX (adsorbable organic halides), SAC (spectral absorption coefficient at 254 nm), and turbidity were reduced significantly. DOC removal was stimulated at higher groundwater temperatures during AGR. Several substances were generally easily removable during both AGR and RBF, regardless of the site, season, discharge or redox regime. For some more refractory substances, however, removal efficiency turned out to be significantly influenced by redox conditions.

Trace Element Study of MORB Glasses from 14¡ã-16¡ãN along Mid-Atlantic Ridge by LA-ICP- MS

NASA Astrophysics Data System (ADS)

Barzoi, C. A.; Casey, J. F.; Gao, Y.; Lapen, T.

2007-12-01

A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic rocks in the region indicate that 1) the enriched basalts have positive Ta-Nb anomalies, enriched relative to U, Th, and La 2) basalts have relatively high SiO2 abundances compared to the global average, 3) basalts show a HIMU isotopic signature, and 4) bulk major element abundances and mineral chemistry in mantle rocks indicate that they are among the most depleted,although variably refertilized, residual mantle assemblages sampled to date along MORs.We suggest that much of the regional variation in major and trace element data, as well as isotopic data and the unusual regional geology (multiple core complexes) can be explained by melting of a sub-axial mantle that contains two end members, one highly depleted and the other enriched. These components appear to involve ancient recycled ocean crust and lithospheric mantle.

Can we use high precision metal isotope analysis to improve our understanding of cancer?

PubMed

Larner, Fiona

2016-01-01

High precision natural isotope analyses are widely used in geosciences to trace elemental transport pathways. The use of this analytical tool is increasing in nutritional and disease-related research. In recent months, a number of groups have shown the potential this technique has in providing new observations for various cancers when applied to trace metal metabolism. The deconvolution of isotopic signatures, however, relies on mathematical models and geochemical data, which are not representative of the system under investigation. In addition to relevant biochemical studies of protein-metal isotopic interactions, technological development both in terms of sample throughput and detection sensitivity of these elements is now needed to translate this novel approach into a mainstream analytical tool. Following this, essential background healthy population studies must be performed, alongside observational, cross-sectional disease-based studies. Only then can the sensitivity and specificity of isotopic analyses be tested alongside currently employed methods, and important questions such as the influence of cancer heterogeneity and disease stage on isotopic signatures be addressed.

Tracing fluid transfer across subduction zones using iron and zinc stable isotopes

NASA Astrophysics Data System (ADS)

Williams, H. M.; Debret, B.; Pons, M. L.; Bouilhol, P.

2016-12-01

In subduction zones, serpentinite devolatilization within the downgoing slab and the fluids released play a fundamental role in volatile transfer as well as the redox evolution of the sub-arc mantle. Constraining subduction-related serpentinite devolatilisation is essential in order to better understand of the nature and composition of slab-derived fluids and fluid/rock interactions. Fe and Zn stable isotopes can trace fluid composition and speciation as isotope partitioning is driven by changes in oxidation state, coordination, and bonding environment. In the case of serpentinite devolatilisation, Fe isotope fractionation should reflect changes in Fe redox state and the formation of Fe-Cl- and SO42- complexes (Hill et al., GCA 2010); Zn isotope fractionation should be sensitive to complexation with CO32-, HS- and SO42- anions (Fujii et al., GCA 2011). We targeted samples from Western Alps ophiolite complexes, interpreted as remnants of serpentinized oceanic lithosphere metamorphosed and devolatilized during subduction (Hattori and Guillot, G3 2007; Debret et al., Chem. Geol. 2013). A striking negative correlation is present between bulk serpentinite Fe isotope composition and Fe3+/Fetot, with the highest grade samples displaying the heaviest Fe isotope compositions and lowest Fe3+/Fetot (Debret et al., Geology, 2016). The same samples also display a corresponding variation in Zn isotopes, with the highest grade samples displaying isotopically light compositions (Pons et al., in revision). The negative correlation between Fe and Zn isotopes and decrease in Fe3+/Fetot can explained by serpentinite sulfide breakdown and the release of fluids enriched in isotopically light Fe and heavy Zn sulphate complexes. The migration of these SOX-bearing fluids from the slab to the slab-mantle interface or mantle wedge has important implications for the redox evolution of the sub-arc mantle and the transport of metals from the subducting slab.

Electrolytes Based on TEMPO–Co Tandem Redox Systems Outperform Single Redox Systems in Dye‐sensitized Solar Cells

PubMed Central

Cong, Jiayan; Hao, Yan; Boschloo, Gerrit

2014-01-01

Abstract A new TEMPO–Co tandem redox system with TEMPO and Co(bpy)3 2+/3+ has been investigated for the use in dye‐sensitized solar cells (DSSCs). A large open‐circuit voltage (V OC) increase, from 862 mV to 965 mV, was observed in the tandem redox system, while the short‐circuit current density (J SC) was maintained. The conversion efficiency was observed to increase from 7.1 % for cells containing the single Co(bpy)3 2+/3+ redox couple, to 8.4 % for cells containing the TEMPO–Co tandem redox system. The reason for the increase in V OC and overall efficiency is ascribed to the involvement of partial regeneration of the sensitizing dye molecules by TEMPO. This assumption can be verified through the observed much faster regeneration dynamics exhibited in the presence of the tandem system. Using the tandem redox system, the faster recombination problem of the single TEMPO redox couple is resolved and the mass‐transport of the metal‐complex‐based electrolyte is also improved. This TEMPO–Co tandem system is so far the most effienct tandem redox electrolyte reported not involving iodine. The current results show a promising future for tandem system as replacements for single redox systems in electrolytes for DSSCs. PMID:25504818

Atmospheric oxygenation three billion years ago.

PubMed

Crowe, Sean A; Døssing, Lasse N; Beukes, Nicolas J; Bau, Michael; Kruger, Stephanus J; Frei, Robert; Canfield, Donald E

2013-09-26

It is widely assumed that atmospheric oxygen concentrations remained persistently low (less than 10(-5) times present levels) for about the first 2 billion years of Earth's history. The first long-term oxygenation of the atmosphere is thought to have taken place around 2.3 billion years ago, during the Great Oxidation Event. Geochemical indications of transient atmospheric oxygenation, however, date back to 2.6-2.7 billion years ago. Here we examine the distribution of chromium isotopes and redox-sensitive metals in the approximately 3-billion-year-old Nsuze palaeosol and in the near-contemporaneous Ijzermyn iron formation from the Pongola Supergroup, South Africa. We find extensive mobilization of redox-sensitive elements through oxidative weathering. Furthermore, using our data we compute a best minimum estimate for atmospheric oxygen concentrations at that time of 3 × 10(-4) times present levels. Overall, our findings suggest that there were appreciable levels of atmospheric oxygen about 3 billion years ago, more than 600 million years before the Great Oxidation Event and some 300-400 million years earlier than previous indications for Earth surface oxygenation.

Redox sensor proteins for highly sensitive direct imaging of intracellular redox state.

PubMed

Sugiura, Kazunori; Nagai, Takeharu; Nakano, Masahiro; Ichinose, Hiroshi; Nakabayashi, Takakazu; Ohta, Nobuhiro; Hisabori, Toru

2015-02-13

Intracellular redox state is a critical factor for fundamental cellular functions, including regulation of the activities of various metabolic enzymes as well as ROS production and elimination. Genetically-encoded fluorescent redox sensors, such as roGFP (Hanson, G. T., et al. (2004)) and Redoxfluor (Yano, T., et al. (2010)), have been developed to investigate the redox state of living cells. However, these sensors are not useful in cells that contain, for example, other colored pigments. We therefore intended to obtain simpler redox sensor proteins, and have developed oxidation-sensitive fluorescent proteins called Oba-Q (oxidation balance sensed quenching) proteins. Our sensor proteins derived from CFP and Sirius can be used to monitor the intracellular redox state as their fluorescence is drastically quenched upon oxidation. These blue-shifted spectra of the Oba-Q proteins enable us to monitor various redox states in conjunction with other sensor proteins. Copyright © 2015 Elsevier Inc. All rights reserved.

Measuring the content of 17 elements in the flesh of Prunus cerasifera and its cultivars by ICP-MS.

PubMed

Shen, Jing; Xue, Hai-Yan; Li, Gai-Ru; Lu, Yi; Yao, Jun

2014-09-01

The present study compared the contents of inorganic elements in the pulp of purple, red, and yellow Prunus cerasifera with its cultivars. A method was established for the analysis of 17 kinds of trace elements (K, Ca, Mg, Na, Fe, Mn, Cu, Zn, Be, Li, Se, Sr, Cr, Pb, Cd, As and Hg) in the flesh of Prunus cerasifera by microwave digestion-ICP-MS. The detection method is simple and quick, yet shoes high precision and high sensitivity. The recovery rate of 17 elements ranged, from 93.5% to 110.4%. The analysis results showed that the contents of 17 elements in the flesh of purple, red, and yellow Prunus cerasifera and its cultivars are similar, containing extremely rich K elements (as high as 1 per thousand) and higher contents of Ca, Mg, Na, Fe and Mn. The contents of Cu, Zn, Li, Se, Sr and Cr are also present. The contents of Pb, Cd, As, Hg and other harmful element are either very low or not detectable. The experimental results for the study of trace elements in pulp of Prunus cerasifera and its cultivars provide empirical data for. future research in this area.

Minor Elements in Nakhlite Pyroxenes: Does Cr Record Changes in REDOX Conditions during Crystallization?

NASA Technical Reports Server (NTRS)

McKay, G.; Schwandt, C.; Le, L.; Mikouchi, T.

2007-01-01

Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998

Effects of dietary lipid, vitamins and minerals on total amounts and redox status of glutathione and ubiquinone in tissues of Atlantic salmon (Salmo salar): a multivariate approach.

PubMed

Hamre, Kristin; Torstensen, Bente E; Maage, Amund; Waagbø, Rune; Berge, Rolf K; Albrektsen, Sissel

2010-10-01

The hypothesis of the present study was that Atlantic salmon (Salmo salar) would respond to large variations in supplementation of dietary pro- and antioxidants, and marine lipid, with adjustment of the endogenously synthesised antioxidants, glutathione (GSH) and ubiquinone (UQ). An experiment with 2(7-3) reduced factorial design (the number of cases reduced systematically from 2(7) (full design) to 2(4) (reduced design)) was conducted, where vitamins, minerals and lipid were supplemented in the diet at high and low levels. For the vitamins and minerals the high levels were chosen to be just below anticipated toxic levels and the low levels were just above the requirement (vitamin C, 30 and 1000 mg/kg; vitamin E, 70 and 430 mg/kg; Fe, 70 and 1200 mg/kg; Cu, 8 and 110 mg/kg; Mn, 12 and 200 mg/kg). For astaxanthin, the dietary levels were 10 and 50 mg/kg and for lipid, 150 and 330 g/kg. The experiment was started with post-smolts (148 (sd 17 g)) and lasted for 5 months. The only effect on GSH was a minor increase ( < 10 %) in total concentration in the liver in response to high dietary lipid. GSH redox state was not affected. UQ responded to dietary lipid, astaxanthin and vitamin E, both with regard to total concentration and redox state. Except for an effect of Fe on plasma GSH, the trace elements and vitamin C had no effect on tissue levels and oxidation state of GSH and UQ. This shows that the endogenous redox state is quite robust with regard to variation of dietary pro- and antioxidants in Atlantic salmon.

Information processing through a bio-based redox capacitor: signatures for redox-cycling.

PubMed

Liu, Yi; Kim, Eunkyoung; White, Ian M; Bentley, William E; Payne, Gregory F

2014-08-01

Redox-cycling compounds can significantly impact biological systems and can be responsible for activities that range from pathogen virulence and contaminant toxicities, to therapeutic drug mechanisms. Current methods to identify redox-cycling activities rely on the generation of reactive oxygen species (ROS), and employ enzymatic or chemical methods to detect ROS. Here, we couple the speed and sensitivity of electrochemistry with the molecular-electronic properties of a bio-based redox-capacitor to generate signatures of redox-cycling. The redox capacitor film is electrochemically-fabricated at the electrode surface and is composed of a polysaccharide hydrogel with grafted catechol moieties. This capacitor film is redox-active but non-conducting and can engage diffusible compounds in either oxidative or reductive redox-cycling. Using standard electrochemical mediators ferrocene dimethanol (Fc) and Ru(NH3)6Cl3 (Ru(3+)) as model redox-cyclers, we observed signal amplifications and rectifications that serve as signatures of redox-cycling. Three bio-relevant compounds were then probed for these signatures: (i) ascorbate, a redox-active compound that does not redox-cycle; (ii) pyocyanin, a virulence factor well-known for its reductive redox-cycling; and (iii) acetaminophen, an analgesic that oxidatively redox-cycles but also undergoes conjugation reactions. These studies demonstrate that the redox-capacitor can enlist the capabilities of electrochemistry to generate rapid and sensitive signatures of biologically-relevant chemical activities (i.e., redox-cycling). Published by Elsevier B.V.

An alpha particle instrument with alpha, proton, and X-ray modes for planetary chemical analyses

NASA Technical Reports Server (NTRS)

Economou, T. E.; Turkevich, A. L.

1976-01-01

The interaction of alpha particles with matter is employed in a compact instrument that could provide rather complete in-situ chemical analyses of surfaces and thin atmospheres of extraterrestrial bodies. The instrument is a miniaturized and improved version of the Surveyor lunar instrument. The backscattering of alpha particles and (alpha, p) reactions provide analytical data on the light elements (carbon-iron). An X-ray mode that detects the photons produced by the alpha sources provides sensitivity and resolution for the chemical elements heavier than about silicon. The X-rays are detected by semiconductor detectors having a resolution between 150 and 250 eV at 5.9 keV. Such an instrument can identify and determine with good accuracy 99 percent of the atoms (except hydrogen) in rocks. For many trace elements, the detecting sensitivity is a few ppm. Auxiliary sources could be used to enhance the sensitivities for elements of special interest. The instrument could probably withstand the acceleration involved in semi-hard landings.

Redox-responsive theranostic nanoplatforms based on inorganic nanomaterials.

PubMed

Han, Lu; Zhang, Xiao-Yong; Wang, Yu-Long; Li, Xi; Yang, Xiao-Hong; Huang, Min; Hu, Kun; Li, Lu-Hai; Wei, Yen

2017-08-10

Spurred on by advances in materials chemistry and nanotechnology, scientists have developed many novel nanopreparations for cancer diagnosis and therapy. To treat complex malignant tumors effectively, multifunctional nanomedicines with targeting ability, imaging properties and controlled drug release behavior should be designed and exploited. The therapeutic efficiency of loaded drugs can be dramatically improved using redox-responsive nanoplatforms which can sense the differences in the redox status of tumor tissues and healthy ones. Redox-sensitive nanocarriers can be constructed from both organic and inorganic nanomaterials; however, at present, drug delivery nanovectors progressively lean towards inorganic nanomaterials because of their facile synthesis/modification and their unique physicochemical properties. In this review, we focus specifically on the preparation and application of redox-sensitive nanosystems based on mesoporous silica nanoparticles (MSNs), carbon nanomaterials, magnetic nanoparticles, gold nanomaterials and other inorganic nanomaterials. We discuss relevant examples of redox-sensitive nanosystems in each category. Finally, we discuss current challenges and future strategies from the aspect of material design and practical application. Copyright © 2017 Elsevier B.V. All rights reserved.

Mercury (II) reduction and co-precipitation of metallic mercury on hydrous ferric oxide in contaminated groundwater.

PubMed

Richard, Jan-Helge; Bischoff, Cornelia; Ahrens, Christian G M; Biester, Harald

2016-01-01

Mercury (Hg) speciation and sorption analyses in contaminated aquifers are useful for understanding transformation, retention, and mobility of Hg in groundwater. In most aquifers hydrous ferric oxides (HFOs) are among the most important sorbents for trace metals; however, their role in sorption or mobilization of Hg in aquifers has been rarely analyzed. In this study, we investigated Hg chemistry and Hg sorption to HFO under changing redox conditions in a highly HgCl2-contaminated aquifer (up to 870μgL(-1) Hg). Results from aqueous and solid phase Hg measurements were compared to modeled (PHREEQC) data. Speciation analyses of dissolved mercury indicated that Hg(II) forms were reduced to Hg(0) under anoxic conditions, and adsorbed to or co-precipitated with HFO. Solid phase Hg thermo-desorption measurements revealed that between 55 and 93% of Hg bound to HFO was elemental Hg (Hg(0)). Hg concentrations in precipitates reached more than 4 weight %, up to 7000 times higher than predicted by geochemical models that do not consider unspecific sorption to and co-precipitation of elemental Hg with HFO. The observed process of Hg(II) reduction and Hg(0) formation, and its retention and co-precipitation by HFO is thought to be crucial in HgCl2-contaminated aquifers with variable redox-conditions regarding the related decrease in Hg solubility (factor of ~10(6)), and retention of Hg in the aquifer. Copyright © 2015 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Distribution of siderophile and other trace elements in melt rock at the Chicxulub impact structure

NASA Technical Reports Server (NTRS)

Schuraytz, B. C.; Lindstrom, D. J.; Martinez, R. R.; Sharpton, V. L.; Marin, L. E.

1994-01-01

Recent isotopic and mineralogical studies have demonstrated a temporal and chemical link between the Chicxulub multiring impact basin and ejecta at the Cretaceous-Tertiary boundary. A fundamental problem yet to be resolved, however, is identification of the projectile responsible for this cataclysmic event. Drill core samples of impact melt rock from the Chichxulub structure contain Ir and Os abundances and Re-Os isotopic ratios indicating the presence of up to approx. 3 percent meteoritic material. We have used a technique involving microdrilling and high sensitivity instrumental neutron activation analysis (INAA) in conjunction with electron microprobe analysis to characterize further the distribution of siderophile and other trace elements among phases within the C1-N10 melt rock.

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

NASA Astrophysics Data System (ADS)

Leitzke, F. P.; Fonseca, R. O. C.; Sprung, P.; Mallmann, G.; Lagos, M.; Michely, L. T.; Münker, C.

2017-09-01

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO-CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite-magnetite-quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt ∼ 0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt ∼ 0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

Trace element distribution in waters of the northern catchment area of Lake Linneret, northern Israel

NASA Astrophysics Data System (ADS)

Sandler, A.; Brenner, I. B.; Halicz, L.

1988-02-01

Waters of the northern watershed of Lake Kineret, sampled during the period 1978 1983, were analyzed for their major and trace element contents. The trace element concentrations of the major water sources of the watershed (the Dan and Banias springs) represent background values. After emergence, the waters are subjected to human activity. In crossing the populated and cultivated Hula Basin in man-made canals, the major and trace element contents increase. In comparison to the trace element concentrations, those of the major elements have narrow ranges and small temporal fluctuations. Trace element concentrations varied by 3 orders of magnitude, and temporal variations were large but not neccessarily seasonal. Point sources of trace elements were urban effluents, fish pond wastes, and peat soil drainage. The trace element concentrations decrease in the waters of the last segment of the Jordan River. All measured trace elements were below the criteria levels established by regulatory agencies. Several, however, were of the same order of magnitude. Addition of wastes from enhanced recycling, and morphologic modification of the final course of the Jordan River could result in increase in the trace element concentrations in the water.

Non-destructive trace element microanalysis of as-received cometary nucleus samples using synchrotron x ray fluorescence

NASA Technical Reports Server (NTRS)

Sutton, S. R.

1989-01-01

The Synchrotron X ray Fluorescence (SXRF) microprobe at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory, will be an excellent instrument for non-destructive trace element analyses of cometary nucleus samples. Trace element analyses of as-received cometary nucleus material will also be possible with this technique. Bulk analysis of relatively volatile elements will be important in establishing comet formation conditions. However, as demonstrated for meteorites, microanalyses of individual phases in their petrographic context are crucial in defining the histories of particular components in unequilibrated specimens. Perhaps most informative in comparing cometary material with meteorites will be the halogens and trace metals. In-situ, high spatial resolution microanalyses will be essential in establishing host phases for these elements and identifying terrestrial (collection/processing) overprints. The present SXRF microprobe is a simple, yet powerful, instrument in which specimens are excited with filtered, continuum synchrotron radiation from a bending magnet on a 2.5 GeV electron storage ring. A refrigerated cell will be constructed to permit analyses at low temperatures. The cell will consist essentially of an air tight housing with a cold stage. Kapton windows will be used to allow the incident synchrotron beam to enter the cell and fluorescent x rays to exit it. The cell will be either under vacuum or continuous purge by ultrapure helium during analyses. Several other improvements of the NSLS microprobe will be made prior to the cometary nucleus sample return mission that will greatly enhance the sensitivity of the technique.

Status of essential elements in autism spectrum disorder: systematic review and meta-analysis.

PubMed

Saghazadeh, Amene; Ahangari, Narges; Hendi, Kasra; Saleh, Fatemeh; Rezaei, Nima

2017-10-26

Autism spectrum disorder (ASD) is a lifelong neurodevelopmental disorder that imposes heavy financial burden on governments and families of affected children. It is considered a multifactorial condition, where trace elements are among environmental factors that may contribute to ASD. Meanwhile, the between-study variance is high. The present systematic review was designed to investigate the difference in trace element measures between patients with ASD and control subjects. Meta-analyses showed that the hair concentrations of chromium (p=0.024), cobalt (p=0.012), iodine (p=0.000), iron (p=0.017), and magnesium (p=0.007) in ASD patients were significantly lower than those of control subjects, while there were higher magnesium levels in the hair of ASD patients compared to that of controls (p=0.010). Patients with ASD had higher blood levels of copper (p=0.000) and lower levels of zinc compared to controls (p=0.021). Further urinary iodine levels in patients with ASD were decreased in comparison with controls (p=0.026). Sensitivity analyses showed that ASD patients in non-Asian but not in Asian countries had lower hair concentrations of chromium compared to controls. Also, such analyses indicated that ASD patients in Asian countries had lower hair zinc concentrations, whereas ASD patients in non-Asian countries had higher hair zinc concentrations in comparison with control subjects. This study found significant differences in the content of trace elements between patients with ASD compared to controls. The findings help highlighting the role of trace elements as environmental factors in the etiology of ASD.

Ferritin-Triggered Redox Cycling for Highly Sensitive Electrochemical Immunosensing of Protein.

PubMed

Akanda, Md Rajibul; Ju, Huangxian

2018-06-04

Electrochemical immunoassay amplified with redox cycling has become a challenging topic in highly sensitive analysis of biomarkers. Here a ferritin-triggered redox cycling is reported by using a highly outersphere reaction-philic (OSR-philic) redox mediator ruthenium hexamine (Ru(NH3)63+) to perform the OSR-philic/innersphere reaction-philic (ISR-philic) controlled signal amplification. The screened mediator can meet the needs of lower E0 than ferritin, low reactivity with ISR-philic species, and quick electron exchange with ferritin redox couple. The ferritin-labeled antibody is firstly bounded to immunosensor surface by recognizing the target antigen capured by the immobilized primary antibody. The ferritin then mediates OSR-philic/ISR-philic transfer from Ru(NH3)63+/2+/immunosensor to ferritin-H2O2 redox system. The fast mediation and excellent resistant of highly OSR-philic Ru(NH3)63+ against radical oxygen species lead to highly sensitive electrochemical readout and high signal-to-background ratio. The proposed redox cycling greatly enhances the readout signal and the sensitivity of traditional ferritin-labelled sandwich immunoassay. Using Enteropathogenic Coli (E. Coli) antigen as a model analyte, the developed method shows excellent linearity over the concentration range from 10.0 pg/mL to 0.1 µg/mL and a detection limit of 10.0 fg/mL. The acceptable accuracy, good reproducibility and selectivity of the proposed immunoassay method in real samples indicate the superior practicability of the ferritin-triggered redox cycling.

Essential trace elements in amyotrophic lateral sclerosis (ALS): Results in a population of a risk area of Italy.

PubMed

Forte, Giovanni; Bocca, Beatrice; Oggiano, Riccardo; Clemente, Simonetta; Asara, Yolande; Sotgiu, Maria Alessandra; Farace, Cristiano; Montella, Andrea; Fois, Alessandro Giuseppe; Malaguarnera, Michele; Pirina, Pietro; Madeddu, Roberto

2017-09-01

Sardinian (Italy) island population has a uniquely high incidence of amyotrophic lateral sclerosis (ALS). Essential trace element levels in blood, hair, and urine of ALS Sardinian patients were investigated in search of valid biomarkers to recognize and predict ALS. Six elements (Ca, Cu, Fe, Mg, Se, and Zn) were measured in 34 patients compared to 30 age- and sex-matched healthy controls by a validated method. Levels of Ca and Cu in blood and of Se and Zn in hair were significantly higher in ALS than in controls, while urinary excretion of Mg and Se was significantly decreased. The selected cut-off concentrations for these biomarkers may distinguish patients with or without ALS with sufficient sensitivity and specificity. Many positive (as Se-Cu and Se-Zn) and negative associations (as Ca-Mg and Ca-Zn) between elements suggested that multiple metals involved in multiple mechanisms have a role in the ALS degeneration.

Serum trace elements in obese women with or without diabetes

PubMed Central

Yerlikaya, F. Hümeyra; Toker, Aysun; Arıbaş, Alpay

2013-01-01

Background & objectives: Relationship of trace elements with obesity and diabetes is complex, alterations in their metabolism can be induced by the diseases and their complications. To study the role of the trace elements in diabetes and obesity, serum trace elements levels (Cr, Se, Fe, Zn, Cu and Mn) were measured in obese women with or without diabetes as well as healthy women. Further, correlation between serum trace elements levels and glucose, insulin, homeostasis model assessment (HOMA-IR), glycated haemoglobin (HbA1c), body mass index (BMI), waist circumferences, waist -to -hip ratio and high-sensitivity C-reactive protein(hsCRP) were also determined in these women. Methods: This study was performed with morbidly obese (BMI >40 kg/m2) women with diabetes (n=41), without diabetes (n=45) and 50 healthly non obese women. Anthropometric measurements were taken and levels of serum Zn, Cr, Fe Cu and Mn were determined. Biochemical parameters included serum glucose, insulin, lipids, haemoglobin, hsCRP and HbA1C. Results: The levels of Zn (P<0.001), Mn (P<0.05), Fe (P<0.05) were significantly lower and the level of Cu (P<0.001) and Cu / Zn ratio (P<0.05) were significantly higher in the diabetic obese women than those of the healthy women. Also, the levels of Zn and Fe were significantly lower and the levels of Cu were significantly higher in the non diabetic obese women than those of the healthy group. Serum Zn levels negatively and serum Cu levels positively correlated with anthropometric values in diabetic and non diabetic obese women. Further, serum Zn, Mn and Cr levels negatively correlated and serum Se levels positively correlated glycaemia control parameters in diabetic obese women. In addition, serum Zn levels negatively correlated with hsCRP in diabetic and nondiabetic obese females. Interpretation & conclusions: Our findings showed significant association between Zn and Fe deficiencies and obesity. Also, obese women with diabetes may be at a greater risk of developing imbalances and deficiencies of trace elements compared with obese women without diabetes. PMID:23563378

A city scale study on the effects of intensive groundwater heat pump systems on heavy metal contents in groundwater.

PubMed

García-Gil, Alejandro; Epting, Jannis; Garrido, Eduardo; Vázquez-Suñé, Enric; Lázaro, Jesús Mateo; Sánchez Navarro, José Ángel; Huggenberger, P; Calvo, Miguel Ángel Marazuela

2016-12-01

As a result of the increasing use of shallow geothermal resources, hydraulic, thermal and chemical impacts affecting groundwater quality can be observed with ever increasing frequency (Possemiers et al., 2014). To overcome the uncertainty associated with chemical impacts, a city scale study on the effects of intensive geothermal resource use by groundwater heat pump systems on groundwater quality, with special emphasis on heavy metal contents was performed. Statistical analysis of geochemical data obtained from several field campaigns has allowed studying the spatiotemporal relationship between temperature anomalies in the aquifer and trace element composition of groundwater. The relationship between temperature and the concentrations of trace elements resulted in weak correlations, indicating that temperature changes are not the driving factor in enhancing heavy metal contaminations. Regression models established for these correlations showed a very low reactivity or response of heavy metal contents to temperature changes. The change rates of heavy metal contents with respect to temperature changes obtained indicate a low risk of exceeding quality threshold values by means of the exploitation regimes used, neither producing nor enhancing contamination significantly. However, modification of pH, redox potential, electrical conductivity, dissolved oxygen and alkalinity correlated with the concentrations of heavy metals. In this case, the change rates of heavy metal contents are higher, with a greater risk of exceeding threshold values. Copyright © 2016 Elsevier B.V. All rights reserved.

New data concerning the geochemistry of unconsolidated sediments collected from the anoxic zone of the Black Sea

NASA Astrophysics Data System (ADS)

Duliu, Octavian G.; Cristache, Carmen; Florea, Nelida; Oaie, Gheorghe; Culicov, Otilia A.; Frontasyeva, Marina V.

2010-05-01

The content of eight major, rock forming elements (Na, Cl, Al, Si, K, Ca, Ti, Fe) and 34 trace elements (B, S, Sc, V, Cr, Mn, Co, Ni, Zn, As, Se, Br, Rb, Sr, Zr, Mo, Sn, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Hf, Ta, W, Th and U) were determined by Prompt Gamma and Epithermal Neutron Activation Analysis in 45 samples of the uppermost 50 cm of undisturbed sediments collected from an anoxic continental zone of the Black Sea at a depth of 600 m, off the City of Constanta. 137Cs geochronology has evidenced a sedimentation ratio of 0,42 ± 0,12 mm/y which, by extrapolation to the entire 50 cm column gave an age of 1300 ± 300 y for the oldest sediments. Principal Component Analysis (PCA), Sc-La-Th and Co-Hf-Th ternary diagrams as well as La/Th ratio were used to interpret these data in correlation with the corresponding ones for the Upper Continental Crust (UCC), North American Shale Composite (NASC), as well as Atlantic, Pacific and Indian MORBs. At the same time the Se/Al, Se/Sc, Se/Mn, Mo/Al, Mo/Sc and Mo/Mn, ratios were used as indicators for anoxic conditions along sedimentary core. Major components distribution showed, that excepting CaO, their contents are very close to UCC and NASC, while the Principal Component Analysis evidenced three clusters consisting of Na, K and Cl, Al, Ti and Fe and respectively Ca, in concordance with the sediments' mineralogical composition. The Trace Elements Distribution was also close to UCC except for redox sensitive metals Se and Mo whose contents were 10 to 100 times higher than the corresponding UCC ones, this fact reflecting the anoxic conditions along the entire column of sediments. Moreover, by using Se and Mo as proxies for an anoxic environment, we estimated a relative consistency of the local conditions for a period between 350 ± 60 and 1300 ± 300 BP followed by a more fluctuant one during the last 300 years, this peculiarity also being confirmed by PCA, as well as by the vertical distribution of La/Th ratio. A chondrite normalized plot of nine Rare Earth Elements (La, Ne, Nd, Sm, Eu, Gd, Tb, Dy and Yb) showed the presence of a weak Ce positive anomaly, explained by the existing anoxic environment as well as a significant Eu negative anomaly, confirming the continental origin of the sedimentary material.

Numerical simulation of trace element transport on subsurface environment pollution in coal mine spoil.

PubMed

Qiang, Xue; Bing, Liang; Hui-yun, Wang; Lei, Liu

2006-01-01

An understanding of the dynamic behavior of trace elements leaching from coal mine spoil is important in predicting the groundwater quality. The relationship between trace element concentrations and leaching times, pH values of the media is studied. Column leaching tests conducted in the laboratory showed that there was a close correlation between pH value and trace element concentrations. The longer the leaching time, the higher the trace element concentrations. Different trace elements are differently affected by pH values of leaching media. A numerical model for water flow and trace element transport has been developed based on analyzing the characteristics of migration and transformation of trace elements leached from coal mine spoil. Solutions to the coupled model are accomplished by Eulerian-Lagrangian localized adjoint method. Numerical simulation shows that rainfall intensity determined maximum leaching depth. As rainfall intensity is 3.6ml/s, the outflow concentrations indicate a breakthrough of trace elements beyond the column base, with peak concentration at 90cm depth. And the subsurface pollution range has a trend of increase with time. The model simulations are compared to experimental results of trace element concentrations, with reasonable agreement between them. The analysis and modeling of trace elements suggested that the infiltration of rainwater through the mine spoil might lead to potential groundwater pollution. It provides theoretical evidence for quantitative assessment soil-water quality of trace element transport on environment pollution.

Trace elements in fish from Taihu Lake, China: levels, associated risks, and trophic transfer.

PubMed

Hao, Ying; Chen, Liang; Zhang, Xiaolan; Zhang, Dongping; Zhang, Xinyu; Yu, Yingxin; Fu, Jiamo

2013-04-01

Concentrations of eight trace elements [iron (Fe), manganese (Mn), zinc (Zn), chromium (Cr), mercury (Hg), cadmium (Cd), lead (Pb), and arsenic (As)] were measured in a total of 198 samples covering 24 fish species collected from Taihu Lake, China, in September 2009. The trace elements were detected in all samples, and the total mean concentrations ranged from 18.2 to 215.8 μg/g dw (dry weight). The concentrations of the trace elements followed the sequence of Zn>Fe>Mn>Cr>As>Hg>Pb>Cd. The measured trace element concentrations in fish from Taihu Lake were similar to or lower than the reported values in fish around the world. The metal pollution index was used to compare the total trace element accumulation levels among various species. Toxabramis swinhonis (1.606) accumulated the highest level of the total trace elements, and Saurogobio dabryi (0.315) contained the lowest. The concentrations of human non-essential trace elements (Hg, Cd, Pb, and As) were lower than the allowable maximum levels in fish in China and the European Union. The relationships between the trace element concentrations and the δ(15)N values of fish species were used to investigate the trophic transfer potential of the trace elements. Of the trace elements, Hg might be biomagnified through the food chain in Taihu Lake if the significant level of p-value was set at 0.1. No biomagnification and biodilution were observed for other trace elements. Copyright © 2012 Elsevier Inc. All rights reserved.

Interplay between Selenium Levels, Selenoprotein Expression, and Replicative Senescence in WI-38 Human Fibroblasts*

PubMed Central

Legrain, Yona; Touat-Hamici, Zahia; Chavatte, Laurent

2014-01-01

Selenium is an essential trace element, which is incorporated as selenocysteine into at least 25 selenoproteins using a unique translational UGA-recoding mechanism. Selenoproteins are important enzymes involved in antioxidant defense, redox homeostasis, and redox signaling pathways. Selenium levels decline during aging, and its deficiency is associated with a marked increase in mortality for people over 60 years of age. Here, we investigate the relationship between selenium levels in the culture medium, selenoprotein expression, and replicative life span of human embryonic lung fibroblast WI-38 cells. Selenium levels regulate the entry into replicative senescence and modify the cellular markers characteristic for senescent cells. Whereas selenium supplementation extends the number of population doublings, its deficiency impairs the proliferative capacity of WI-38 cells. We observe that the expression of several selenoproteins involved in antioxidant defense is specifically affected in response to cellular senescence. Their expression is selectively controlled by the modulation of mRNA levels and translational recoding efficiencies. Our data provide novel mechanistic insights into how selenium impacts the replicative life span of mammalian cells by identifying several selenoproteins as new targets of senescence. PMID:24425862

First-principles calculations of the thermodynamic properties of transuranium elements in a molten salt medium

NASA Astrophysics Data System (ADS)

Noh, Seunghyo; Kwak, Dohyun; Lee, Juseung; Kang, Joonhee; Han, Byungchan

2014-03-01

We utilized first-principles density-functional-theory (DFT) calculations to evaluate the thermodynamic feasibility of a pyroprocessing methodology for reducing the volume of high-level radioactive materials and recycling spent nuclear fuels. The thermodynamic properties of transuranium elements (Pu, Np and Cm) were obtained in electrochemical equilibrium with a LiCl-KCl molten salt as ionic phases and as adsorbates on a W(110) surface. To accomplish the goal, we rigorously calculated the double layer interface structures on an atomic resolution, on the thermodynamically most stable configurations on W(110) surfaces and the chemical activities of the transuranium elements for various coverages of those elements. Our results indicated that the electrodeposition process was very sensitive to the atomic level structures of Cl ions at the double-layer interface. Our studies are easily expandable to general electrochemical applications involving strong redox reactions of transition metals in non-aqueous solutions.

Micron to Mine: Synchrotron Science for Mineral Exploration, Production, and Remediation

NASA Astrophysics Data System (ADS)

Banerjee, N.; Van Loon, L.; Flynn, T.

2017-12-01

Synchrotron science for mineral exploration, production, and remediation studies is a powerful tool that provides industry with relevant micron to macro geochemical information. Synchrotron micro X-ray fluorescence (SR-µXRF) offers a direct, high-resolution, rapid, and cost-effective chemical analysis while preserving the context of the sample by mapping ore minerals with ppm detection limits. Speciation of trace and deleterious elements can then be probed using X-ray absorption near-edge structure (XANES) spectroscopy. Large-scale (tens of cm) µXRF mapping and XANES analysis of samples collected at various mine locations have been undertaken to address questions regarding mineralization history to develop novel trace element exploration vectors. This information provides integral insights into trace element associations with ore minerals, local redox conditions responsible for mineralization, and mineralizing mechanisms. Gold is commonly intimately associated with sulfide mineralization (e.g., pyrite, arsenopyrite, etc.) and is present both as inclusions and filling fractures in sulfide grains. Gold may also occur as nanoparticles and/or in the sulfide mineral crystal lattice, known as "invisible gold". Understanding the nature and distribution of invisible gold in ore is integral to processing efficiency. The high flux and energy of a synchrotron light source allows for the detection of invisible gold by µXRF, and can probe its nature (metallic Au0 vs. lattice bound Au1+) using XANES spectroscopy. The long-term containment and management of arsenic is necessary to protect the health of both humans and the environment. Understanding the relationship of arsenic mineralization to gold deposits can lead to more sophisticated planning for mineral processing and the eventual storage of gangue materials. µXANES spectroscopy is an excellent tool for determining arsenic speciation within the context of the sample. Mineral phases such as arsenopyrite, scorodite, and arsenic trioxide can be accurately identified as well as relative amounts determined. With this information the oxidation-reduction of arsenic-bearing compounds can be monitored to optimize management practices for the long-term capture of arsenic contaminants.

Determination of elemental content off rocks by laser ablation inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Lichte, F.E.

1995-01-01

A new method of analysis for rocks and soils is presented using laser ablation inductively coupled plasma mass spectrometry. It is based on a lithium borate fusion and the free-running mode of a Nd/YAG laser. An Ar/N2 sample gas improves sensitivity 7 ?? for most elements. Sixty-three elements are characterized for the fusion, and 49 elements can be quantified. Internal standards and isotopic spikes ensure accurate results. Limits of detection are 0.01 ??g/g for many trace elements. Accuracy approaches 5% for all elements. A new quality assurance procedure is presented that uses fundamental parameters to test relative response factors for the calibration.

Effects of field-realistic doses of glyphosate on honeybee appetitive behaviour.

PubMed

Herbert, Lucila T; Vázquez, Diego E; Arenas, Andrés; Farina, Walter M

2014-10-01

Glyphosate (GLY) is a broad-spectrum herbicide used for weed control. The sub-lethal impact of GLY on non-target organisms such as insect pollinators has not yet been evaluated. Apis mellifera is the main pollinator in agricultural environments and is a well-known model for behavioural research. Honeybees are also accurate biosensors of environmental pollutants and their appetitive behavioural response is a suitable tool with which to test sub-lethal effects of agrochemicals. We studied the effects of field-realistic doses of GLY on honeybees exposed chronically or acutely to the herbicide. We focused on sucrose sensitivity, elemental and non-elemental associative olfactory conditioning of the proboscis extension response (PER), and foraging-related behaviour. We found a reduced sensitivity to sucrose and learning performance for the groups chronically exposed to GLY concentrations within the range of recommended doses. When olfactory PER conditioning was performed with sucrose reward with the same GLY concentrations (acute exposure), elemental learning and short-term memory retention decreased significantly compared with controls. Non-elemental associative learning was also impaired by an acute exposure to GLY traces. Altogether, these results imply that GLY at concentrations found in agro-ecosystems as a result of standard spraying can reduce sensitivity to nectar reward and impair associative learning in honeybees. However, no effect on foraging-related behaviour was found. Therefore, we speculate that successful forager bees could become a source of constant inflow of nectar with GLY traces that could then be distributed among nestmates, stored in the hive and have long-term negative consequences on colony performance. © 2014. Published by The Company of Biologists Ltd.

Biogeochemical Gradients in Wetland Sediments and their Effect on the Fate Trace Metals

NASA Astrophysics Data System (ADS)

Jaffe, P. R.; Choi, J.; Xu, S.

2005-12-01

The interactions between sediment biogeochemistry processes and higher plants play a major role on trace metal mobility in wetlands. Most wetland sediments are characterized by steep redox gradients, resulting from the sequential utilization of different electron acceptors during the degradation of organic matter provided by leaf litter and root turnover. Metals in wetland sediments may be immobilized due to precipitation or adsorption to different organic and inorganic sediment constituents. Adsorption onto iron, and manganese oxides, are important in the rhizosphere where iron oxyhydroxide plaques may form on the surface of roots. As the sediments becomes more reduced, bioavailable iron and manganese oxides are used as electron acceptor and are gradually depleted, resulting in the mobilization of some adsorbed species (i.e., As(V), phosphate, etc.), the reduction of some trace metals such as Cr(VI) (which is then immobilized as Cr(III)), and for more reduced conditions the immobilization of trace metals (i.e., Cd, Pb, Zn) as sulfides. Results from numerical simulations, laboratory experiments, and field measurements will be presented, showing how redox gradients and hence, trace-metal immobilization, in wetlands respond to external forcing functions such as changes in nutrient loading, plant distribution, seasonal and diurnal plant activity (specifically evapotranspiration and oxygen release), and temporal or spatial changes in the profile of iron and manganese oxides.

Application of the flow-through time-resolved analysis technique to trace element determination in ostracod shells

NASA Astrophysics Data System (ADS)

Börner, Nicole; De Baere, Bart; Francois, Roger; Frenzel, Peter; Schwalb, Antje

2014-05-01

Trace element analyses of ostracod shells are a vital tool for paleoenvironmental reconstructions from lake sediments (Börner et al., 2013). Conventional batch dissolution ICP-MS is the most common way for analyzing trace elements in ostracod shells. However, due to dissolution or secondary overgrowth the primary signal may be masked. Resulting variations in trace element composition have been identified to be in the order of a magnitude range. Therefore, the application of the newly developed flow-through technique will be assessed. The flow-through time-resolved analysis technique allows to chemically separate mineral phases of different solubility such as, in particular, original shell calcite from overgrowth calcite, and thus to correct the measurements for the biogenic signal. During a flow-through experiment, eluent is continuously pumped through a sample column, typically a filter in which the ostracod valves are loaded. The gradual dissolution of the substrate is controlled by a combination of eluent type, eluent temperature and eluent flow rate. The dissolved sample then flows directly to a mass spectrometer. The resulting data is a chromatogram, featuring different mineral phases dissolving as time progresses. Hence, the flow-through technique provides a detailed geochemical fingerprint of the substrate and therefore additional data relative to conventional methods. To calibrate this technique for the application to ostracods we use ostracod shells from Southern Tibetan Plateau lakes, which feature an alkaline environment but show highly diverse hydrochemistry. Cleaned as well as uncleaned ostracod shells show similarity in their trace element signals, allowing measurements without prior cleaning of the shells, and thus more time-efficient sample throughput. Measurements of unclean shells are corrected for the biogenic signal using an equation from Klinkhammer et al. (2004). Another advantage is that the measurements can be carried out on single ostracod shells, as not every single sediment sample contains enough adult intact specimens of all required genera, making batch cleaning dissolution impossible. The flow-through time-resolved analysis technique gives an accurate and high-resolution dataset. The trace elemental data for living ostracods compared to the hydrological data from each sampling site provides a calibration dataset for further hydrological and thus climatological reconstruction of a sediment core from Nam Co. Mg/Ca and Sr/Ca ratios in ostracod shells will provide information about past water temperature and salinity resulting from changes in precipitation vs. evaporation ratios and monsoon activity. Further, we will exploit Mn/Ca, Fe/Ca and U/Ca ratios as redox indicators to reconstruct oxygenation cycles and Ba/Ca ratios to detect changes in productivity and/or salinity. This reconstruction should provide a more extensive insight in past climatic change, e.g. precipitation - evaporation balance, lake level and circulation changes, and the recording of environmental signatures by ostracod shells. Börner, N., De Baere, B., Yang, Q., Jochum, K.P., Frenzel, P., Andreae, M.O., Schwalb, A., 2013. Ostracod shell chemistry as proxy for paleoenvironmental change. Quaternary International 313-314, 17-37. Klinkhammer, G.P., Haley, B.A., Mix, A.C., Benway, H., Cheseby, M., 2004. Evaluation of automated flow-through time-resolved analysis of foraminifera for Mg/Ca paleothermometry. Paleoceanography 19, PA4030.

Trace element distribution in the rat cerebellum

NASA Astrophysics Data System (ADS)

Kwiatek, W. M.; Long, G. J.; Pounds, J. G.; Reuhl, K. R.; Hanson, A. L.; Jones, K. W.

1990-04-01

Spatial distributions and concentrations of trace elements (TE) in the brain are important because TE perform catalytic and structural functions in enzymes which regulate brain function and development. We have investigated the distributions of TE in rat cerebellum. Structures were sectioned and analyzed by the Synchrotron Radiation Induced X-ray Emission (SRIXE) method using the NSLS X-26 white-light microprobe facility. Advantages important for TE analysis of biological specimens with X-ray microscopy include short time of measurement, high brightness and flux, good spatial resolution, multielemental detection, good sensitivity, and nondestructive irradiation. Trace elements were measured in thin rat brain sections of 20 μm thickness. The analyses were performed on sample volumes as small as 0.2 nl with Minimum Detectable Limits (MDL) of 50 ppb wet weight for Fe, 100 ppb wet weight for Cu, and Zn, and 1 ppm wet weight for Pb. The distribution of TE in the molecular cell layer, granule cell layer and fiber tract of rat cerebella was investigated. Both point analyses and two-dimensional semiquantitative mapping of the TE distribution in a section were used. All analyzed elements were observed in each structure of the cerebellum except mercury which was not observed in granule cell layer or fiber tract. This approach permits an exacting correlation of the TE distribution in complex structure with the diet, toxic elements, and functional status of the animal.

Recycling of trace elements required for humans in CELSS.

PubMed

Ashida, A

1994-11-01

Recycle of complete nourishment necessary for human should be constructed in CELSS (Controlled Ecological Life Support Systems). Essential elements necessary for human support are categorized as major elements, semi-major elements and trace elements. Recently, trace elements have been identified from considerations of local diseases, food additive problems, pollution problems and adult diseases, consisting of Fe, Zn, Cu, Se, Co, F, Si, Mn, Cr, I, As, Mo, Ni, V, Sn, Li, Br, Cd, Pb, B. A review of the biogeochemical history of the earth's biosphere and the physiological nature of humans and plants explains some of the requirements. A possible route for intake of trace elements is considered that trace elements are dissolved in some chemical form in water, absorbed by plants through their roots and then transfered to human as foods. There may be a possibility that living things absorb some trace elements from atmosphere. Management and recycling of trace elements in CELSS is discussed.

Recycling of trace elements required for humans in CELSS

NASA Astrophysics Data System (ADS)

Ashida, A.

1994-11-01

Recycle of complete nourishment necessary for human should be constructed in CELSS (Controlled Ecological Life Support Systems). Essential elements necessary for human support are categorized as major elements, semi-major elements and trace elements. Recently, trace elements have been identified from considerations of local diseases, food additive problems, pollution problems and adult diseases, consisting of Fe, Zn, Cu, Se, Co, F, Si, Mn, Cr, I, As, Mo, Ni, V, Sn, Li, Br, Cd, Pb, B. A review of the biogeochemical history of the earth's biosphere and the physiological nature of humans and plants explains some of the requirements. A possible route for intake of trace elements is considered that trace elements are dissolved in some chemical form in water, absorbed by plants through their roots and then transfered to human as foods. There may be a posibility that living things absorb some trace elements from atmosphere. Management and recycling of trace elements in CELSS is discussed.

Scaling up in the face of uncertainty - controls on trace gas fluxes in heterogeneous landscapes (Invited)

NASA Astrophysics Data System (ADS)

Bernhardt, E. S.; Helton, A. M.; Morse, J. L.; Poole, G. C.

2013-12-01

Wetlands are the dominant natural source of methane to the global atmosphere and can be important sites of either N2O emission or consumption. Changes in the spatial extent or inundation frequency and duration may lead to substantial shifts in the contribution of wetland ecosystems to global CH4 and N2O emissions. Trace gases are produced at the scale of individual microbes, each of which respond dynamically to the local availability of electron donors and acceptors. Within landscape patches, substrate supply and redox conditions are strongly controlled by variation in water table elevation and vertical hydrologic exchange. At the landscape scale, lateral exchange between patches and the extent and duration of inundation. Accurate estimates of trace gas emissions from wetlands are hard to estimate given the dynamic patterns of redox potential within the soil column and across the landscape that redistribute electron donors and acceptors both vertically and laterally. In five years of trace gas flux measurement and modeling at TOWER, a 440 ha restored wetland in coastal NC, we have developed both simulation and statistical models to estimate landscape level trace gas fluxes. Yet, because trace gas emissions are highly variable in both time and space, our qualitative and quantitative attempts at upscaling trace gas emissions typically generate estimates with extremely high uncertainty. In this talk we will explore the challenges inherent to the estimation of landscape scale trace gas fluxes at the scale of our individual ecosystem as well as the difficulties in extrapolating across multiple ecosystem studies.

The role of the seagrass Posidonia oceanica in the cycling of trace elements

NASA Astrophysics Data System (ADS)

Sanz-Lázaro, C.; Malea, P.; Apostolaki, E. T.; Kalantzi, I.; Marín, A.; Karakassis, I.

2012-03-01

The aim of this work was to study the role of the seagrass Posidonia oceanica on the cycling of a wide set of trace elements (Ag, As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Fe, Ga, Li, Mn, Ni, Pb, Rb, Sr, Tl, V and Zn). We measured the concentration of these trace elements in the different compartments of P. oceanica (leaves, rhizomes, roots and epibiota) in a non-polluted seagrass meadow representative of the Mediterranean and calculated the annual budget from a mass balance. We provide novel data on accumulation dynamics of many trace elements in P. oceanica compartments and demonstrate that trace element accumulation patterns are mainly determined by plant compartment rather than by temporal variability. Epibiota was the compartment which showed the greatest concentrations for most trace elements. Thus, they constitute a key compartment when estimating trace element transfer to higher trophic levels by P. oceanica. For most trace elements, translocation seemed to be low and acropetal. Zn, Cd, Sr and Rb were the trace elements that showed the highest release rate through decomposition of plant detritus, while Cs, Tl and Bi the lowest. P. oceanica acts as a sink of potentially toxic trace elements (Ni, Cr, As and Ag), which can be sequestered, decreasing their bioavailability. P. oceanica may have a relevant role in the cycling of trace elements in the Mediterranean.

The role of the seagrass Posidonia oceanica in the cycling of trace elements

NASA Astrophysics Data System (ADS)

Sanz-Lázaro, C.; Malea, P.; Apostolaki, E. T.; Kalantzi, I.; Marín, A.; Karakassis, I.

2012-07-01

The aim of this study was to investigate the role of the seagrass Posidonia oceanica on the cycling of a wide set of trace elements (Ag, As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Fe, Ga, Li, Mn, Ni, Pb, Rb, Sr, Tl, V and Zn). We measured the concentration of these trace elements in different compartments of P. oceanica (leaves, rhizomes, roots and epiphytes) in a non-polluted seagrass meadow representative of the Mediterranean and calculated the annual budget from a mass balance. We provide novel data on accumulation dynamics of many trace elements in P. oceanica compartments and demonstrate that trace element accumulation patterns are mainly determined by plant compartment rather than by temporal variability. Epiphytes were the compartment, which showed the greatest concentrations for most trace elements. Thus, they constitute a key compartment when estimating trace element transfer to higher trophic levels by P. oceanica. Trace element translocation in P. oceanica seemed to be low and acropetal in most cases. Zn, Cd, Sr and Rb were the trace elements that showed the highest release rate through decomposition of plant detritus, while Cs, Tl and Bi showed the lowest. P. oceanica acts as a sink of potentially toxic trace elements (Ni, Cr, As and Ag), which can be sequestered, decreasing their bioavailability. P. oceanica may have a relevant role in the cycling of trace elements in the Mediterranean.

Protective effect and mechanism of glutaredoxin 1 on coronary arteries endothelial cells damage induced by high glucose.

PubMed

Li, Shuyan; Sun, Yan; Qi, Xiaodan; Shi, Yan; Gao, Han; Wu, Qi; Liu, Xiucai; Yu, Haitao; Zhang, Chunjing

2014-01-01

In recent years, diabetes and its associated complications have become a major public health concern. The cardiovascular risk increases significantly in diabetes patients. It is a complex disease characterized by multiple metabolic derangements and is known to impair cardiac function by disrupting the balance between pro-oxidants and antioxidants at the cellular level. The subsequent generation of reactive oxygen species (ROS) and accompanying oxidative stress are hallmarks of the molecular mechanisms responsible for cardiovascular disease. Protein thiols act as redox-sensitive switches and are believed to be a key element in maintaining the cellular redox balance. The redox state of protein thiols is regulated by oxidative stress and redox signaling and is important to cellular functions. The potential of the thiol-disulfide oxidoreductase enzymes (thioredoxin and glutaredoxin systems) in defense against oxidative stress has been noted previously. Increasing evidence demonstrates that glutaredoxin 1 (Grx1), a cytosolic enzyme responsible for the catalysis of protein deglutathionylation, plays distinct roles in inflammation and apoptosis by inducing changes in the cellular redox system. This study investigates whether and how Grx1 protects coronary artery vascular endothelial cells against high glucose (HG) induced damage. Results indicate that the activation of eNOS/NO system is regulated by Grx 1 and coupled with inhibition of JNK and NF-κB signaling pathway which could alleviate the oxidative stress and apoptosis damage in coronary arteries endothelial cells induced by HG.

Trace Elements and Healthcare: A Bioinformatics Perspective.

PubMed

Zhang, Yan

2017-01-01

Biological trace elements are essential for human health. Imbalance in trace element metabolism and homeostasis may play an important role in a variety of diseases and disorders. While the majority of previous researches focused on experimental verification of genes involved in trace element metabolism and those encoding trace element-dependent proteins, bioinformatics study on trace elements is relatively rare and still at the starting stage. This chapter offers an overview of recent progress in bioinformatics analyses of trace element utilization, metabolism, and function, especially comparative genomics of several important metals. The relationship between individual elements and several diseases based on recent large-scale systematic studies such as genome-wide association studies and case-control studies is discussed. Lastly, developments of ionomics and its recent application in human health are also introduced.

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

NASA Astrophysics Data System (ADS)

Mercadier, Julien; Cuney, Michel; Cathelineau, Michel; Lacorde, Mathieu

2011-02-01

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation-reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6-1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution-precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400-300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.

Micromechanical potentiometric sensors

DOEpatents

Thundat, Thomas G.

2000-01-01

A microcantilever potentiometric sensor utilized for detecting and measuring physical and chemical parameters in a sample of media is described. The microcantilevered spring element includes at least one chemical coating on a coated region, that accumulates a surface charge in response to hydrogen ions, redox potential, or ion concentrations in a sample of the media being monitored. The accumulation of surface charge on one surface of the microcantilever, with a differing surface charge on an opposing surface, creates a mechanical stress and a deflection of the spring element. One of a multitude of deflection detection methods may include the use of a laser light source focused on the microcantilever, with a photo-sensitive detector receiving reflected laser impulses. The microcantilevered spring element is approximately 1 to 100 .mu.m long, approximately 1 to 50 .mu.m wide, and approximately 0.3 to 3.0 .mu.m thick. An accuracy of detection of deflections of the cantilever is provided in the range of 0.01 nanometers of deflection. The microcantilever apparatus and a method of detection of parameters require only microliters of a sample to be placed on, or near the spring element surface. The method is extremely sensitive to the detection of the parameters to be measured.

Atmospheric transport of trace elements and nutrients to the oceans

PubMed Central

Chance, R.

2016-01-01

This paper reviews atmospheric inputs of trace elements and nutrients to the oceans in the context of the GEOTRACES programme and provides new data from two Atlantic GEOTRACES cruises. We consider the deposition of nitrogen to the oceans, which is now dominated by anthropogenic emissions, the deposition of mineral dust and related trace elements, and the deposition of other trace elements which have a mixture of anthropogenic and dust sources. We then consider the solubility (as a surrogate for bioavailability) of the various elements. We consider briefly the sources, atmospheric transport and transformations of these elements and how this results in strong spatial deposition gradients. Solubility of the trace elements also varies systematically between elements, reflecting their sources and cycling, and for some trace elements there are also systematic gradients in solubility related to dust loading. Together, these effects create strong spatial gradients in the inputs of bioavailable trace elements to the oceans, and we are only just beginning to understand how these affect ocean biogeochemistry. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035252

The role of plant-associated bacteria in the mobilization and phytoextraction of trace elements in contaminated soils

PubMed Central

Sessitsch, Angela; Kuffner, Melanie; Kidd, Petra; Vangronsveld, Jaco; Wenzel, Walter W.; Fallmann, Katharina; Puschenreiter, Markus

2013-01-01

Phytoextraction makes use of trace element-accumulating plants that concentrate the pollutants in their tissues. Pollutants can be then removed by harvesting plants. The success of phytoextraction depends on trace element availability to the roots and the ability of the plant to intercept, take up, and accumulate trace elements in shoots. Current phytoextraction practises either employ hyperaccumulators or fast-growing high biomass plants; the phytoextraction process may be enhanced by soil amendments that increase trace element availability in the soil. This review will focus on the role of plant-associated bacteria to enhance trace element availability in the rhizosphere. We report on the kind of bacteria typically found in association with trace element – tolerating or – accumulating plants and discuss how they can contribute to improve trace element uptake by plants and thus the efficiency and rate of phytoextraction. This enhanced trace element uptake can be attributed to a microbial modification of the absorptive properties of the roots such as increasing the root length and surface area and numbers of root hairs, or by increasing the plant availability of trace elements in the rhizosphere and the subsequent translocation to shoots via beneficial effects on plant growth, trace element complexation and alleviation of phytotoxicity. An analysis of data from literature shows that effects of bacterial inoculation on phytoextraction efficiency are currently inconsistent. Some key processes in plant–bacteria interactions and colonization by inoculated strains still need to be unravelled more in detail to allow full-scale application of bacteria assisted phytoremediation of trace element contaminated soils. PMID:23645938

The role of plant-associated bacteria in the mobilization and phytoextraction of trace elements in contaminated soils.

PubMed

Sessitsch, Angela; Kuffner, Melanie; Kidd, Petra; Vangronsveld, Jaco; Wenzel, Walter W; Fallmann, Katharina; Puschenreiter, Markus

2013-05-01

Phytoextraction makes use of trace element-accumulating plants that concentrate the pollutants in their tissues. Pollutants can be then removed by harvesting plants. The success of phytoextraction depends on trace element availability to the roots and the ability of the plant to intercept, take up, and accumulate trace elements in shoots. Current phytoextraction practises either employ hyperaccumulators or fast-growing high biomass plants; the phytoextraction process may be enhanced by soil amendments that increase trace element availability in the soil. This review will focus on the role of plant-associated bacteria to enhance trace element availability in the rhizosphere. We report on the kind of bacteria typically found in association with trace element - tolerating or - accumulating plants and discuss how they can contribute to improve trace element uptake by plants and thus the efficiency and rate of phytoextraction. This enhanced trace element uptake can be attributed to a microbial modification of the absorptive properties of the roots such as increasing the root length and surface area and numbers of root hairs, or by increasing the plant availability of trace elements in the rhizosphere and the subsequent translocation to shoots via beneficial effects on plant growth, trace element complexation and alleviation of phytotoxicity. An analysis of data from literature shows that effects of bacterial inoculation on phytoextraction efficiency are currently inconsistent. Some key processes in plant-bacteria interactions and colonization by inoculated strains still need to be unravelled more in detail to allow full-scale application of bacteria assisted phytoremediation of trace element contaminated soils.

Microbial biofilms control economic metal mobility in an acid-sulfate hydrothermal system

NASA Astrophysics Data System (ADS)

Phillips-Lander, C. M.; Roberts, J. A.; Hernandez, W.; Mora, M.; Fowle, D. A.

2012-12-01

Trace metal cycling in hydrothermal systems has been the subject of a variety of geochemical and economical geology studies. Typically in these settings these elements are sequestered in sulfide and oxide mineral fractions, however in near-surface low-temperature environments organic matter and microorganisms (typically in mats) have been implicated in their mobility through sorption. Here we specifically examine the role of microbial biofilms on metal partitioning in an acid-sulfate hydrothermal system. We studied the influence of microorganisms and microbial biofilms on trace metal adsorption in Pailas de Aguas I, an acid-sulfate hot spring on the southwest flank of Rincon de la Vieja, a composite stratovolcano in the Guanacaste Province, Costa Rica. Spring waters contain high suspended loads, and are characterized by high T (79.6-89.3oC), low pH (2.6-4), and high ionic strengths (I= 0.5-0.8). Waters contain high concentrations of the biogeochemically active elements Fe (4-6 mmol/l) and SO42- (38 mmol/l), but PO43- are below detection limits (bdl). Silver, Ni, and Mo concentrations are bdl; however other trace metals are present in solution in concentrations of 0.1-0.2 mg/l Cd, 0.2-0.4 mg/l Cr and V, 0.04-1 mg/l Cu,. Preliminary 16S rRNA analyses of microorganisms in sediments reveal several species of algae, including Galderia sp., Cyanidium sp, γ-proteobacteria, Acidithiobacillus caldus, Euryarcheota, and methanogens. To evaluate microbial biofilms' impact on trace metal mobility we analyzed a combination of suspended, bulk and biofilm associated sediment samples via X-ray diffraction (XRD) and trace element sequential extractions (SE). XRD analysis indicated all samples were primarily composed of Fe/Al clay minerals (nontronite, kaolinite), 2- and 6-line ferrihydrite, goethite, and hematite, quartz, and opal-α. SE showed the highest concentrations of Cu, Mo, and V were found in the suspended load. Molybdenum was found primarily in the residual and organic fractions of suspended sediments. Copper is distributed in all but the carbonate fraction of suspended sediments. Vanadium was bound primarily to the oxide and residual fractions with Si, which is probably found as opal-α. In contrast, biofilm sediments had the highest concentrations of Fe, Si, Cd, Al, Zn, Ag, and Ni. Trace metals were sequestered mainly in the organic fraction in decreasing concentrations of: Cu

Reoxidation of estuarine sediments during simulated resuspension events: Effects on nutrient and trace metal mobilisation

NASA Astrophysics Data System (ADS)

Vidal-Durà, Andrea; Burke, Ian T.; Stewart, Douglas I.; Mortimer, Robert J. G.

2018-07-01

Estuarine environments are considered to be nutrient buffer systems as they regulate the delivery of nutrients from rivers to the ocean. In the Humber Estuary (UK) seawater and freshwater mixing during tidal cycles leads to the mobilisation of oxic surface sediments (0-1 cm). However, less frequent seasonal events can also mobilise anoxic subsurface (5-10 cm) sediments, which may have further implications for the estuarine geochemistry. A series of batch experiments were carried out on surface and subsurface sediments taken from along the salinity gradient of the Humber Estuary. The aim was to investigate the geochemical processes driving major element (N, Fe, S, and Mn) redox cycling and trace metal behaviour during simulated resuspension events. The magnitude of major nutrient and metal release was significantly greater during the resuspension of outer estuarine sediments rather than from inner estuarine sediments. When comparing resuspension of surface versus subsurface sediment, only the outer estuary experiments showed significant differences in major nutrient behaviour with sediment depth. In general, any ammonium, manganese and trace metals (Cu and Zn) released during the resuspension experiments were rapidly removed from solution as new sorption sites (i.e. Fe/Mn oxyhydroxides) formed. Therefore Humber estuary sediments showed a scavenging capacity for these dissolved species and hence may act as an ultimate sink for these elements. Due to the larger aerial extent of the outer estuary intertidal mudflats in comparison with the inner estuary area, the mobilisation of the outer estuary sediments (more reducing and richer in sulphides and iron) may have a greater impact on the transport and cycling of nutrients and trace metals. Climate change-associated sea level rise combined with an increasing frequency of major storm events in temperate zones, which are more likely to mobilise deeper sediment regions, will impact the nutrient and metal inputs to the coastal waters, and therefore enhance the likelihood of eutrophication in this environment.

Thioredoxin and Thioredoxin Target Proteins: From Molecular Mechanisms to Functional Significance

PubMed Central

Lee, Samuel; Kim, Soo Min

2013-01-01

Abstract The thioredoxin (Trx) system is one of the central antioxidant systems in mammalian cells, maintaining a reducing environment by catalyzing electron flux from nicotinamide adenine dinucleotide phosphate through Trx reductase to Trx, which reduces its target proteins using highly conserved thiol groups. While the importance of protecting cells from the detrimental effects of reactive oxygen species is clear, decades of research in this field revealed that there is a network of redox-sensitive proteins forming redox-dependent signaling pathways that are crucial for fundamental cellular processes, including metabolism, proliferation, differentiation, migration, and apoptosis. Trx participates in signaling pathways interacting with different proteins to control their dynamic regulation of structure and function. In this review, we focus on Trx target proteins that are involved in redox-dependent signaling pathways. Specifically, Trx-dependent reductive enzymes that participate in classical redox reactions and redox-sensitive signaling molecules are discussed in greater detail. The latter are extensively discussed, as ongoing research unveils more and more details about the complex signaling networks of Trx-sensitive signaling molecules such as apoptosis signal-regulating kinase 1, Trx interacting protein, and phosphatase and tensin homolog, thus highlighting the potential direct and indirect impact of their redox-dependent interaction with Trx. Overall, the findings that are described here illustrate the importance and complexity of Trx-dependent, redox-sensitive signaling in the cell. Our increasing understanding of the components and mechanisms of these signaling pathways could lead to the identification of new potential targets for the treatment of diseases, including cancer and diabetes. Antioxid. Redox Signal. 18, 1165–1207. PMID:22607099

The effects of chromium(VI) on the thioredoxin system: Implications for redox regulation

PubMed Central

Myers, Charles R.

2014-01-01

Hexavalent chromium [Cr(VI)] compounds are highly redox active and have long been recognized as potent cytotoxins and carcinogens. The intracellular reduction of Cr(VI) generates reactive Cr intermediates, which are themselves strong oxidants, as well as superoxide, hydrogen peroxide, and hydroxyl radical. These probably contribute to the oxidative damage and effects on redox-sensitive transcription factors that have been reported. However, the identification of events that initiate these signaling changes has been elusive. More recent studies show that Cr(VI) causes irreversible inhibition of thioredoxin reductase (TrxR) and oxidation of thioredoxin (Trx) and peroxiredoxin (Prx). Mitochondrial Trx2/Prx3 are more sensitive to Cr(VI) treatment than cytosolic Trx1/Prx1, although both compartments show thiol oxidation with higher doses or longer treatments. Thiol redox proteomics demonstrate that Trx2, Prx3, and Trx1 are among the most sensitive proteins in cells to Cr(VI) treatment. Their oxidation could therefore represent initiating events that have widespread implications for protein thiol redox control and for multiple aspects of redox signaling. This review summarizes the effects of Cr(VI) on the TrxR/Trx system and how these events could influence a number of downstream redox signaling systems that are influenced by Cr(VI) exposure. Some of the signaling events discussed include the activation of apoptosis signal regulating kinase and MAP kinases (p38 and JNK) and the modulation of a number of redox-sensitive transcription factors including AP-1, NF-κB, p53, and Nrf2. PMID:22542445

Trace Elements and Carbon and Nitrogen Stable Isotopes in Organisms from a Tropical Coastal Lagoon

PubMed Central

van Hattum, B.; de Boer, J.; van Bodegom, P. M.; Rezende, C. E.; Salomons, W.

2010-01-01

Trace elements (Fe, Mn, Al, Zn, Cr, Cu, Ni, Pb, Cd, Hg, and As) and stable isotope ratios (δ13C and δ15N) were analyzed in sediments, invertebrates, and fishes from a tropical coastal lagoon influenced by iron ore mining and processing activities to assess the differences in trace element accumulation patterns among species and to investigate relations with trophic levels of the organisms involved. Overall significant negative relations between trophic level (given by 15N) and trace element concentrations in gastropods and crustaceans showed differences in internal controls of trace element accumulation among the species of different trophic positions, leading to trace element dilution. Generally, no significant relation between δ15N and trace element concentrations was observed among fish species, probably due to omnivory in a number of species as well as fast growth. Trace element accumulation was observed in the fish tissues, with higher levels of most trace elements found in liver compared with muscle and gill. Levels of Fe, Mn, Al, and Hg in invertebrates, and Fe and Cu in fish livers, were comparable with levels in organisms and tissues from other contaminated areas. Trace element levels in fish muscle were below the international safety baseline standards for human consumption. PMID:20217062

Trace elements and carbon and nitrogen stable isotopes in organisms from a tropical coastal lagoon.

PubMed

Pereira, A A; van Hattum, B; de Boer, J; van Bodegom, P M; Rezende, C E; Salomons, W

2010-10-01

Trace elements (Fe, Mn, Al, Zn, Cr, Cu, Ni, Pb, Cd, Hg, and As) and stable isotope ratios (delta(13)C and delta(15)N) were analyzed in sediments, invertebrates, and fishes from a tropical coastal lagoon influenced by iron ore mining and processing activities to assess the differences in trace element accumulation patterns among species and to investigate relations with trophic levels of the organisms involved. Overall significant negative relations between trophic level (given by (15)N) and trace element concentrations in gastropods and crustaceans showed differences in internal controls of trace element accumulation among the species of different trophic positions, leading to trace element dilution. Generally, no significant relation between delta(15)N and trace element concentrations was observed among fish species, probably due to omnivory in a number of species as well as fast growth. Trace element accumulation was observed in the fish tissues, with higher levels of most trace elements found in liver compared with muscle and gill. Levels of Fe, Mn, Al, and Hg in invertebrates, and Fe and Cu in fish livers, were comparable with levels in organisms and tissues from other contaminated areas. Trace element levels in fish muscle were below the international safety baseline standards for human consumption.

High-efficiency dye-sensitized solar cells with ferrocene-based electrolytes.

PubMed

Daeneke, Torben; Kwon, Tae-Hyuk; Holmes, Andrew B; Duffy, Noel W; Bach, Udo; Spiccia, Leone

2011-03-01

Dye-sensitized solar cells based on iodide/triiodide (I(-)/I(3)(-)) electrolytes are viable low-cost alternatives to conventional silicon solar cells. However, as well as providing record efficiencies of up to 12.0%, the use of I(-)/I(3)(-) in such solar cells also brings about certain limitations that stem from its corrosive nature and complex two-electron redox chemistry. Alternative redox mediators have been investigated, but these generally fall well short of matching the performance of conventional I(-)/I(3)(-) electrolytes. Here, we report energy conversion efficiencies of 7.5% (simulated sunlight, AM1.5, 1,000 W m(-2)) for dye-sensitized solar cells combining the archetypal ferrocene/ferrocenium (Fc/Fc(+)) single-electron redox couple with a novel metal-free organic donor-acceptor sensitizer (Carbz-PAHTDTT). These Fc/Fc(+)-based devices exceed the efficiency achieved for devices prepared using I(-)/I(3)(-) electrolytes under comparable conditions, revealing the great potential of ferrocene-based electrolytes in future dye-sensitized solar cells applications. This improvement results from a more favourable matching of the redox potential of the ferrocene couple with that of the new donor-acceptor sensitizer.

Measurement techniques for trace metals in coal-plant effluents: A brief review

NASA Technical Reports Server (NTRS)

Singh, J. J.

1979-01-01

The strong features and limitations of techniques for determining trace elements in aerosols emitted from coal plants are discussed. Techniques reviewed include atomic absorption spectroscopy, charged particle scattering and activation, instrumental neutron activation analysis, gas/liquid chromatography, gas chromatographic/mass spectrometric methods, X-ray fluorescence, and charged-particle-induced X-ray emission. The latter two methods are emphasized. They provide simultaneous, sensitive multielement analyses and lend themselves readily to depth profiling. It is recommended that whenever feasible, two or more complementary techniques should be used for analyzing environmental samples.

Mineralogical constraints on the paleoenvironments of the Ediacaran Doushantuo Formation

PubMed Central

Bristow, Thomas F.; Kennedy, Martin J.; Derkowski, Arkadiusz; Droser, Mary L.; Jiang, Ganqing; Creaser, Robert A.

2009-01-01

Assemblages of clay minerals are routinely used as proxies for paleoclimatic change and paleoenvironmental conditions in Phanerozoic rocks. However, this tool is rarely applied in older sedimentary units. In this paper, the clay mineralogy of the Doushantuo Formation in South China is documented, providing constraints on depositional conditions of the Ediacaran Yangtze platform that host the earliest animal fossils in the geological record. In multiple sections from the Yangtze Gorges area, trioctahedral smectite (saponite) and its diagenetic products (mixed-layer chlorite/smectite, corrensite, and chlorite) are the dominant clays through the lower 80 m of the formation and constitute up to 30 wt% of the bulk rock. Saponite is interpreted as an in situ early diagenetic phase that formed in alkaline conditions (pH ≥ 9). The absence of saponite in stratigraphically equivalent basin sections, 200–400 km to the south, indicates that alkaline conditions were localized in a nonmarine basin near the Yangtze Gorges region. This interpretation is consistent with crustal abundances of redox-sensitive trace elements in saponitic mudstones deposited under anoxic conditions, as well as a 10‰ difference in the carbon isotope record between Yangtze Gorges and basin sections. Our findings suggest that nonmarine environments may have been hospitable for the fauna preserved in the Yangtze Gorges, which includes the oldest examples of animal embryo fossils and acanthomorphic acritarchs. PMID:19666508

Increased Muscle Stress-Sensitivity Induced by Selenoprotein N Inactivation in Mouse: A Mammalian Model for SEPN1-Related Myopathy

PubMed Central

Arbogast, Sandrine; Lainé, Jeanne; Vassilopoulos, Stéphane; Beuvin, Maud; Dubourg, Odile; Vignaud, Alban; Ferry, Arnaud; Krol, Alain; Allamand, Valérie; Guicheney, Pascale; Ferreiro, Ana; Lescure, Alain

2011-01-01

Selenium is an essential trace element and selenoprotein N (SelN) was the first selenium-containing protein shown to be directly involved in human inherited diseases. Mutations in the SEPN1 gene, encoding SelN, cause a group of muscular disorders characterized by predominant affection of axial muscles. SelN has been shown to participate in calcium and redox homeostasis, but its pathophysiological role in skeletal muscle remains largely unknown. To address SelN function in vivo, we generated a Sepn1-null mouse model by gene targeting. The Sepn1−/− mice had normal growth and lifespan, and were macroscopically indistinguishable from wild-type littermates. Only minor defects were observed in muscle morphology and contractile properties in SelN-deficient mice in basal conditions. However, when subjected to challenging physical exercise and stress conditions (forced swimming test), Sepn1−/− mice developed an obvious phenotype, characterized by limited motility and body rigidity during the swimming session, as well as a progressive curvature of the spine and predominant alteration of paravertebral muscles. This induced phenotype recapitulates the distribution of muscle involvement in patients with SEPN1-Related Myopathy, hence positioning this new animal model as a valuable tool to dissect the role of SelN in muscle function and to characterize the pathophysiological process. PMID:21858002

Surface-water-quality assessment of the Yakima River basin in Washington; spatial and temporal distribution of trace elements in water, sediment, and aquatic biota, 1987-91; with a section on geology

USGS Publications Warehouse

Fuhrer, Gregory J.; Cain, Daniel J.; McKenzie, Stuart W.; Rinella, Joseph F.; Crawford, J. Kent; Skach, Kenneth A.; Hornberger, Michelle I.; Gannett, Marshall W.

1999-01-01

The report describes the distribution of trace elements in sediment, water, and aquatic biota in the Yakima River basin, Washington. Trace elements were determined from streambed sediment, suspended sediment, filtered and unfiltered water samples, aquatic insects, clams, fish livers, and fish fillets between 1987 and 1991. The distribution of trace elements in these media was related to local geology and anthropogenic sources. Additionally, annual and instantaneous loads were estimated for trace elements associated with suspended sediment and trace elements in filtered water samples. Trace elements also were screened against U.S. Environmental Protection Agency guidelines established for the protection of human health and aquatic life.

Content and distribution of arsenic, bismuth, lithium and selenium in mineral and synthetic fertilizers and their contribution to soil

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

Senesi, N.; Polemio, M.; Lorusso, L.

1979-01-01

Concentrations of arsenic, bismuth, lithium and selenium were determined by atomic absorption spectrophotometry in 32 samples of commercial fertilizers from various manufacturers and distributors. Arsenic and lithium were detected in all investigated samples, bismuth in 50% of samples and selenium only in two samples. Arsenic content ranged from 2 to 321 ppM; lithium varied from 5 to 0.1 ppM; bismuth was always lower than 0.5 ppM; selenium was detectable at the levels of 10 and 13 ppM. Fertilizers made from rock phosphates contained trace element amounts generally higher than those derived from rock carbonates, synthetic nitrogen fertilizers and potassium sulphate.more » Additions of trace elements from fertilizers applied at common rates to cultivated soils are tabulated and discussed on the basis of the natural soil reserves and toxicity levels for plants. Whereas applications of bismuth resulted always very low to influence the usual soil content and plant uptakes and selenium was only rarely present in fertilizers, lithium and moreover arsenic additions by fertilizers could influence the trace element status in soil, overcoming occasionally the toxicity levels for more sensitive crops.« less

A new perspective of using sequential extraction: To predict the deficiency of trace elements during anaerobic digestion.

PubMed

Cai, Yafan; Wang, Jungang; Zhao, Yubin; Zhao, Xiaoling; Zheng, Zehui; Wen, Boting; Cui, Zongjun; Wang, Xiaofen

2018-09-01

Trace elements were commonly used as additives to facilitate anaerobic digestion. However, their addition is often blind because of the complexity of reaction conditions, which has impeded their widespread application. Therefore, this study was conducted to evaluate deficiencies in trace elements during anaerobic digestion by establishing relationships between changes in trace element bioavailability (the degree to which elements are available for interaction with biological systems) and digestion performance. To accomplish this, two batch experiments were conducted. In the first, sequential extraction was used to detect changes in trace element fractions and then to evaluate trace element bioavailability in the whole digestion cycle. In the second batch experiment, trace elements (Co, Fe, Cu, Zn, Mn, Mo and Se) were added to the reaction system at three concentrations (low, medium and high) and their effects were monitored. The results showed that sequential extraction was a suitable method for assessment of the bioavailability of trace elements (appropriate coefficient of variation and recovery rate). The results revealed that Se had the highest (44.2%-70.9%) bioavailability, while Fe had the lowest (1.7%-3.0%). A lack of trace elements was not directly related to their absolute bioavailability, but was instead associated with changes in their bioavailability throughout the digestion cycle. Trace elements were insufficient when their bioavailability was steady or increased over the digestion cycle. These results indicate that changes in trace element bioavailability during the digestion cycle can be used to predict their deficiency. Copyright © 2018 Elsevier Ltd. All rights reserved.

Total reflection X-ray fluorescence as a tool for food screening

NASA Astrophysics Data System (ADS)

Borgese, Laura; Bilo, Fabjola; Dalipi, Rogerta; Bontempi, Elza; Depero, Laura E.

2015-11-01

This review provides a comprehensive overview of the applications of total reflection X-ray fluorescence (TXRF) in the field of food analysis. Elemental composition of food is of great importance, since food is the main source of essential, major and trace elements for animals and humans. Some potentially toxic elements, dangerous for human health may contaminate food, entering the food chain from the environment, processing, and storage. For this reason the elemental analysis of food is fundamental for safety assessment. Fast and sensitive analytical techniques, able to detect major and trace elements, are required as a result of the increasing demand on multi-elemental information and product screening. TXRF is suitable for elemental analysis of food, since it provides simultaneous multi-elemental identification in a wide dynamic range of concentrations. Several different matrices may be analyzed obtaining results with a good precision and accuracy. In this review, the most recent literature about the use of TXRF for the analysis of food is reported. The focus is placed on the applications within food quality monitoring of drinks, beverages, vegetables, fruits, cereals, animal derivatives and dietary supplements. Furthermore, this paper provides a critical outlook on the developments required to transfer these methods from research to the industrial and analytical laboratories contexts.

Advances in high-resolution synchrotron micro-XANES for constraining the redox evolution of terrestrial and extraterrestrial magma

NASA Astrophysics Data System (ADS)

Lanzirotti, A.; Sutton, S. R.; Dyar, M. D.; McCanta, M. C.; Head, E.

2017-12-01

Quantifying the redox evolution of geological materials is of fundamental importance for understanding the evolution of the Earth and terrestrial planets. Microfocused, synchrotron X-ray Absorption Spectroscopy (XAS) provides direct, in-situ analyses of the valence state for elements that can be used as proxies for oxygen fugacity (Fe, V, Cr, Ti, S, Eu, and Ce). Such proxies span the entire fO2 range of solar system evolution, covering at least 16 log units. Recent technical improvements at the Advanced Photon Source 13-ID-E microspectroscopy beamline have improved the energy, spatial resolution and detection sensitivity for XAS. The application of multiple valence state oxybarometers to individual mineral grains is valuable as demonstrated in a study of Ti, V and Cr valence in olivine and pyroxene of the ungrouped achondrite NWA 7325 [1], results which yielded a very reduced fO2 estimate of IW-3 and suggested a likely origin of NWA 7325 in a parent body with similar redox conditions to the ureilite parent body. Simultaneously, we have made advances using multivariate prediction models to more precisely measure ever-smaller variations in elemental valence [2]. Applied to V XAS spectra in glasses, we have developed an MVA calibration model that directly relates the measured spectra to predicted fO2, improving the precision in calculating fO2 with more robust error analysis. These machine learning based algorithms also allow for XAS to be collected in an imaging modality to spatially map elemental redox states within samples. For example for imaging changes in Fe oxidation state in natural lunar picritic glasses [3] that may be related to magmatic degassing. This presentation highlights recent examples of this research at 13-ID-E, including application of Fe, S and V valence state oxybarometers in the analysis of terrestrial volcanic glasses and melt inclusions for looking at long term evolution of oxygen fugacity of magmas. [1] Sutton S. et al. (2017) GCA, 211, 115-132. [2] Dyar M. D et al. (2016) Amer. Mineral., 101, 744-748. [3] McCanta et al. (2017) Icarus, 285, 95-102.

Trace elements transport in western Siberia rivers across a permafrost gradient

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Manasypov, R. M.; Loiko, S.; Krickov, I. A.; Kopysov, S. G.; Kolesnichenko, L. G.; Vorobyev, S. N.; Kirpotin, S. N.

2015-11-01

Towards a better understanding of trace element transport in permafrost-affected Earth surface environments, we sampled ∼ 60 large and small rivers (< 100 to ≤ 150 000 km2 watershed area) of Western Siberia Lowland (WSL) during spring flood and summer and winter base-flow across a 1500 km latitudinal gradient covering continuous, discontinuous, sporadic and permafrost-free zones. Analysis of ∼ 40 major and trace elements in dissolved (< 0.45 μm) fraction allowed establishing main environmental factors controlling the transport of metals and trace elements in rivers of this environmentally important region. No statistically significant effect of the basin size on most TE concentration was evidenced. Three category of trace elements were distinguished according to their concentration - latitude pattern: (i) increasing northward in spring and winter (Fe, Al, Ga (only winter), Ti (only winter), REEs, Pb, Zr, Hf, Th (only winter)), linked to leaching from peat and/or redox processes and transport in the form of Fe-rich colloids, (ii) decreasing northward during all seasons (Sr, Mo, U, As, Sb) marking the underground water influence of river feeding and (iii) elements without distinct trend from S to N whose variations within each latitude range were higher than the difference between latitudinal ranges (B, Li, Ti (except summer), Cr, V, Mn, Zn, Cd, Cs, Hf, Th). In addition to these general features, specific, northward increase during spring period was mostly pronounced for Fe, Mn, Co, Zn and Ba and may stem from a combination of enhanced leaching from the topsoil and vegetation and bottom waters of the lakes (spring overturn). A spring time northward decrease was observed for Ni, Cu, Zr, Rb. The southward increase in summer was strongly visible for Fe, Ni, Ba, Rb and V, probably due to peat/moss release (Ni, Ba, Rb) or groundwater feeding (Fe, V). The Principal Component Analysis demonstrated two main factors potentially controlling the ensemble of TE concentration variation. The first factor, responsible for 16-20 % of overall variation, included trivalent and tetravalent hydrolysates, Cr, V, and DOC and presumably reflected the presence of organo-mineral colloids, as also confirmed by previous studies in Siberian rivers. The 2nd factor (8-14 % variation) was linked to the latitude of the watershed and acted on elements affected by the groundwater feeding (DIC, Sr, Mo, As, Sb, U), whose concentration decreased significantly northward during all seasons. Overall, the rank of environmental factors on TE concentration in western Siberian rivers was latitude (3 permafrost zones) > season > watershed size. The effect of the latitude was minimal in spring for most TE but highly visible for Sr, Mo, Sb and U. The main factors controlling the shift of river feeding from surface and subsurface flow to deep underground flow in the permafrost-bearing zone were the depth of the active (unfrozen) seasonal layer and its position in organic or mineral horizons of the soil profile. In the permafrost-free zone, the relative role of carbonate mineral-bearing base rock feeding vs. bog water feeding determined the pattern of trace element concentration and fluxes in rivers of various size as a function of season. Comparison of obtained TE fluxes in WSL rivers with those of other subarctic rivers demonstrated reasonable agreement for most trace elements; the lithology of base rocks was the major factor controlling the magnitude of TE fluxes. The climate change in western Siberia and permafrost boundary migration will affect essentially the elements controlled by underground water feeding (DIC, alkaline-earth elements (Ca, Sr), oxyanions (Mo, Sb, As) and U). The thickening of the active layer may increase the export of trivalent and tetravalent hydrolysates in the form of organo-ferric colloids. Plant litter-originated divalent metals present as organic complexes may be retained via adsorption on mineral horizon. However, due to various counterbalanced processes controlling element source and sinks in plants - peat - mineral soil - river systems, the overall impact of the permafrost thaw on TE export from the land to the ocean may be smaller than that foreseen by merely active layer thickening and permafrost boundary shift.

Advanced functional materials in solid phase extraction for ICP-MS determination of trace elements and their species - A review.

PubMed

He, Man; Huang, Lijin; Zhao, Bingshan; Chen, Beibei; Hu, Bin

2017-06-22

For the determination of trace elements and their species in various real samples by inductively coupled plasma mass spectrometry (ICP-MS), solid phase extraction (SPE) is a commonly used sample pretreatment technique to remove complex matrix, pre-concentrate target analytes and make the samples suitable for subsequent sample introduction and measurements. The sensitivity, selectivity/anti-interference ability, sample throughput and application potential of the methodology of SPE-ICP-MS are greatly dependent on SPE adsorbents. This article presents a general overview of the use of advanced functional materials (AFMs) in SPE for ICP-MS determination of trace elements and their species in the past decade. Herein the AFMs refer to the materials featuring with high adsorption capacity, good selectivity, fast adsorption/desorption dynamics and satisfying special requirements in real sample analysis, including nanometer-sized materials, porous materials, ion imprinting polymers, restricted access materials and magnetic materials. Carbon/silica/metal/metal oxide nanometer-sized adsorbents with high surface area and plenty of adsorption sites exhibit high adsorption capacity, and porous adsorbents would provide more adsorption sites and faster adsorption dynamics. The selectivity of the materials for target elements/species can be improved by using physical/chemical modification, ion imprinting and restricted accessed technique. Magnetic adsorbents in conventional batch operation offer unique magnetic response and high surface area-volume ratio which provide a very easy phase separation, greater extraction capacity and efficiency over conventional adsorbents, and chip-based magnetic SPE provides a versatile platform for special requirement (e.g. cell analysis). The performance of these adsorbents for the determination of trace elements and their species in different matrices by ICP-MS is discussed in detail, along with perspectives and possible challenges in the future development. Copyright © 2017 Elsevier B.V. All rights reserved.

Glow discharge spectrometry for the characterization of nuclear and radioactively contaminated environmental samples

NASA Astrophysics Data System (ADS)

Betti, Maria; Aldave de las Heras, Laura

2004-09-01

Glow discharge (GD) spectrometry as applied to characterize nuclear samples as well as for the determination of radionuclides in environmental samples is reviewed. The use of instrumentation for direct current (d.c.) glow discharge mass spectrometry (GDMS) and radio frequency glow discharge optical emission spectrometry (rf GDOES), installed inside a glove-box for the handling of radioactive samples as well as the two installations and their analytical possibilities, is described in detail. The applications of GD techniques for the characterization of samples of nuclear concern both with respect to their major and trace elements, as well as to the matrix isotopic composition are presented. Procedures for quantitative determination of major, minor, and trace elements in conductive samples are reported. As for non-conductive samples three different approaches for their measurement can be followed. Namely, the use of rf sources, the mixing of the sample with a binder conducting host matrix, and the use of a secondary cathode. In the case of oxide-based samples, the employment of a tantalum secondary cathode, acting as an oxygen getter, reduces the availability of oxygen to form polyatomic species and to produce quenching. Considerations on the use of the relative sensitivity factors (RSFs) in different matrices are reported. The analytical capabilities of GDMS are compared with ICP-MS in terms of accuracy, precision, and detection limit for the determination of trace elements in uranium oxide specimens. As for the determination of isotopic composition, GDMS was found to be competitive with thermal ionisation mass spectrometry (TIMS) as well as for bulk determinations of major elements with titration methods. Applications of GDMS to the determination of radioisotopes in environmental samples, as well for depth profiling of trace elements in oxide layers, are discussed.

Trace Element Zoning and Incipient Metamictization in a Lunar Zircon: Application of Three Microprobe Techniques

NASA Technical Reports Server (NTRS)

Wopenka, Brigitte; Jollife, Bradley L.; Zinner, Ernst; Kremser, Daniel T.

1996-01-01

We have determined major (Si, Zr, Hf), minor (Al, Y, Fe, P), and trace element (Ca, Sc, Ti, Ba, REE, Th, U) concentrations and Raman spectra of a zoned, 200 microns zircon grain in lunar sample 14161,7069, a quartz monzodiorite breccia collected at the Apollo 14 site. Analyses were obtained on a thin section in situ with an ion microprobe, an electron microprobe, and a laser Raman microprobe. The zircon grain is optically zoned in birefringence, a reflection of variable (incomplete) metamictization resulting from zo- nation in U and Th concentrations. Variations in the concentrations of U and Th correlate strongly with those of other high-field-strength trace elements and with changes in Raman spectral parameters. Concentrations of U and Th range from 21 to 55 ppm and 6 to 31 ppm, respectively, and correlate with lower Raman peak intensities, wider Raman peaks, and shifted Si-O peak positions. Concentrations of heavy rare earth elements range over a factor of three to four and correlate with intensities of fluorescence peaks. Correlated variations in trace element concentrations reflect the original magmatic differentiation of the parental melt approx. 4 b.y. ago. Degradation of the zircon structure, as reflected by the observed Raman spectral parameters, has occurred in this sample over a range of alpha-decay event dose from approx. 5.2 x 10(exp 14) to 1.4 x 10(exp 15) decay events per milligram of zircon, as calculated from the U and Th concentrations. This dose is well below the approx. 10(exp 16) events per milligram cumulative dose that causes complete metamictization and indicates that laser Raman microprobe spectroscopy is an analytical technique that is very sensitive to the radiation-induced damage in zircon.

Trace element profiles of the sea anemone Anemonia viridis living nearby a natural CO2 vent

PubMed Central

Borell, Esther M.; Fine, Maoz; Shaked, Yeala

2014-01-01

Ocean acidification (OA) is not an isolated threat, but acts in concert with other impacts on ecosystems and species. Coastal marine invertebrates will have to face the synergistic interactions of OA with other global and local stressors. One local factor, common in coastal environments, is trace element contamination. CO2 vent sites are extensively studied in the context of OA and are often considered analogous to the oceans in the next few decades. The CO2 vent found at Levante Bay (Vulcano, NE Sicily, Italy) also releases high concentrations of trace elements to its surrounding seawater, and is therefore a unique site to examine the effects of long-term exposure of nearby organisms to high pCO2 and trace element enrichment in situ. The sea anemone Anemonia viridis is prevalent next to the Vulcano vent and does not show signs of trace element poisoning/stress. The aim of our study was to compare A. viridis trace element profiles and compartmentalization between high pCO2 and control environments. Rather than examining whole anemone tissue, we analyzed two different body compartments—the pedal disc and the tentacles, and also examined the distribution of trace elements in the tentacles between the animal and the symbiotic algae. We found dramatic changes in trace element tissue concentrations between the high pCO2/high trace element and control sites, with strong accumulation of iron, lead, copper and cobalt, but decreased concentrations of cadmium, zinc and arsenic proximate to the vent. The pedal disc contained substantially more trace elements than the anemone’s tentacles, suggesting the pedal disc may serve as a detoxification/storage site for excess trace elements. Within the tentacles, the various trace elements displayed different partitioning patterns between animal tissue and algal symbionts. At both sites iron was found primarily in the algae, whereas cadmium, zinc and arsenic were primarily found in the animal tissue. Our data suggests that A. viridis regulates its internal trace element concentrations by compartmentalization and excretion and that these features contribute to its resilience and potential success at the trace element-rich high pCO2 vent. PMID:25250210

Exercise and Glycemic Control: Focus on Redox Homeostasis and Redox-Sensitive Protein Signaling

PubMed Central

Parker, Lewan; Shaw, Christopher S.; Stepto, Nigel K.; Levinger, Itamar

2017-01-01

Physical inactivity, excess energy consumption, and obesity are associated with elevated systemic oxidative stress and the sustained activation of redox-sensitive stress-activated protein kinase (SAPK) and mitogen-activated protein kinase signaling pathways. Sustained SAPK activation leads to aberrant insulin signaling, impaired glycemic control, and the development and progression of cardiometabolic disease. Paradoxically, acute exercise transiently increases oxidative stress and SAPK signaling, yet postexercise glycemic control and skeletal muscle function are enhanced. Furthermore, regular exercise leads to the upregulation of antioxidant defense, which likely assists in the mitigation of chronic oxidative stress-associated disease. In this review, we explore the complex spatiotemporal interplay between exercise, oxidative stress, and glycemic control, and highlight exercise-induced reactive oxygen species and redox-sensitive protein signaling as important regulators of glucose homeostasis. PMID:28529499

Europium anomalies in plagioclase-free deep arc cumulates constrain the redox evolution of arc magmas

NASA Astrophysics Data System (ADS)

Tang, M.; Erdman, M.; Eldridge, G.; Lee, C. T.

2017-12-01

Arc lavas are generally more oxidized than mid-ocean-ridge basalts, but how arc lavas acquire their oxidized signatures remains poorly understood. Iron oxidation state in melts have been used to suggest that fluids released from subducted slab may oxidize the sub-arc mantle and produce oxidized arc magmas from the source (e.g., Carmichael, 1991; Kelley and Cottrell), but redox-sensitive trace element and Fe isotope signatures of basalts also suggest that oxidation may happen during magma differentiation (e.g., Dauphas et al., 2009; Lee et al., 2005, 2010). One potential problem, however, is that all of these studies, represent indirect constraints on the primary, pre-erupted magma oxidation state. Here, we examine the Eu systematics of primitive, deep-seated (>45-80 km) arc cumulates, which provide the most direct constraint on arc magmas before they rise into the crust. The ratio of Eu2+/Eu3+ is a function of fo2, temperature and composition. Eu2+ is more incompatible than Eu3+ except in plagioclase. Combining Eu partitioning in minerals and experimentally calibrated Eu oxybarometer (Burnham et al., 2015) allows the application of mineral Eu anomalies in constraining magma redox conditions. The cumulates are represented by garnet-bearing pyroxenites from Arizona, USA and are arc cumulates. Because they derive from depths > 60 km, plagioclase was never present during their petrogenesis, hence any Eu anomalies reflect the effects of oxygen fugacity. We find that the most primitive cumulates have negative Eu anomalies in garnet and clinopyroxene (Eu/Eu*<1), despite the fact that depths of differentiation were too high to stabilize plagioclase. We further show that garnet and clinopyroxene Eu/Eu* increases with differentiation (decreasing Mg#), consistent with Eu2+ being more incompatible than Eu3+. Based on the Eu oxybarometer calibrated by Burnham et al. (2015), the Eu deficits in the most primitive cumulate (Mg# = 77) suggest crystallization at Dlogfo2 of FMQ-1, similar to that of mid-ocean-ridge basalts. Crystal fractionation modelling shows that the increasing Eu/Eu* in the evolved cumulates require fo2 to increase by at least 2 log units as the fractionated cumulate Mg# decreases from 77 to 53. These observations suggest that the oxidized nature of arc magmas occurs during intracrustal differentiation.

Euxinia prior to end-Permian main extinction at Xiaojiaba section, Sichuan Province, South China

NASA Astrophysics Data System (ADS)

Wei, H.; Algeo, T. J.; Chen, D.; Yu, H.

2013-12-01

Redox conditions in the global ocean prior to, during, and following the end-Permian mass extinction at 252.28 Ma remain contentious. Previous studies in western Australia, South China, and East Greenland have shown that photic-zone euxinia was present at least intermittently from the early Changhsingian through the Dienerian1-3. Here we report a study of organic carbon isotopes, pyrite sulfur isotopes, TOC, pyritic sulfur content, REE, and major and trace elements from the Upper Permian Xiaojiaba section in the Chaotian district of Guangyuan City, Sichuan Province, China. During the Permian-Triassic transition, this section was located on the northwestern margin of the South China Block, facing the Paleo-Tethys Ocean. Our results indicate that suboxic conditions prevailed during the Wuchiapingian and suboxic to anoxic conditions with several pulses of euxinia during the Changhsingian. δ13Corg values are mostly -28‰ to -26‰ but show three positive excursions (to -22‰) prior to the end-Permian mass extinction horizon. These positive excursions are associated with higher Spy concentrations (to ~1%). δ34Spy values are variable (from -41‰ to +5‰) but show a sharp negative excursion in the late Changhsingian (to -43.4‰) that coincided with the most positive δ13Corg values. This horizon is also associated with increases in Eu/Eu*, Baxs, ∑REE, Si, and redox-sensitive metals such as V. These patterns reflect linkage of the C and S cycles during the latest Permian, possibly in response to redox controls. The observed positive excursions in δ13Corg may be due to organic inputs from green sulfur bacteria, which exhibit a smaller photosynthetic fractionation (-12.5‰4) than eukaryotic algae. The pronounced negative excursion of δ34Spy corresponds to a sulfate-sulfide S isotope fractionation of about -60‰, suggesting a large flux of syngenetic framboidal pyrite, which would be indicative of euxinic water-column conditions. We infer that the euxinia prior to the main extinction horizon may have been caused by oceanic oxygen-minimum zone expansion and upward movement of the chemocline5. The coupled increases in Eu/Eu* and Baxs may record hydrothermal influence, possibly accompanied by increased ocean acidity and high seawater temperatures. Collectively, our results document major changes in seawater chemistry during the Changhsingian prior to the main end-Permian crisis.

End-member modelling as a tool for climate reconstruction-An Eastern Mediterranean case study.

PubMed

Beuscher, Sarah; Krüger, Stefan; Ehrmann, Werner; Schmiedl, Gerhard; Milker, Yvonne; Arz, Helge; Schulz, Hartmut

2017-01-01

The Eastern Mediterranean Sea is a sink for terrigenous sediments from North Africa, Europe and Asia Minor. Its sediments therefore provide valuable information on the climate dynamics in the source areas and the associated transport processes. We present a high-resolution dataset of sediment core M40/4_SL71, which was collected SW of Crete and spans the last ca. 180 kyr. We analysed the clay mineral composition, the grain size distribution within the silt fraction, and the abundance of major and trace elements. We tested the potential of end-member modelling on these sedimentological datasets as a tool for reconstructing the climate variability in the source regions and the associated detrital input. For each dataset, we modelled three end members. All end members were assigned to a specific provenance and sedimentary process. In total, three end members were related to the Saharan dust input, and five were related to the fluvial sediment input. One end member was strongly associated with the sapropel layers. The Saharan dust end members of the grain size and clay mineral datasets generally suggest enhanced dust export into the Eastern Mediterranean Sea during the dry phases with short-term increases during Heinrich events. During the African Humid Periods, dust export was reduced but may not have completely ceased. The loading patterns of two fluvial end members show a strong relationship with the Northern Hemisphere insolation, and all fluvial end members document enhanced input during the African Humid Periods. The sapropel end member most likely reflects the fixation of redox-sensitive elements within the anoxic sapropel layers. Our results exemplify that end-member modelling is a valuable tool for interpreting extensive and multidisciplinary datasets.

End-member modelling as a tool for climate reconstruction—An Eastern Mediterranean case study

PubMed Central

Krüger, Stefan; Ehrmann, Werner; Schmiedl, Gerhard; Milker, Yvonne; Arz, Helge; Schulz, Hartmut

2017-01-01

The Eastern Mediterranean Sea is a sink for terrigenous sediments from North Africa, Europe and Asia Minor. Its sediments therefore provide valuable information on the climate dynamics in the source areas and the associated transport processes. We present a high-resolution dataset of sediment core M40/4_SL71, which was collected SW of Crete and spans the last ca. 180 kyr. We analysed the clay mineral composition, the grain size distribution within the silt fraction, and the abundance of major and trace elements. We tested the potential of end-member modelling on these sedimentological datasets as a tool for reconstructing the climate variability in the source regions and the associated detrital input. For each dataset, we modelled three end members. All end members were assigned to a specific provenance and sedimentary process. In total, three end members were related to the Saharan dust input, and five were related to the fluvial sediment input. One end member was strongly associated with the sapropel layers. The Saharan dust end members of the grain size and clay mineral datasets generally suggest enhanced dust export into the Eastern Mediterranean Sea during the dry phases with short-term increases during Heinrich events. During the African Humid Periods, dust export was reduced but may not have completely ceased. The loading patterns of two fluvial end members show a strong relationship with the Northern Hemisphere insolation, and all fluvial end members document enhanced input during the African Humid Periods. The sapropel end member most likely reflects the fixation of redox-sensitive elements within the anoxic sapropel layers. Our results exemplify that end-member modelling is a valuable tool for interpreting extensive and multidisciplinary datasets. PMID:28934332

Impurity measurements in semiconductor materials using trace element accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

McDaniel, F. D.; Datar, S. A.; Nigam, M.; Ravi Prasad, G. V.

2002-05-01

Accelerator mass spectrometry (AMS) is commonly used to determine the abundance ratios of long-lived isotopes such as 10B, 14C, 36Cl, 129I, etc. to their stable counterparts at levels as low as 10 -16. Secondary ion mass spectrometry (SIMS) is routinely used to determine impurity levels in materials by depth profiling techniques. Trace-element accelerator mass spectrometry (TEAMS) is a combination of AMS and SIMS, presently being used at the University of North Texas, for high-sensitivity (ppb) impurity analyses of stable isotopes in semiconductor materials. The molecular break-up characteristics of AMS are used with TEAMS to remove the molecular interferences present in SIMS. Measurements made with different substrate/impurity combinations demonstrate that TEAMS has higher sensitivity for many elements than other techniques such as SIMS and can assist with materials characterization issues. For example, measurements of implanted As in the presence of Ge in Ge xSi 1- x/Si is difficult with SIMS because of molecular interferences from 74GeH, 29Si 30Si 16O, etc. With TEAMS, the molecular interferences are removed and higher sensitivities are obtained. Measured substrates include Si, SiGe, CoSi 2, GaAs and GaN. Measured impurities include B, N, F, Mg, P, Cl, Cr, Fe, Ni, Co, Cu, Zn, Ge, As, Se, Mo, Sn and Sb. A number of measurements will be presented to illustrate the range and power of TEAMS.

Review of the inorganic geochemistry of peats and peatland waters

NASA Astrophysics Data System (ADS)

Shotyk, William

1988-06-01

The major floristic and geochemical differences between bogs, fens, and swamps are summarized, and the most common peat types described. This is followed by a critical, historical review of the literature. The methods used to measure the pH of peatland (mire) waters are examined, and the pH range of various peatland types is reported. In addition, horizontal and vertical pH variations are illustrated, and factors affecting the pH of these waters reviewed. The cause of the low pH of surface waters of Sphagnum bogs (approximately pH 4) is critically investigated, and the relative importance of dissolved CO 2 and other inorganic acids, and organic acids to the low pH is assessed. Cation exchange on the surfaces of Sphagnum mosses is found to be a relatively unimportant acidification mechanism, but important to the chemical ecology of the plants. The redox chemistry of mire waters is described in terms of the geochemistry of such redox indicators as O 2, CO 2, CH 4, CO, H 2, H 2S, SO 42-, native Cu, and siderite (FeCO 3). Published studies of Eh in peatlands are cited, and the problems of Eh measurement and interpretation are explored. The chemical composition of mire waters (major and trace metals, and nonmetallic species) is examined, and factors affecting their composition reported. The abundance and distribution of mineral matter in peats is described, and the occurrence and formation of minerals of Fe (pyrite and other sulphides, siderite, vivianite), Cu (chalcopyrite, native Cu, covellite) and Zn (smithsonite and wurtzite) investigated. The abundance and distribution of major elements (Si, Al, Na, K, Mg, Ca) and trace metals (Ni, V, Cr, Fe, Mn, Cu, U, Zn, Pb) is described, and factors affecting their solubility examined.

Laser-ablation ICP-MS as a tool for whole rock trace element analyses on fused powders

NASA Astrophysics Data System (ADS)

Girard, G.; Rooney, T. O.

2013-12-01

Here we present an accurate and precise technique for routine trace element analysis of geologic materials by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We focus on rock powders previously prepared for X-ray fluorescence by fusion in a Li2B4O7 flux, and subsequently quenched in a Pt mold to form a glass disk. Our method allows for the analysis up to 30 trace elements by LA-ICP-MS using a Photon-Machines Analyte G2 193 nm excimer laser coupled to a Thermo-Fisher Scientific ICAP Q quadrupole ICP-MS. Analyses are run as scans on the surface of the disks. Laser ablation conditions for which trace element fractionation effects are minimal have been empirically determined to be ~ 4 J m-2 fluence, at 10 Hz , and 10 μm s-1 scan speed, using a 110 μm laser beam size. Ablated material is carried into the ICP-MS by a He carrier at a rate of 0.75 L min-1. Following pre-ablation to remove surface particles, samples are ablated for 200 s, of which 140 s are used for data acquisition. At the end of each scan, a gas blank is collected for 30 s. Dwell times for each element vary between 15 and 60 μs, depending on abundance and instrument sensitivity, allowing 120 readings of each element during the data acquisition time window. To correct for variations in the total volume of material extracted by the laser, three internal standards are used, Ca, Fe and Zr. These elements are routinely analyzed by X-ray fluorescence by the Geoanalytical laboratory at Michigan State University with precision and accuracy of <5%. The availability of several internal standards allows for better correction of possible persisting laser ablation fractionation effects; for a particular trace element, we correct using the internal standard that best reproduces its ablation behavior. Our calibration is based on a combination of fused powders of US Geological Survey and Geological Survey of Japan rock standards, NIST SRM 612 glass, and US Geological Survey natural and synthetic basalt glasses. Instrumental drift is monitored during each run using two fused standards analyzed multiple times as unknowns. We routinely achieve an external precision of <5% on multiple replicates of standards run as unknowns, which are also within <5% of certified values. Elements analyzed include most first row transition metals, large ion lithophile elements, high field strength elements, lanthanide and actinide rare earth elements.

Trace elements as quantitative probes of differentiation processes in planetary interiors

NASA Technical Reports Server (NTRS)

Drake, M. J.

1980-01-01

The characteristic trace element signature that each mineral in the source region imparts on the magma constitutes the conceptual basis for trace element modeling. It is shown that abundances of trace elements in extrusive igneous rocks may be used as petrological and geochemical probes of the source regions of the rocks if differentiation processes, partition coefficients, phase equilibria, and initial concentrations in the source region are known. Although compatible and incompatible trace elements are useful in modeling, the present review focuses primarily on examples involving the rare-earth elements.

Parenteral trace element provision: recent clinical research and practical conclusions

PubMed Central

Stehle, P; Stoffel-Wagner, B; Kuhn, K S

2016-01-01

The aim of this systematic review (PubMed, www.ncbi.nlm.nih.gov/pubmed and Cochrane, www.cochrane.org; last entry 31 December 2014) was to present data from recent clinical studies investigating parenteral trace element provision in adult patients and to draw conclusions for clinical practice. Important physiological functions in human metabolism are known for nine trace elements: selenium, zinc, copper, manganese, chromium, iron, molybdenum, iodine and fluoride. Lack of, or an insufficient supply of, these trace elements in nutrition therapy over a prolonged period is associated with trace element deprivation, which may lead to a deterioration of existing clinical symptoms and/or the development of characteristic malnutrition syndromes. Therefore, all parenteral nutrition prescriptions should include a daily dose of trace elements. To avoid trace element deprivation or imbalances, physiological doses are recommended. PMID:27049031

Trace Elements Characteristic Based on ICP-AES and the Correlation of Flavonoids from Sparganii rhizoma.

PubMed

Wang, Xinsheng; Wu, Yanfang; Wu, Chengying; Wu, Qinan; Niu, Qingshan

2018-04-01

The aim of the present work was to investigate the trace elements and the correlation with flavonoids from Sparganii rhizoma. The ICP-AES and ultraviolet-visible spectroscopy were employed to analyze trace elements and flavonoids. The concentrations of trace elements and flavonoids were calculated using standard curve. The content of flavonoids was expressed as rutin equivalents. The cluster analysis was applied to evaluate geographical features of S. rhizoma from different geographical regions. The correlation analysis was used to obtain the relationship between the trace elements and flavonoids. The results indicated that the 15 trace elements were measured and the K, Ca, Mg, Na, Mn, Al, Cu, and Zn are rich in Sparganii rhizome. The different producing regions samples were classified into four groups. There was a weak relationship between trace elements and flavonoids.

Trace Elements in Ovaries: Measurement and Physiology.

PubMed

Ceko, Melanie J; O'Leary, Sean; Harris, Hugh H; Hummitzsch, Katja; Rodgers, Raymond J

2016-04-01

Traditionally, research in the field of trace element biology and human and animal health has largely depended on epidemiological methods to demonstrate involvement in biological processes. These studies were typically followed by trace element supplementation trials or attempts at identification of the biochemical pathways involved. With the discovery of biological molecules that contain the trace elements, such as matrix metalloproteinases containing zinc (Zn), cytochrome P450 enzymes containing iron (Fe), and selenoproteins containing selenium (Se), much of the current research focuses on these molecules, and, hence, only indirectly on trace elements themselves. This review focuses largely on two synchrotron-based x-ray techniques: X-ray absorption spectroscopy and x-ray fluorescence imaging that can be used to identify the in situ speciation and distribution of trace elements in tissues, using our recent studies of bovine ovaries, where the distribution of Fe, Se, Zn, and bromine were determined. It also discusses the value of other techniques, such as inductively coupled plasma mass spectrometry, used to garner information about the concentrations and elemental state of the trace elements. These applications to measure trace elemental distributions in bovine ovaries at high resolutions provide new insights into possible roles for trace elements in the ovary. © 2016 by the Society for the Study of Reproduction, Inc.

The geochemical proxies for the eutrophic and hypoxia in the Changjiang estuary: evidence from sedimentary records

NASA Astrophysics Data System (ADS)

Xuwen, F.

2013-12-01

Three cores were selected in the Changjiang Estuary to study potential hundrend-years eutrophication and hypoxia. The sediment record in the Changjiang Estuary mud area (CEMA) within the region of pronounced hypoxia showed that an increase in TOC (21%), biomarkers (141%) and δ13 Corg (1.6‰PDB ) occurred since 1950s and a marked increase since 1970s. Some redox sensitive elements (RSEs) have been enriched significantly since the late 1960s to 1970s, the rates of Mo/Al, Cd/Al and As/Al increased about 83%, 73% and 50% respectively. And the contents of some biogenic elements also increased since the late 1960s, e.g. Ca(129%), Sr(65%) and P(38%) respectively. For the core sediment in the Cheju Island mud area (SCIMA) outside the hypoxia region, the organic geochemical indicators (TOC, biomarkers and δ13Corg ) increased in difference degrees before 1950s~1970s and then were almost the constant. The RSEs were controlled by 'grain size effects' which indicated no hypoxia occurred. For the core sediment in the Zhejiang coastal mud area (ZCMA) within the region of milder hypoxia, the distribution of biomarkers is highly similar to the CEMA, but the other indictactors such as δ13 Corg et al.were different from the above two cores. Productivity in the SCIMA have been mainly influenced by climate ocean circulation changes over the last 100 years. Productivities in the hypoxia areas were corresponding with the fertilizer consumption and high nutrient inputs from the Changjiang River, which stimulated the algae (e g. brassicasterol, dinosterol) blooming and resulted an enrichment of organic matter. Hypoxia invoked organic matter preserved in the sediment. This study concluded that biomarkers in sediment could be as the eutrophic proxies in the Changjiang Estuary and its adjacent region, and δ13 Corg, RSEs and biogenic elements could be as the proxies to trace or reconstruct history of eutrophication and hypoxia in the CEMA.

A study of the impact of moist-heat and dry-heat treatment processes on hazardous trace elements migration in food waste.

PubMed

Chen, Ting; Jin, Yiying; Qiu, Xiaopeng; Chen, Xin

2015-03-01

Using laboratory experiments, the authors investigated the impact of dry-heat and moist-heat treatment processes on hazardous trace elements (As, Hg, Cd, Cr, and Pb) in food waste and explored their distribution patterns for three waste components: oil, aqueous, and solid components. The results indicated that an insignificant reduction of hazardous trace elements in heat-treated waste-0.61-14.29% after moist-heat treatment and 4.53-12.25% after dry-heat treatment-and a significant reduction in hazardous trace elements (except for Hg without external addition) after centrifugal dehydration (P < 0.5). Moreover, after heat treatment, over 90% of the hazardous trace elements in the waste were detected in the aqueous and solid components, whereas only a trace amount of hazardous trace elements was detected in the oil component (<0.01%). In addition, results indicated that heat treatment process did not significantly reduce the concentration of hazardous trace elements in food waste, but the separation process for solid and aqueous components, such as centrifugal dehydration, could reduce the risk considerably. Finally, combined with the separation technology for solid and liquid components, dry-heat treatment is superior to moist-heat treatment on the removal of external water-soluble ionic hazardous trace elements. An insignificant reduction of hazardous trace elements in heat-treated waste showed that heat treatment does not reduce trace elements contamination in food waste considerably, whereas the separation process for solid and aqueous components, such as centrifugal dehydration, could reduce the risk significantly. Moreover, combined with the separation technology for solid and liquid components, dry-heat treatment is superior to moist-heat treatment for the removal of external water-soluble ionic hazardous trace elements, by exploring distribution patterns of trace elements in three waste components: oil, aqueous, and solid components.

Corticosterone levels in relation to trace element contamination along an urbanization gradient in the common blackbird (Turdus merula).

PubMed

Meillère, Alizée; Brischoux, François; Bustamante, Paco; Michaud, Bruno; Parenteau, Charline; Marciau, Coline; Angelier, Frédéric

2016-10-01

In a rapidly urbanizing world, trace element pollution may represent a threat to human health and wildlife, and it is therefore crucial to assess both exposition levels and associated effects of trace element contamination on urban vertebrates. In this study, we investigated the impact of urbanization on trace element contamination and stress physiology in a wild bird species, the common blackbird (Turdus merula), along an urbanization gradient (from rural to moderately urbanized areas). Specifically, we described the contamination levels of blackbirds by 4 non-essential (Ag, Cd, Hg, Pb) and 9 essential trace elements (As, Co, Cr, Cu, Fe, Mn, Ni, Se, Zn), and explored the putative disrupting effects of the non-essential element contamination on corticosterone levels (a hormonal proxy for environmental challenges). We found that non-essential trace element burden (Cd and Pb specifically) increased with increasing urbanization, indicating a significant trace element contamination even in medium sized cities and suburban areas. Interestingly, the increased feather non-essential trace element concentrations were also associated with elevated feather corticosterone levels, suggesting that urbanization probably constrains birds and that this effect may be mediated by trace element contamination. Future experimental studies are now required to disentangle the influence of multiple urban-related constraints on corticosterone levels and to specifically test the influence of each of these trace elements on corticosterone secretion. Copyright © 2016 Elsevier B.V. All rights reserved.

Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance

NASA Astrophysics Data System (ADS)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.; Couëslan, Christopher; Xu, Cheng; Kynický, Jindřich; Mumin, A. Hamid; Yang, Panseok

2017-03-01

Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data ( 600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥ 0.3 apfu F) with 0.2-2.7 wt.% SrO, 0-4.5 wt.% LREE2O3, 0-0.8 wt.% Na2O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO4)2 - and (VO4)3 - anions, substituting for (PO4)3 -, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO2, 1.5 wt.% SO3 and 660 ppm V). Although (CO3)2 - groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.

Redox sensing: Orthogonal control in cell cycle and apoptosis signaling

PubMed Central

Jones, Dean P.

2010-01-01

Living systems have three major types of cell signaling systems that are dependent upon high-energy chemicals, redox environment and transmembranal ion gating mechanisms. Development of integrated systems biology descriptions of cell signaling require conceptual models incorporating all three. Recent advances in redox biology show that thiol/disulfide redox systems are regulated under dynamic, non-equilibrium conditions, progressively oxidized with the life cycle of cells and distinct in terms of redox potentials among subcellular compartments. The present article uses these observations as a basis to distinguish “redox-sensing” mechanisms, which are more global biologic redox control mechanisms, from “redox signaling”, which involves conveyance of discrete activating or inactivating signals. Both redox sensing and redox signaling use sulfur switches, especially cysteine (Cys) residues in proteins which are sensitive to reversible oxidation, nitrosylation, glutathionylation, acylation, sulfhydration or metal binding. Unlike specific signaling mechanisms, the redox-sensing mechanisms provide means to globally affect the rates and activities of the high-energy, ion gating and redox-signaling systems by controlling sensitivity, distribution, macromolecular interactions and mobility of signaling proteins. Effects mediated through Cys residues not directly involved in signaling means redox-sensing control can be orthogonal to the signaling mechanisms. This provides a capability to integrate signals according to cell cycle and physiologic state without fundamentally altering the signaling mechanisms. Recent findings that thiol/disulfide pools in humans are oxidized with age, environmental exposures and disease risk suggest that redox-sensing thiols could provide a central mechanistic link in disease development and progression. PMID:20964735

Peat bogs and their organic soils: Archives of atmospheric change and global environmentalsignificance (Philippe Duchaufour Medal Lecture)

NASA Astrophysics Data System (ADS)

Shotyk, William

2013-04-01

A bog is much more than a waterlogged ecosystem where organic matter accumulates as peat. Peatlands such as bogs represent a critical link between the atmosphere, hydrosphere, and biosphere. Plants growing at the surface of ombrotrophic bogs receive nutrients exclusively from the atmosphere. Despite the variations in redox status caused by seasonal fluctuations in depth to water table, the low pHof the waters, and abundance of dissolved organic matter, bogs preserve a remarkably reproducible history of atmospheric pollution, climate change, landscape evolution and human history. For example, peat cores from bogs in Europe and North America have provided detailed reconstructions of the changing rates and sources of Ag, Cd, Hg, Pb, Sb, and Tl, providing new insights into the geochemical cycles of these elements, including the massive perturbations induced by human activities beginning many thousands of years ago. Despite the low pH, and perhaps because of the abundance of dissolved organic matter, bogs preserve many silicate and aluminosilicate minerals which renders them valuable archives of atmospheric dust deposition and the climate changes which drive them. In the deeper, basal peat layers of the bog, in the minerotrophic zone where pore waters are affected bymineral-water interactions in the underlying and surrounding soils and sediments, peat serves as animportant link to the hydrosphere, efficiently removing from the imbibed groundwaters such trace elements as As, Cu, Mo, Ni, Se, V, and U. These removal processes, while incompletely understood, are so effective that measuring the dissolved fraction of trace elements in the pore waters becomes a considerable challenge even for the most sophisticated analytical laboratories. While the trace elements listed above are removed from groundwaters (along with P and S), elements such as Fe and Mn are added to the waters because of reductive dissolution, an important first step in the formation of lacustrine Fe and Mn nodules. While these important chemical reactions have taken place silently and imperceptibly over millenia acrossthe Earth wherever climate and water allow bogs to form, at the same time, peat bogs represent an important component of the biosphere and provide a home to many unique plants and animals, thereby contributing to the vast biodiversity found on Earth.

A Method for Assessing the Retention of Trace Elements in Human Body Using Neural Network Technology

PubMed Central

Ragimov, Aligejdar; Faizullin, Rashat; Valiev, Vsevolod

2017-01-01

Models that describe the trace element status formation in the human organism are essential for a correction of micromineral (trace elements) deficiency. A direct trace element retention assessment in the body is difficult due to the many internal mechanisms. The trace element retention is determined by the amount and the ratio of incoming and excreted substance. So, the concentration of trace elements in drinking water characterizes the intake, whereas the element concentration in urine characterizes the excretion. This system can be interpreted as three interrelated elements that are in equilibrium. Since many relationships in the system are not known, the use of standard mathematical models is difficult. The artificial neural network use is suitable for constructing a model in the best way because it can take into account all dependencies in the system implicitly and process inaccurate and incomplete data. We created several neural network models to describe the retentions of trace elements in the human body. On the model basis, we can calculate the microelement levels in the body, knowing the trace element levels in drinking water and urine. These results can be used in health care to provide the population with safe drinking water. PMID:29065586

Assessment of trace element impacts on agricultural use of water from the Dan River following the Eden coal ash release.

PubMed

Hesterberg, Dean; Polizzotto, Matthew L; Crozier, Carl; Austin, Robert E

2016-04-01

Catastrophic events require rapid, scientifically sound decision making to mitigate impacts on human welfare and the environment. The objective of this study was to analyze potential impacts of coal ash-derived trace elements on agriculture following a 35,000-tonne release of coal ash into the Dan River at the Duke Energy Steam Station in Eden, North Carolina. We performed scenario calculations to assess the potential for excessive trace element loading to soils via irrigation and flooding with Dan River water, uptake of trace elements by crops, and livestock consumption of trace elements via drinking water. Concentrations of 13 trace elements measured in Dan River water samples within 4 km of the release site declined sharply after the release and were equivalent within 5 d to measurements taken upriver. Mass-balance calculations based on estimates of soil trace-element concentrations and the nominal river water concentrations indicated that irrigation or flooding with 25 cm of Dan River water would increase soil concentrations of all trace elements by less than 0.5%. Calculations of potential increases of trace elements in corn grain and silage, fescue, and tobacco leaves suggested that As, Cr, Se, Sr, and V were elements of most concern. Concentrations of trace elements measured in river water following the ash release never exceeded adopted standards for livestock drinking water. Based on our analyses, we present guidelines for safe usage of Dan River water to diminish negative impacts of trace elements on soils and crop production. In general, the approach we describe here may serve as a basis for rapid assessment of environmental and agricultural risks associated with any similar types of releases that arise in the future. © 2015 SETAC.

Redox-sensitive self-assembled nanoparticles based on alpha-tocopherol succinate-modified heparin for intracellular delivery of paclitaxel.

PubMed

Yang, Xiaoye; Cai, Xiaoqing; Yu, Aihua; Xi, Yanwei; Zhai, Guangxi

2017-06-15

To remedy the problems riddled in cancer chemotherapy, such as poor solubility, low selectivity, and insufficient intra-cellular release of drugs, novel heparin-based redox-sensitive polymeric nanoparticles were developed. The amphiphilic polymer, heparin-alpha-tocopherol succinate (Hep-cys-TOS) was synthesized by grafting hydrophobic TOS to heparin using cystamine as the redox-sensitive linker, which could self-assemble into nanoparticles in phosphate buffer saline (PBS) with low critical aggregation concentration (CAC) values ranging from 0.026 to 0.093mg/mL. Paclitaxel (PTX)-loaded Hep-cys-TOS nanoparticles were prepared via a dialysis method, exhibiting a high drug-loading efficiency of 18.99%. Physicochemical properties of the optimized formulation were characterized by dynamic light scattering (DLS), transmission electron microscope (TEM) and differential scanning calorimetry (DSC). Subsequently, the redox-sensitivity of Hep-cys-TOS nanoparticles was confirmed by the changes in size distribution, morphology and appearance after dithiothreitol (DTT) treatment. Besides, the in vitro release of PTX from Hep-cys-TOS nanoparticles also exhibited a redox-triggered profile. Also, the uptake behavior and pathways of coumarin 6-loaded Hep-cys-TOS nanoparticles were investigated, suggesting the nanoparticles could be taken into MCF-7 cells in energy-dependent, caveolae-mediated and cholesterol-dependent endocytosis manners. Later, MTT assays of different PTX-free and PTX-loaded formulations revealed the desirable safety of PTX-free nanoparticles and the enhanced anti-cancer activity of PTX-loaded Hep-cys-TOS nanoparticles (IC 50 =0.79μg/mL). Apoptosis study indicated the redox-sensitive formulation could induce more apoptosis of MCF-7 cells than insensitive one (55.2% vs. 41.7%), showing the importance of intracellular burst release of PTX. Subsequently, the hemolytic toxicity confirmed the safety of the nanoparticles for intravenous administration. The results indicated the developed redox-sensitive nanoparticles were promising as intracellular drug delivery vehicles for cancer treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

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 and particularly phosphate mineral weathering (apatite) is the main contributor to labile REE in the soil.

New Perspectives on the Essential Trace Elements.

ERIC Educational Resources Information Center

Frieden, Earl

1985-01-01

Provides a comprehensive overview of the 19 essential trace elements, examining: the concept of essentiality; evolution of these elements; possible future essential elements; the lanthanides and actinides; how essential trace elements work; the metalloenzymes; the nonmetals; iodine and the thyroid hormones; and antagonism among these elements. (JN)

Factors influencing the biogeochemistry of sedimentary carbon and phosphorus in the Sacramento-San Joaquin Delta

USGS Publications Warehouse

Nilsen, E.B.; Delaney, M.L.

2005-01-01

This study characterizes organic carbon (Corganic) and phosphorus (P) geochemistry in surface sediments of the Sacramento-San Joaquin Delta, California. Sediment cores were collected from five sites on a sample transect from the edge of the San Francisco Bay eastward to the freshwater Consumnes River. The top 8 cm of each core were analyzed (in 1-cm intervals) for Corganic, four P fractions, and redox-sensitive trace metals (uranium and manganese). Sedimentary Corganic concentrations and Corganic:P ratios decreased, while reactive P concentrations increased moving inland in the Delta. The fraction of total P represented by organic P increased inland, while that of authigenic P was higher bayward than inland reflecting increased diagenetic alteration of organic matter toward the bayward end of the transect. The redox indicator metals are consistent with decreasing sedimentary suboxia inland. The distribution of P fractions and C:P ratios reflect the presence of relatively labile organic matter in upstream surface sediments. Sediment C and P geochemistry is influenced by site-specific particulate organic matter sources, the sorptive power of the sedimentary material present, physical forcing, and early diagenetic transformations presumably driven by Corganic oxidation. ?? 2005 Estuarine Research Federation.

Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites.

PubMed

Saunders, James A; Pivetz, Bruce E; Voorhies, Nathan; Wilkin, Richard T

2016-12-01

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are important in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of uranium ores is a process of contacting the uranium mineral deposit with leaching and oxidizing (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality degradation from: 1) potential excursions of leaching solutions away from the injection zone into down-gradient, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential mobilization and migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies data gaps in mitigating these vulnerabilities, and discusses the hydrogeological characterization involved in developing a monitoring program. Published by Elsevier Ltd.

Mitochondrial Redox Signaling and Tumor Progression.

PubMed

Chen, Yuxin; Zhang, Haiqing; Zhou, Huanjiao Jenny; Ji, Weidong; Min, Wang

2016-03-25

Cancer cell can reprogram their energy production by switching mitochondrial oxidative phosphorylation to glycolysis. However, mitochondria play multiple roles in cancer cells, including redox regulation, reactive oxygen species (ROS) generation, and apoptotic signaling. Moreover, these mitochondrial roles are integrated via multiple interconnected metabolic and redox sensitive pathways. Interestingly, mitochondrial redox proteins biphasically regulate tumor progression depending on cellular ROS levels. Low level of ROS functions as signaling messengers promoting cancer cell proliferation and cancer invasion. However, anti-cancer drug-initiated stress signaling could induce excessive ROS, which is detrimental to cancer cells. Mitochondrial redox proteins could scavenger basal ROS and function as "tumor suppressors" or prevent excessive ROS to act as "tumor promoter". Paradoxically, excessive ROS often also induce DNA mutations and/or promotes tumor metastasis at various stages of cancer progression. Targeting redox-sensitive pathways and transcriptional factors in the appropriate context offers great promise for cancer prevention and therapy. However, the therapeutics should be cancer-type and stage-dependent.

Trace element contaminants in mineral fertilizers used in Iran.

PubMed

Latifi, Zahra; Jalali, Mohsen

2018-05-25

The application of mineral fertilizers which have contaminants of trace elements may impose concern regarding the entry and toxic accumulation of these elements in agro-ecosystems. In this study, 57 mineral fertilizers (nitrogen, potassium, phosphate, and compound fertilizers) distributed in Iran were analyzed for their contents of Cd, Co, Cr, Cu, Mn, Ni, Pb, Zn, and Fe. The results revealed that the contents of these trace elements varied considerably depending on the type of the element and the fertilizer. Among these elements, Fe displayed the highest average content, whereas Cd showed the lowest. Generally, the trace element contents in P-containing fertilizers were higher than those in nitrogen and potassium fertilizers. The mean values of trace elements (mg kg -1 ) in P-containing fertilizers were 4.0 (Cd), 5.5 (Co), 35.7 (Cr), 24.4 (Cu), 272 (Mn), 14.3 (Ni), 6.0 (Pb), 226 (Zn), and 2532 (Fe). Comparing trace element contents to limit values set by the German Fertilizer Ordinance showed that the mean contents of potentially toxic trace elements, such as Cd and Pb, were lower than their limit values in all groups of fertilizers. On the other hand, while a number of fertilizers contained a high content of some essential trace elements, particularly Fe, they were not labeled as such.

Analysis of trace metals in water by inductively coupled plasma emission spectrometry using sodium dibenzyldithiocarbamate for preconcentration

USGS Publications Warehouse

Smith, C.L.; Motooka, J.M.; Willson, W.R.

1984-01-01

Since concentrations of trace elements in most natural waters seldom exceed the ??g/L level, analysis of trace elements in natural waters by inductively coupled plasma emission spectrometry (ICP) requires a preconcentration procedure. The elements Ag, Bi, Cd, Co, Cu, Fe, Mo, Ni, Pb, Sn, V, W, and Zn were separated and concentrated from 500 mL of water by coprecipitating them with sodium dibenzyldithiocarbamate (NaDBDTC) using nickel or silver as a carrier. The precipitated trace elements were collected on a membrane filter, redissolved from the filter with hot nitric and hydrochloric acids, and analyzed using ICP. Recoveries for all the trace elements except tungsten exceeded 80%. Coprecipitation of trace elements with NaDBDTC eliminated the use of difficult-to-inject organic solvents, and NaDBDTC coprecipitated a wider array of trace elements than ammoniumpyrrolidinedithiocarbamate (APDC), another commonly used coprecipitate.

Origin and spatial distribution of metals in moss samples in Albania: A hotspot of heavy metal contamination in Europe.

PubMed

Lazo, Pranvera; Steinnes, Eiliv; Qarri, Flora; Allajbeu, Shaniko; Kane, Sonila; Stafilov, Trajce; Frontasyeva, Marina V; Harmens, Harry

2018-01-01

This study presents the spatial distribution of 37 elements in 48 moss samples collected over the whole territory of Albania and provides information on sources and factors controlling the concentrations of elements in the moss. High variations of trace metals indicate that the concentrations of elements are affected by different factors. Relations between the elements in moss, geochemical interpretation of the data, and secondary effects such as redox conditions generated from local soil and/or long distance atmospheric transport of the pollutants are discussed. Zr normalized data, and the ratios of different elements are calculated to assess the origin of elements present in the current moss samples with respect to different geogenic and anthropogenic inputs. Factor analysis (FA) is used to identify the most probable sources of the elements. Four dominant factors are identified, i.e. natural contamination; dust emission from local mining operations; atmospheric transport of contaminants from local and long distance sources; and contributions from air borne marine salts. Mineral particle dust from local emission sources is classified as the most important factor affecting the atmospheric deposition of elements accumulated in the current moss samples. The open slag dumps of mining operation in Albania is probably the main factor contributing to high contents of Cr, Ni, Fe, Ti and Al in the moss. Enrichment factors (EF) were calculated to clarify whether the elements in the present moss samples mainly originate from atmospheric deposition and/or local substrate materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characteristics of the iodide/triiodide redox mediator in dye-sensitized solar cells.

PubMed

Boschloo, Gerrit; Hagfeldt, Anders

2009-11-17

Dye-sensitized solar cells (DSCs) have gained widespread interest because of their potential for low-cost solar energy conversion. Currently, the certified record efficiency of these solar cells is 11.1%, and measurements of their durability and stability suggest lifetimes exceeding 10 years under operational conditions. The DSC is a photoelectrochemical system: a monolayer of sensitizing dye is adsorbed onto a mesoporous TiO(2) electrode, and the electrode is sandwiched together with a counter electrode. An electrolyte containing a redox couple fills the gap between the electrodes. The redox couple is a key component of the DSC. The reduced part of the couple regenerates the photo-oxidized dye. The formed oxidized species diffuses to the counter electrode, where it is reduced. The photovoltage of the device depends on the redox couple because it sets the electrochemical potential at the counter electrode. The redox couple also affects the electrochemical potential of the TiO(2) electrode through the recombination kinetics between electrons in TiO(2) and oxidized redox species. This Account focuses on the special properties of the iodide/triiodide (I(-)/I(3)(-)) redox couple in dye-sensitized solar cells. It has been the preferred redox couple since the beginning of DSC development and still yields the most stable and efficient DSCs. Overall, the iodide/triiodide couple has good solubility, does not absorb too much light, has a suitable redox potential, and provides rapid dye regeneration. But what distinguishes I(-)/I(3)(-) from most redox mediators is the very slow recombination kinetics between electrons in TiO(2) and the oxidized part of the redox couple, triiodide. Certain dyes adsorbed at TiO(2) catalyze this recombination reaction, presumably by binding iodine or triiodide. The standard potential of the iodide/triiodide redox couple is 0.35 V (versus the normal hydrogen electrode, NHE), and the oxidation potential of the standard DSC-sensitizer (Ru(dcbpy)(2)(NCS)(2)) is 1.1 V. The driving force for reduction of oxidized dye is therefore as large as 0.75 V. This process leads to the largest internal potential loss in DSC devices. We expect that overall efficiencies above 15% might be achieved if half of this internal potential loss could be gained. The regeneration of oxidized dye with iodide leads to the formation of the diiodide radical (I(2)(-*)). The redox potential of the I(2)(-*)/I(-) couple must therefore be considered when determining the actual driving force for dye regeneration. The formed I(2)(-*) disproportionates to I(3)(-) and I(-), which leads to a large loss in potential energy.

Determination of trace rare earth elements in gadolinium aluminate by inductively coupled plasma time of flight mass spectrometry

NASA Astrophysics Data System (ADS)

Saha, Abhijit; Deb, S. B.; Nagar, B. K.; Saxena, M. K.

An analytical methodology was developed for the precise quantification of ten trace rare earth elements (REEs), namely, La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Tm, in gadolinium aluminate (GdAlO3) employing an ultrasonic nebulizer (USN)-desolvating device based inductively coupled plasma mass spectrometry (ICP-MS). A microwave digestion procedure was optimized for digesting 100 mg of the refractory oxide using a mixture of sulphuric acid (H2SO4), phosphoric acid (H3PO4) and water (H2O) with 1400 W power, 10 min ramp and 60 min hold time. An USN-desolvating sample introduction system was employed to enhance analyte sensitivities by minimizing their oxide ion formation in the plasma. Studies on the effect of various matrix concentrations on the analyte intensities revealed that precise quantification of the analytes was possible with matrix level of 250 mg L- 1. The possibility of using indium as an internal standard was explored and applied to correct for matrix effect and variation in analyte sensitivity under plasma operating conditions. Individual oxide ion formation yields were determined in matrix matched solution and employed for correcting polyatomic interferences of light REE (LREE) oxide ions on the intensities of middle and heavy rare earth elements (MREEs and HREEs). Recoveries of ≥ 90% were achieved for the analytes employing standard addition technique. Three real samples were analyzed for traces of REEs by the proposed method and cross validated for Eu and Nd by isotope dilution mass spectrometry (IDMS). The results show no significant difference in the values at 95% confidence level. The expanded uncertainty (coverage factor 1σ) in the determination of trace REEs in the samples were found to be between 3 and 8%. The instrument detection limits (IDLs) and the method detection limits (MDLs) for the ten REEs lie in the ranges 1-5 ng L- 1 and 7-64 μg kg- 1 respectively.

Trace element partitioning between coexisting biotite and muscovite from metamorphic rocks, western Labrador: Structural, compositional and thermal controls

NASA Astrophysics Data System (ADS)

Yang, Panseok; Rivers, Toby

2000-04-01

Coexisting biotite and muscovite in ten metapelitic and quartzofeldspathic rocks from western Labrador have been analyzed by electron microprobe for major and minor elements and by a laser ablation microprobe coupled to ICP-MS (LAM-ICP-MS) for selected trace elements - Li, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf and Ta. The samples have experienced a single prograde Grenvillian metamorphism ranging from 490 to 680°C and from 7 to 12 kbar. The trace element compositions of coexisting micas in the metamorphic rocks are used to assess the effects of crystal structure, major element composition and temperature on the partitioning of each element between biotite and muscovite. Overall, trace element distributions are systematic across the range of metamorphic grade and bulk composition, suggesting that chemical equilibrium was approached. Most distribution coefficients (biotite/muscovite) show good agreement with published data. However, distribution coefficients for Co and Sr are significantly different from previous determinations, probably because of contamination associated with older data obtained by bulk analysis techniques. The sequence of distribution coefficients is governed mainly by the ionic radii and charges of substituting cations compared to the optimum ionic radius of each crystallographic site in the micas. In particular, distribution coefficients exhibit the sequence Cr 3+ (0.615 Å) > V 3+ (0.64 Å) > Sc 3+ (0.745 Å) in VI-sites, and Ba 2+ (1.61 Å) > Sr 2+ (1.44 Å) and Cs + (1.88 Å) > K + (1.64 Å) > Rb + (1.72 Å) > Na + (1.39 Å) in XII-sites. The distributions of Li, Sc, Sr and Ba appear to be thermally sensitive but are also controlled by major element compositions of micas. V and Zr partitioning is dependent on T and may be used to cross-check thermometry calculations where the latter suffer from retrograde re-equilibration and/or high concentrations of Fe 3+. The ranges and dependence of distribution coefficients on major element compositions provide important constraints on the values that can be used in geochemical modeling.

Linking trace element variations with macronutrients and major cations in marine mussels Mytilus edulis and Perna viridis.

PubMed

Liu, Fengjie; Wang, Wen-Xiong

2015-09-01

Marine mussels have long been used as biomonitors of contamination of trace elements, but little is known about whether variation in tissue trace elements is significantly associated with those of macronutrients and major cations. The authors examined the variability of macronutrients and major cations and their potential relationships with bioaccumulation of trace elements. The authors analyzed the concentrations of macronutrients (C, N, P, S), major cations (Na, Mg, K, Ca), and trace elements (Al, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Pb) in the whole soft tissues of marine mussels Mytilus edulis and Perna viridis collected globally from 21 sites. The results showed that 12% to 84% of the variances in the trace elements was associated with major cations, and the tissue concentration of major cations such as Na and Mg in mussels was a good proxy for ambient seawater concentrations of the major cations. Specifically, bioaccumulation of most of the trace elements was significantly associated with major cations, and the relationships of major cations with trace cations and trace oxyanions were totally opposite. Furthermore, 14% to 69% of the variances in the trace elements were significantly associated with macronutrients. Notably, more than half of the variance in the tissue concentrations of As, Cd, V, Ba, and Pb was explained by the variance in macronutrients in one or both species. Because the tissue macronutrient concentrations were strongly associated with animal growth and reproduction, the observed coupling relationships indicated that these biological processes strongly influenced the bioaccumulation of some trace elements. The present study indicated that simultaneous quantification of macronutrients and major cations with trace elements can improve the interpretation of biomonitoring data. © 2015 SETAC.

[Proposal of new trace elements classification to be used in nutrition, oligotherapy and other therapeutics strategies].

PubMed

Ramírez Hernández, Javier; Bonete Pérez, María José; Martínez Espinosa, Rosa María

2014-12-17

1) to propose a new classification of the trace elements based on a study of the recently reported research; 2) to offer detailed and actualized information about trace elements. the analysis of the research results recently reported reveals that the advances of the molecular analysis techniques point out the importance of certain trace elements in human health. A detailed analysis of the catalytic function related to several elements not considered essential o probably essentials up to now is also offered. To perform the integral analysis of the enzymes containing trace elements informatics tools have been used. Actualized information about physiological role, kinetics, metabolism, dietetic sources and factors promoting trace elements scarcity or toxicity is also presented. Oligotherapy uses catalytic active trace elements with therapeutic proposals. The new trace element classification here presented will be of high interest for different professional sectors: doctors and other professions related to medicine; nutritionist, pharmaceutics, etc. Using this new classification and approaches, new therapeutic strategies could be designed to mitigate symptomatology related to several pathologies, particularly carential and metabolic diseases. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Redox state of the Archean mantle: Evidence from V partitioning in 3.5-2.4 Ga komatiites

NASA Astrophysics Data System (ADS)

Nicklas, Robert W.; Puchtel, Igor S.; Ash, Richard D.

2018-02-01

Oxygen fugacity of the mantle is a crucial thermodynamic parameter that controls such fundamental processes as planetary differentiation, mantle melting, and possible core-mantle exchange. Constraining the evolution of the redox state of the mantle is of paramount importance for understanding the chemical evolution of major terrestrial reservoirs, including the core, mantle, and atmosphere. In order to evaluate the secular evolution of the redox state of the mantle, oxygen fugacities of six komatiite systems, ranging in age from 3.48 to 2.41 Ga, were determined using high-precision partitioning data of the redox-sensitive element vanadium between liquidus olivine, chromite and komatiitic melt. The calculated oxygen fugacities range from -0.11 ± 0.30 ΔFMQ log units in the 3.48 Ga Komati system to +0.43 ± 0.26 ΔFMQ log units in the 2.41 Ga Vetreny system. Although there is a slight hint in the data for an increase in the oxygen fugacity of the mantle between 3.48 and 2.41 Ga, these values generally overlap within their respective uncertainties; they are also largely within the range of oxygen fugacity estimates for modern MORB lavas of +0.60 ± 0.30 ΔFMQ log units that we obtained using the same technique. Our results are consistent with the previous findings that argued for little change in the mantle oxygen fugacity since the early Archean and indicate that the mantle had reached its nearly-present day redox state by at least 3.48 Ga.

Trace elements have limited utility for studying migratory connectivity in shorebirds that winter in Argentina

USGS Publications Warehouse

Torres-Dowdall, J.; Farmer, A.H.; Abril, M.; Bucher, E.H.; Ridley, I.

2010-01-01

Trace-element analysis has been suggested as a tool for the study of migratory connectivity because (1) trace-element abundance varies spatially in the environment, (2) trace elements are assimilated into animals' tissues through the diet, and (3) current technology permits the analysis of multiple trace elements in a small tissue sample, allowing the simultaneous exploration of several elements. We explored the potential of trace elements (B, Na, Mg, Al, Si, P, S, K, Ca, Ti, Cr, Mn, Ni, Cu, Zn, As, Sr, Cs, Hg, Tl, Pb, Bi, Th, and U) to clarify the migratory connectivity of shorebirds that breed in North America and winter in southern South America. We collected 66 recently replaced secondary feathers from Red Knots (Calidris canutus) at three sites in Patagonia and 76 from White-rumped Sandpipers (C. fuscicollis) at nine sites across Argentina. There were significant differences in trace-element abundance in shorebird feathers grown at different nonbreeding sites, and annual variability within a site was small compared to variability among sites. Across Argentina, there was no large-scale gradient in trace elements. The lack of such a gradient restricts the application of this technique to questions concerning the origin of shorebirds to a small number of discrete sites. Furthermore, our results including three additional species, the Pectoral Sandpiper (C. melanotos), Wilson's Phalarope (Phalaropus tricolor), and Collared Plover (Charadrius collaris), suggest that trace-element profiles change as feathers age. Temporal instability of trace-element values could undermine their application to the study of migratory connectivity in shorebirds. ?? The Cooper Ornithological Society 2010.

Influence of fly ash aided phytostabilisation of Pb, Cd and Zn highly contaminated soils on Lolium perenne and Trifolium repens metal transfer and physiological stress.

PubMed

Lopareva-Pohu, Alena; Verdin, Anthony; Garçon, Guillaume; Lounès-Hadj Sahraoui, Anissa; Pourrut, Bertrand; Debiane, Djouher; Waterlot, Christophe; Laruelle, Frédéric; Bidar, Géraldine; Douay, Francis; Shirali, Pirouz

2011-06-01

Due to anthropogenic activities, large extends of soils are highly contaminated by Metal Trace Element (MTE). Aided phytostabilisation aims to establish a vegetation cover in order to promote in situ immobilisation of trace elements by combining the use of metal-tolerant plants and inexpensive mineral or organic soil amendments. Eight years after Coal Fly Ash (CFA) soil amendment, MTE bioavailability and uptake by two plants, Lolium perenne and Trifolium repens, were evaluated, as some biological markers reflecting physiological stress. Results showed that the two plant species under study were suitable to reduce the mobility and the availability of these elements. Moreover, the plant growth was better on CFA amended MTE-contaminated soils, and the plant sensitivity to MTE-induced physiological stress, as studied through photosynthetic pigment contents and oxidative damage was lower or similar. In conclusion, these results supported the usefulness of aided phytostabilisation of MTE-highly contaminated soils. Copyright © 2011 Elsevier Ltd. All rights reserved.

Transition Metals and Virulence in Bacteria

PubMed Central

Palmer, Lauren D.; Skaar, Eric P.

2016-01-01

Transition metals are required trace elements for all forms of life. Due to their unique inorganic and redox properties, transition metals serve as cofactors for enzymes and other proteins. In bacterial pathogenesis, the vertebrate host represents a rich source of nutrient metals, and bacteria have evolved diverse metal acquisition strategies. Host metal homeostasis changes dramatically in response to bacterial infections, including production of metal sequestering proteins and the bombardment of bacteria with toxic levels of metals. Presumably, in response, bacteria have evolved systems to subvert metal sequestration and toxicity. The coevolution of hosts and their bacterial pathogens in the battle for metals has uncovered emerging paradigms in social microbiology, rapid evolution, host specificity, and metal homeostasis across domains. This review focuses on recent advances and open questions in our understanding of the complex role of transition metals at the host-pathogen interface. PMID:27617971

Redox Conditions on Small Bodies

NASA Technical Reports Server (NTRS)

Jones, J. H.

2004-01-01

The Eucrite Parent Body (4 Vesta). The eucrites are basalts that contain approx. 18 wt% FeO and contain trace metal. The eucrites are very depleted in siderophile elements, so it appears that the source regions of these basalts once equilibrated with Fe-Ni metal. Therefore, it is of interest to ask what fo2 is required to precipitate metal from a liquid of eucrite composition. Or in other words, what f02 did eucrites form under? This fo2 has been determined experimentally by and was found to be IW-1. Therefore, eucrites formed at about IW-1. In addition, it is interesting to note that assuming X(sub feo) = alpha(sub FeO) allows calculation of eucrite fo2 (assuming equilibrium with Fe metal). This calculation yields the same result as the experiments to within approx. 0.25 log units, reinforcing this result.

Transition Metals and Virulence in Bacteria.

PubMed

Palmer, Lauren D; Skaar, Eric P

2016-11-23

Transition metals are required trace elements for all forms of life. Due to their unique inorganic and redox properties, transition metals serve as cofactors for enzymes and other proteins. In bacterial pathogenesis, the vertebrate host represents a rich source of nutrient metals, and bacteria have evolved diverse metal acquisition strategies. Host metal homeostasis changes dramatically in response to bacterial infections, including production of metal sequestering proteins and the bombardment of bacteria with toxic levels of metals. In response, bacteria have evolved systems to subvert metal sequestration and toxicity. The coevolution of hosts and their bacterial pathogens in the battle for metals has uncovered emerging paradigms in social microbiology, rapid evolution, host specificity, and metal homeostasis across domains. This review focuses on recent advances and open questions in our understanding of the complex role of transition metals at the host-pathogen interface.

The chemical characteristics of ground water near Fairbanks, Alaska: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1998

USGS Publications Warehouse

Farmer, G. Lang; Goldfarb, Richard J.; Lilly, Michael R.; Bolton, Bob; Meier, Allen L.; Sanzolone, Richard F.

2000-01-01

Major- and trace-element abundances, and Sr and Pb isotopic compositions, of ground waters in and near Fairbanks, Alaska, were determined to characterize their chemical characteristics and to assess the factors controlling variations in dissolved arsenic concentrations. Collected samples show majorelement (Ca>Mg>Na>K) and strontium and lead isotopic compositions characteristic of waters that have interacted with lithologies comprising the Fairbanks Schist. Dissolved arsenic concentrations are not highly correlated with the abundances of other major and trace elements in these waters; however, waters with high arsenic concentrations (5.4 to 450 parts per billion) tend to have relatively high concentrations of antimony (as much as 1.7 ppb). The correlation between arsenic and antimony suggests that both elements were derived from the oxidation of hypogene sulfide minerals (arsenopyrite) that originally formed within the Fairbanks Schist during hydrothermal activity associated with the emplacement of Cretaceous granitic rocks. Variations in measured arsenic concentrations are due, in part, to the variations in the original abundance of upgradient sulfide minerals from a given well or spring. However, speciation studies on the ground water containing the highest concentration of arsenic in this study (450 ppb) demonstrate that the arsenic occurs primarily in its reduced form (As(III)). In agreement with previous studies, we conclude that relatively reducing ground waters have the highest potential for high arsenic concentrations due to greater mobility of As(III) relative to its oxidized counterpart (As(V)). In light of this conclusion, additional studies are being undertaken to determine how seasonal variations in ground-water redox affect arsenic mobility

Grain-size distribution and selected major and trace element concentrations in bed-sediment cores from the Lower Granite Reservoir and Snake and Clearwater Rivers, eastern Washington and northern Idaho, 2010

USGS Publications Warehouse

Braun, Christopher L.; Wilson, Jennifer T.; Van Metre, Peter C.; Weakland, Rhonda J.; Fosness, Ryan L.; Williams, Marshall L.

2012-01-01

Fifty subsamples from 15 cores were analyzed for major and trace elements. Concentrations of trace elements were low, with respect to sediment quality guidelines, in most cores. Typically, major and trace element concentrations were lower in the subsamples collected from the Snake River compared to those collected from the Clearwater River, the confluence of the Snake and Clearwater Rivers, and Lower Granite Reservoir. Generally, lower concentrations of major and trace elements were associated with coarser sediments (larger than 0.0625 millimeter) and higher concentrations of major and trace elements were associated with finer sediments (smaller than 0.0625 millimeter).

An upwelling model for the Phosphoria sea: A Permian, ocean-margin sea in the northwest United States

USGS Publications Warehouse

Piper, D.Z.; Link, P.K.

2002-01-01

The Permian Phosphoria Formation, a petroleum source rock and world-class phosphate deposit, was deposited in an epicratonic successor basin on the western margin of North America. We calculate the seawater circulation in the basin during deposition of the lower ore zone in the Meade Peak Member from the accumulation rates of carbonate fluorapatite and trace elements. The model gives the exchange rate of water between the Phosphoria sea and the open ocean to the west in terms of an upwelling rate (84 m yr-1) and residence time (4.2 yr) of seawater in the basin. These hydrographic properties supported a mean rate of primary productivity of 0.87 g m-2 d-1 of carbon in the uppermost few tens of meters of the water column (the photic zone) and denitrifying redox conditions in the bottom water (below approximately 150 m depth). High rain rates, onto the sea floor, of the organic matter that hosted the phosphate and several trace elements contributed to the accumulation of phosphorite, chert, and black shales and mudstones. Evaporation in the Goose Egg basin to the east of the Phosphoria basin ensured the import of surface seawater from the Phosphoria sea. Budgets of water, salt, phosphate, and oxygen, plus the minor accumulation of the biomarker gammacerane, show that exchange of water between the two basins was limited, possibly by the shallow carbonate platform that separated the two basins.

Investigation of Acidithiobacillus ferrooxidans in pure and mixed-species culture for bioleaching of Theisen sludge from former copper smelting.

PubMed

Klink, C; Eisen, S; Daus, B; Heim, J; Schlömann, M; Schopf, S

2016-06-01

The aim of this study was to investigate the potential of bioleaching for the treatment of an environmentally hazardous waste, a blast-furnace flue dust designated Theisen sludge. Bioleaching of Theisen sludge was investigated at acidic conditions with Acidithiobacillus ferrooxidans in pure and mixed-species culture with Acidiphilium. In shaking-flask experiments, bioleaching parameters (pH, redox potential, zinc extraction from ZnS, ferrous- and ferric-iron concentration) were controlled regularly. The analysis of the dissolved metals showed that 70% zinc and 45% copper were extracted. Investigations regarding the arsenic and antimony species were performed. When iron ions were lacking, animonate (Sb(V)) and total arsenic concentration were highest in solution. The bioleaching approach was scaled up in stirred-tank bioreactors resulting in higher leaching efficiency of valuable trace elements. Concentrations of dissolved antimony were approx. 23 times, and of cobalt, germanium, and rhenium three times higher in comparison to shaking-flask experiments, when considering the difference in solid load of Theisen sludge. The extraction of base and trace metals from Theisen sludge, despite of its high content of heavy metals and organic compounds, was feasible with iron-oxidizing acidophilic bacteria. In stirred-tank bioreactors, the mixed-species culture performed better. To the best of our knowledge, this study is the first providing an appropriate biological technology for the treatment of Theisen sludge to win valuable elements. © 2016 The Society for Applied Microbiology.

Redox protein noncovalent functionalization of double-wall carbon nanotubes: electrochemical binder-less glucose biosensor.

PubMed

Pumera, Martin; Smíd, Bretislav

2007-10-01

Double wall carbon nanotubes are noncovalently functionalized with redox protein and such assembly is used for construction of electrochemical binder-less glucose biosensor. Redox protein glucose oxidase performs as biorecognition element and double wall carbon nanotubes act both as immobilization platform for redox enzyme and as signal transducer. The double carbon nanotubes are characterized by cyclic voltammetry and specific surface area measurements; the redox protein noncovalently functionalized double wall carbon nanotubes are characterized in detail by X-ray photoelectron spectroscopy, cyclic voltammetry, amperometry, and transmission electron microscopy.

Redox Indicator Mice Stably Expressing Genetically Encoded Neuronal roGFP: Versatile Tools to Decipher Subcellular Redox Dynamics in Neuropathophysiology.

PubMed

Wagener, Kerstin C; Kolbrink, Benedikt; Dietrich, Katharina; Kizina, Kathrin M; Terwitte, Lukas S; Kempkes, Belinda; Bao, Guobin; Müller, Michael

2016-07-01

Reactive oxygen species (ROS) and downstream redox alterations not only mediate physiological signaling but also neuropathology. For long, ROS/redox imaging was hampered by a lack of reliable probes. Genetically encoded redox sensors overcame this gap and revolutionized (sub)cellular redox imaging. Yet, the successful delivery of sensor-coding DNA, which demands transfection/transduction of cultured preparations or stereotaxic microinjections of each subject, remains challenging. By generating transgenic mice, we aimed to overcome limiting cultured preparations, circumvent surgical interventions, and to extend effectively redox imaging to complex and adult preparations. Our redox indicator mice widely express Thy1-driven roGFP1 (reduction-oxidation-sensitive green fluorescent protein 1) in neuronal cytosol or mitochondria. Negative phenotypic effects of roGFP1 were excluded and its proper targeting and functionality confirmed. Redox mapping by ratiometric wide-field imaging reveals most oxidizing conditions in CA3 neurons. Furthermore, mitochondria are more oxidized than cytosol. Cytosolic and mitochondrial roGFP1s reliably report cell endogenous redox dynamics upon metabolic challenge or stimulation. Fluorescence lifetime imaging yields stable, but marginal, response ranges. We therefore developed automated excitation ratiometric 2-photon imaging. It offers superior sensitivity, spatial resolution, and response dynamics. Redox indicator mice enable quantitative analyses of subcellular redox dynamics in a multitude of preparations and at all postnatal stages. This will uncover cell- and compartment-specific cerebral redox signals and their defined alterations during development, maturation, and aging. Cross-breeding with other disease models will reveal molecular details on compartmental redox homeostasis in neuropathology. Combined with ratiometric 2-photon imaging, this will foster our mechanistic understanding of cellular redox signals in their full complexity. Antioxid. Redox Signal. 25, 41-58.

Redox Indicator Mice Stably Expressing Genetically Encoded Neuronal roGFP: Versatile Tools to Decipher Subcellular Redox Dynamics in Neuropathophysiology

PubMed Central

Wagener, Kerstin C.; Kolbrink, Benedikt; Dietrich, Katharina; Kizina, Kathrin M.; Terwitte, Lukas S.; Kempkes, Belinda; Bao, Guobin

2016-01-01

Abstract Aims: Reactive oxygen species (ROS) and downstream redox alterations not only mediate physiological signaling but also neuropathology. For long, ROS/redox imaging was hampered by a lack of reliable probes. Genetically encoded redox sensors overcame this gap and revolutionized (sub)cellular redox imaging. Yet, the successful delivery of sensor-coding DNA, which demands transfection/transduction of cultured preparations or stereotaxic microinjections of each subject, remains challenging. By generating transgenic mice, we aimed to overcome limiting cultured preparations, circumvent surgical interventions, and to extend effectively redox imaging to complex and adult preparations. Results: Our redox indicator mice widely express Thy1-driven roGFP1 (reduction–oxidation-sensitive green fluorescent protein 1) in neuronal cytosol or mitochondria. Negative phenotypic effects of roGFP1 were excluded and its proper targeting and functionality confirmed. Redox mapping by ratiometric wide-field imaging reveals most oxidizing conditions in CA3 neurons. Furthermore, mitochondria are more oxidized than cytosol. Cytosolic and mitochondrial roGFP1s reliably report cell endogenous redox dynamics upon metabolic challenge or stimulation. Fluorescence lifetime imaging yields stable, but marginal, response ranges. We therefore developed automated excitation ratiometric 2-photon imaging. It offers superior sensitivity, spatial resolution, and response dynamics. Innovation and Conclusion: Redox indicator mice enable quantitative analyses of subcellular redox dynamics in a multitude of preparations and at all postnatal stages. This will uncover cell- and compartment-specific cerebral redox signals and their defined alterations during development, maturation, and aging. Cross-breeding with other disease models will reveal molecular details on compartmental redox homeostasis in neuropathology. Combined with ratiometric 2-photon imaging, this will foster our mechanistic understanding of cellular redox signals in their full complexity. Antioxid. Redox Signal. 25, 41–58. PMID:27059697

Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount, equatorial Indian Ocean: Sources and fractionation

USGS Publications Warehouse

Banakar, V.K.; Hein, J.R.; Rajani, R.P.; Chodankar, A.R.

2007-01-01

The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations (r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5-2) and Pt/Ru ratios (7-28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values ( 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations (r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE (r < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.

An induction furnace for the determination of cadmium in solutions and zinc-base metals by atomic-absorption spectroscopy.

PubMed

Headridge, J B; Smith, D R

1971-03-01

An induction furnace coupled to a Unicam SP90 atomic-absorption spectrophotometer is described for the determination of traces of volatile elements in solutions and volatile matrices. The apparatus has been used to obtain calibration graphs for 1-20 and 50-750 ng of cadmium in microl-volumes of solution, the 228.8 and 326.2 nm resonance lines respectively being used, and to determine cadmium in 5-mg samples of zinc-base metals within the concentration range 5-400 microg g by using the less sensitive 326-2-nm line. A furnace temperature of 1,350 degrees was used. Data on accuracy and precision are presented. The apparatus could readily be used to determine trace elements in volatile materials at concentrations of 10-1000 ng/g .

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

NASA Technical Reports Server (NTRS)

Freund, Friedemann

1991-01-01

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Trace element determination using static high-sensitivity inductively coupled plasma optical emission spectrometry (SHIP-OES).

PubMed

Engelhard, Carsten; Scheffer, Andy; Nowak, Sascha; Vielhaber, Torsten; Buscher, Wolfgang

2007-02-05

A low-flow air-cooled inductively coupled plasma (ICP) design for optical emission spectrometry (OES) with axial plasma viewing is described and an evaluation of its analytical capabilities in trace element determinations is presented. Main advantage is a total argon consumption of 0.6 L min(-1) in contrast to 15 L min(-1) using conventional ICP sources. The torch was evaluated in trace element determinations and studied in direct comparison with a conventional torch under the same conditions with the same OES system, ultrasonic nebulization (USN) and single-element optimization. A variety of parameters (x-y-position of the torch, rf power, external air cooling, gas flow rates and USN operation parameters) was optimized to achieve limits of detection (LOD) which are competitive to those of a conventional plasma source. Ionic to atomic line intensity ratios for magnesium were studied at different radio frequency (rf) power conditions and different sample carrier gas flows to characterize the robustness of the excitation source. A linear dynamic range of three to five orders of magnitude was determined under compromise conditions in multi-element mode. The accuracy of the system was investigated by the determination of Co, Cr, Mn, Zn in two certified reference materials (CRM): CRM 075c (Copper with added impurities), and CRM 281 (Trace elements in rye grass). With standard addition values of 2.44+/-0.04 and 3.19+/-0.21 microg g(-1) for Co and Mn in the CRM 075c and 2.32+/-0.09, 81.8+/-0.4, 32.2+/-3.9 for Cr, Mn and Zn, respectively, were determined in the samples and found to be in good agreement with the reported values; recovery rates in the 98-108% range were obtained. No influence on the analysis by the matrix load in the sample was observed.

Nuclear microscopy in trace-element biology — from cellular studies to the clinic

NASA Astrophysics Data System (ADS)

Lindh, Ulf

1993-05-01

The concentration and distribution of trace and major elements in cells are of great interest in cell biology. PIXE can provide elemental concentrations in the bulk of cells or organelles as other bulk techniques such as atomic absorption spectrophotometry and nuclear activation analysis. Supplementary information, perhaps more exciting, on the intracellular distributions of trace elements can be provided using nuclear microscopy. Intracellular distributions of trace elements in normal and malignant cells are presented. The toxicity of mercury and cadmium can be prevented by supplementation of the essential trace element selenium. Some results from an experimental animal model are discussed. The intercellular distribution of major and trace elements in isolated blood cells, as revealed by nuclear microscopy, provides useful clinical information. Examples are given concerning inflammatory connective-tissue diseases and the chronic fatigue syndrome.

Glow discharge detector

DOEpatents

Koo, Jackson C.; Yu, Conrad M.

2002-01-01

A highly sensitive electronic ion cell for the measurement of trace elements in He carrier gas which involves glow discharge. A constant wave (CW) glow discharge detector which is controlled through a biased resistor, can detect the change of electron density caused by impurities in the He carrier gas by many orders of magnitude larger than that caused by direct ionization or electron capture. The glow discharge detector utilizes a floating pseudo-electrode to form a probe in or near the plasma. By using this probe, the large variation of electron density due to trace amounts of impurities can be directly measured.

Exercise-intensity dependent alterations in plasma redox status do not reflect skeletal muscle redox-sensitive protein signaling.

PubMed

Parker, Lewan; Trewin, Adam; Levinger, Itamar; Shaw, Christopher S; Stepto, Nigel K

2018-04-01

Redox homeostasis and redox-sensitive protein signaling play a role in exercise-induced adaptation. The effects of sprint-interval exercise (SIE), high-intensity interval exercise (HIIE) and continuous moderate-intensity exercise (CMIE), on post-exercise plasma redox status are unclear. Furthermore, whether post-exercise plasma redox status reflects skeletal muscle redox-sensitive protein signaling is unknown. In a randomized crossover design, eight healthy adults performed a cycling session of HIIE (5×4min at 75% W max ), SIE (4×30s Wingate's), and CMIE work-matched to HIIE (30min at 50% of W max ). Plasma hydrogen peroxide (H 2 O 2 ), thiobarbituric acid reactive substances (TBARS), superoxide dismutase (SOD) activity, and catalase activity were measured immediately post, 1h, 2h and 3h post-exercise. Plasma redox status biomarkers were correlated with phosphorylation of skeletal muscle p38-MAPK, JNK, NF-κB, and IκBα protein content immediately and 3h post-exercise. Plasma catalase activity was greater with SIE (56.6±3.8Uml -1 ) compared to CMIE (42.7±3.2, p<0.01) and HIIE (49.0±5.5, p=0.07). Peak plasma H 2 O 2 was significantly (p<0.05) greater after SIE (4.6±0.6nmol/ml) and HIIE (4.1±0.4) compared to CMIE (3.3±0.5). Post-exercise plasma TBARS and SOD activity significantly (p<0.05) decreased irrespective of exercise protocol. A significant positive correlation was detected between plasma catalase activity and skeletal muscle p38-MAPK phosphorylation 3h post-exercise (r=0.40, p=0.04). No other correlations were detected (all p>0.05). Low-volume SIE elicited greater post-exercise plasma catalase activity compared to HIIE and CMIE, and greater H 2 O 2 compared to CMIE. Plasma redox status did not, however, adequately reflect skeletal muscle redox-sensitive protein signaling. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Factors affecting trace element content in periurban market garden subsoil in Yunnan Province, China.

PubMed

Zu, Yanqun; Bock, Laurent; Schvartz, Christian; Colinet, Gilles; Li, Yuan

2011-01-01

Field investigations were conducted to measure subsoil trace element content and factors influencing content in an intensive periurban market garden in Chenggong County, Yunnan Province, South-West China. The area was divided into three different geomorphological units: specifically, mountain (M), transition (T) and lacustrine (L). Mean trace element content in subsoil were determined for Pb (58.2 mg/kg), Cd (0.89 mg/kg), Cu (129.2 mg/kg), and Zn (97.0 mg/kg). Strong significant relationships between trace element content in topsoil and subsoil were observed. Both Pb and Zn were accumulated in topsoil (RTS (ratio of mean trace element in topsoil to subsoil) of Pb and Zn > or =1.0) and Cd and Cu in subsoil (RTS of Cd and Cu < or = 1.0). Subsoil trace element content was related to relief, stoniness, soil color, clay content, and cation exchange capacity. Except for 7.5 YR (yellow-red) color, trace element content increased with color intensity from brown to reddish brown. Significant positive relationships were observed between Fe content and that of Pb and Cu. Trace element content in mountain unit subsoil was higher than in transition and lacustrine units (M > T > L), except for Cu (T > M > L). Mean trace element content in calcareous subsoil was higher than in sandstone and shale. Mean trace element content in clay texture subsoil was higher than in sandy and sandy loam subsoil, and higher Cu and Zn content in subsoil with few mottles. It is possible to model Pb, Cd, Cu, and Zn distribution in subsoil physico-chemical characteristics to help improve agricultural practice.

Trace element exposure of whooper swans (Cygnus cygnus) wintering in a marine lagoon (Swan Lake), northern China.

PubMed

Wang, Feng; Xu, Shaochun; Zhou, Yi; Wang, Pengmei; Zhang, Xiaomei

2017-06-30

Trace element poisoning remains a great threat to various waterfowl and waterbirds throughout the world. In this study, we determined the trace element exposure of herbivorous whooper swans (Cygnus cygnus) wintering in Swan Lake (Rongcheng), an important swan protection area in northern China. A total of 70 samples including abiotic factors (seawater, sediments), food sources (seagrass, macroalgae), feathers and feces of whooper swans were collected from the marine lagoon during the winters of 2014/2015 and 2015/2016. Concentrations of Cu, Zn, Pb, Cr, Cd, Hg and As were determined to investigate the trace element exposure of whooper swans wintering in the area. Results showed that there was an increasing trend in sediment trace element concentrations, compared with historical data. The trace element concentrations in swan feces most closely resembled those of Zostera marina leaves, especially for Cd and Cr. The Zn and Hg concentrations in the swan feces (49.57 and 0.01mg/kg, respectively) were lower than the minimum values reported in the literature for other waterfowls, waterbirds and terrestrial birds. However, the concentrations of the other five trace elements fell within the lower and mediate range of values reported for birds across the world. These results suggest that the whooper swans wintering in Swan Lake, Rongcheng are not suffering severe trace element exposure; however, with the increasing input of trace elements to the lagoon, severe adverse impacts may occur in the future, and we therefore suggest that the input of trace elements to this area should be curbed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heavy Metals and Related Trace Elements.

ERIC Educational Resources Information Center

Leland, Harry V.; And Others

1978-01-01

Presents a literature review of heavy metals and related trace elements in the environment, covering publications of 1976-77. This review includes: (1) trace treatment in natural water and in sediments; and (2) bioaccumulation and toxicity of trace elements. A list of 466 references is presented. (HM)

Feedback Interactions between Trace Metal Nutrients and Phytoplankton in the Ocean

PubMed Central

Sunda, William G.

2012-01-01

In addition to control by major nutrient elements (nitrogen, phosphorus, and silicon) the productivity and species composition of marine phytoplankton communities are also regulated by a number of trace metal nutrients (iron, zinc, cobalt, manganese, copper, and cadmium). Of these, iron is most limiting to phytoplankton growth and has the greatest effect on algal species diversity. It also plays an important role in limiting di-nitrogen (N2) fixation rates, and thus is important in controlling ocean inventories of fixed nitrogen. Because of these effects, iron is thought to play a key role in regulating biological cycles of carbon and nitrogen in the ocean, including the biological transfer of carbon to the deep sea, the so-called biological CO2 pump, which helps regulate atmospheric CO2 and CO2-linked global warming. Other trace metal nutrients (zinc, cobalt, copper, and manganese) have lesser effects on productivity; but may exert an important influence on the species composition of algal communities because of large differences in metal requirements among species. The interactions between trace metals and ocean plankton are reciprocal: not only do the metals control the plankton, but the plankton regulate the distributions, chemical speciation, and cycling of these metals through cellular uptake and recycling processes, downward flux of biogenic particles, biological release of organic chelators, and mediation of redox reactions. This two way interaction has influenced not only the biology and chemistry of the modern ocean, but has had a profound influence on biogeochemistry of the ocean and earth system as a whole, and on the evolution of marine and terrestrial biology over geologic history. PMID:22701115

Meteoritic trace element toxification and the terminal Mesozoic mass extinction

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

Dickson, S.M.; Erickson, D.J. III

1985-01-01

Calculations of trace element fluxes to the earth associated with 5 and 10 kilometer diameter Cl chondrites and iron meteorites are presented. The data indicate that the masses of certain trace elements contained in the bolide, such as Fe, Co, Ni, Cr, Pb, and Cu, are as large as or larger than the world ocean burden. The authors believe that this pulse of trace elements was of sufficient magnitude to perturb the biogeochemical cycles operative 65 million years ago, a probably time of meteorite impact. Geochemical anomalies in Cretaceous-Tertiary boundary sediments suggest that elevated concentrations of trace elements may havemore » persisted for thousands of years in the ocean. Through direct exposure and bioaccumulation, many trophic levels of the global food chain, including that of the dinosaurs, would have been adversely affected by these meteoritic trace elements. The trace element toxification hypothesis may account for the selective extinction of both marine and terrestrial species in the enigmatic terminal Mesozoic event.« less

A Seven-Year Major and Trace Element Study of Rain Water in the Barcés River Watershed, A Coruña, NW Spain

NASA Astrophysics Data System (ADS)

Delgado, Jordi; Cereijo-Arango, José Luis; Juncosa-Rivera, Ricardo

2016-04-01

Precipitation constitutes an important source of soluble materials to surface waters and, in areas where they are diluted precipitation (either dry or wet) it can be the most relevant solute source. Certain trace elements may have a limited natural availability in soils and rocks although they can be important with respect the operation of different biogeochemical cycles, for the computation of local/regional atmospheric pollutant loads or from the global mass budget. In the present study we report the results obtained in a long-lasting (December 2008-December 2015) monitoring survey of the chemical composition of bulk precipitation as monthly-integrated samples taken at the headwaters of the Barcés river watershed (A Coruña, Spain). This location was selected based on the necessity of quantification of the chemical composition and elemental loads associated with the different water types (stream water, ground water and precipitation) contributing to the flooding of the Meirama lake. Available data includes information on meteorological parameters (air temperature, relative humidity, atmospheric pressure, wind speed and direction, total and PAR radiation and precipitation) as well as a wide bundle of physico-chemical (pH, redox, electrical conductivity, alkalinity, Li, Na, K, Mg, Ca, Sr, Mn, Fe, NH4, Cs, Rb, Ba, Zn, Cu, Sb, Ni, Co, Cr, V, Cd, Ag, Pb, Se, Hg, Ti, Sn, U, Mo, F, Cl, Br, SO4, NO3, NO2, Al, As, PO4, SIO2, B, O2, DIC, DOC) and isotopic (18Ov-smow and 2Hv-smow) constituents. The average pH of local precipitation is 5.6 (n=65) which is consistent with the expected value for natural, unpolluted rain water. Most of the studied elements (eg. Na, Ca, K, Mg, SiO2, etc.) shows significant increases in their concentration in the dry period of the year. That points towards a more significant contribution of dry deposition in these periods compared with the wet ones. The average electrical conductivity is about 67 S/cm while the average chloride concentration 8 mg/L. Based on standard normalization procedures, the source of some major and trace precipitation elements have been identified, including sea water, soil and pollution/anthropogenic sources as well as multiyear trends. Available data has allowed also the computation of elemental loads in the studied area.

Biochemical and redox characterization of the mediator complex and its associated transcription factor GeBPL, a GLABROUS1 enhancer binding protein.

PubMed

Shaikhali, Jehad; Davoine, Céline; Brännström, Kristoffer; Rouhier, Nicolas; Bygdell, Joakim; Björklund, Stefan; Wingsle, Gunnar

2015-06-15

The eukaryotic mediator integrates regulatory signals from promoter-bound transcription factors (TFs) and transmits them to RNA polymerase II (Pol II) machinery. Although redox signalling is important in adjusting plant metabolism and development, nothing is known about a possible redox regulation of mediator. In the present study, using pull-down and yeast two-hybrid assays, we demonstrate the association of mediator (MED) subunits MED10a, MED28 and MED32 with the GLABROUS1 (GL1) enhancer-binding protein-like (GeBPL), a plant-specific TF that binds a promoter containing cryptochrome 1 response element 2 (CryR2) element. All the corresponding recombinant proteins form various types of covalent oligomers linked by intermolecular disulfide bonds that are reduced in vitro by the thioredoxin (TRX) and/or glutathione/glutaredoxin (GRX) systems. The presence of recombinant MED10a, MED28 and MED32 subunits or changes of its redox state affect the DNA-binding capacity of GeBPL suggesting that redox-driven conformational changes might modulate its activity. Overall, these results advance our understanding of how redox signalling affects transcription and identify mediator as a novel actor in redox signalling pathways, relaying or integrating redox changes in combination with specific TFs as GeBPL. © The Authors Journal compilation © 2015 Biochemical Society.

Redox regulation of neuronal voltage-gated calcium channels.

PubMed

Todorovic, Slobodan M; Jevtovic-Todorovic, Vesna

2014-08-20

Voltage-gated calcium channels are ubiquitously expressed in neurons and are key regulators of cellular excitability and synaptic transmitter release. There is accumulating evidence that multiple subtypes of voltage-gated calcium channels may be regulated by oxidation and reduction. However, the redox mechanisms involved in the regulation of channel function are not well understood. Several studies have established that both T-type and high-voltage-activated subtypes of voltage-gated calcium channel can be redox-regulated. This article reviews different mechanisms that can be involved in redox regulation of calcium channel function and their implication in neuronal function, particularly in pain pathways and thalamic oscillation. A current critical issue in the field is to decipher precise mechanisms of calcium channel modulation via redox reactions. In this review we discuss covalent post-translational modification via oxidation of cysteine molecules and chelation of trace metals, and reactions involving nitric oxide-related molecules and free radicals. Improved understanding of the roles of redox-based reactions in regulation of voltage-gated calcium channels may lead to improved understanding of novel redox mechanisms in physiological and pathological processes. Identification of redox mechanisms and sites on voltage-gated calcium channel may allow development of novel and specific ion channel therapies for unmet medical needs. Thus, it may be possible to regulate the redox state of these channels in treatment of pathological process such as epilepsy and neuropathic pain.

Copper complexes as a source of redox active MRI contrast agents.

PubMed

Dunbar, Lynsey; Sowden, Rebecca J; Trotter, Katherine D; Taylor, Michelle K; Smith, David; Kennedy, Alan R; Reglinski, John; Spickett, Corinne M

2015-10-01

The study reports an advance in designing copper-based redox sensing MRI contrast agents. Although the data demonstrate that copper(II) complexes are not able to compete with lanthanoids species in terms of contrast, the redox-dependent switch between diamagnetic copper(I) and paramagnetic copper(II) yields a novel redox-sensitive contrast moiety with potential for reversibility.

Vascular remodeling: A redox-modulated mechanism of vessel caliber regulation.

PubMed

Tanaka, Leonardo Y; Laurindo, Francisco R M

2017-08-01

Vascular remodeling, i.e. whole-vessel structural reshaping, determines lumen caliber in (patho)physiology. Here we review mechanisms underlying vessel remodeling, with emphasis in redox regulation. First, we discuss confusing terminology and focus on strictu sensu remodeling. Second, we propose a mechanobiological remodeling paradigm based on the concept of tensional homeostasis as a setpoint regulator. We first focus on shear-mediated models as prototypes of remodeling closely dominated by highly redox-sensitive endothelial function. More detailed discussions focus on mechanosensors, integrins, extracellular matrix, cytoskeleton and inflammatory pathways as potential of mechanisms potentially coupling tensional homeostasis to redox regulation. Further discussion of remodeling associated with atherosclerosis and injury repair highlights important aspects of redox vascular responses. While neointima formation has not shown consistent responsiveness to antioxidants, vessel remodeling has been more clearly responsive, indicating that despite the multilevel redox signaling pathways, there is a coordinated response of the whole vessel. Among mechanisms that may orchestrate redox pathways, we discuss roles of superoxide dismutase activity and extracellular protein disulfide isomerase. We then discuss redox modulation of aneurysms, a special case of expansive remodeling. We propose that the redox modulation of vascular remodeling may reflect (1) remodeling pathophysiology is dominated by a particularly redox-sensitive cell type, e.g., endothelial cells (2) redox pathways are temporospatially coordinated at an organ level across distinct cellular and acellular structures or (3) the tensional homeostasis setpoint is closely connected to redox signaling. The mechanobiological/redox model discussed here can be a basis for improved understanding of remodeling and helps clarifying mechanisms underlying prevalent hard-to-treat diseases. Copyright © 2017 Elsevier Inc. All rights reserved.

Physiological and proteome study of sunflowers exposed to a polymetallic constraint.

PubMed

Printz, Bruno; Sergeant, Kjell; Guignard, Cedric; Renaut, Jenny; Hausman, Jean-Francois

2013-06-01

The new energy requirements of the growing world population together with the actual ecological trend of phytoremediation have made challenging the cultivation of energetic crops on nonagricultural lands, such as those contaminated with trace elements. In this study, phenotypical characterization and biochemical analyses were combined to emphasize the global response of young sunflowers (Helianthus annuus L.) grown in hydroponic media contaminated with different Cd, Ni, and Zn concentrations. Leaves and roots of sunflowers reaching the stage "2-extended leaves" and exposed to different trace metal concentrations were harvested and analyzed by 2D-DIGE in order to study in depth the molecular responses of the young plants upon the polymetallic exposure. Proteomics confirmed the observed global reduction in growth and development. If photosynthetic light reactions and carbon metabolism were the most affected in leaves, in roots significant disruptions were observed in proteins involved in respiration, oxidative balance, protein and gene expression, and in the induction of programmed cell death. Elemental analyses of the plantlets indicated a profound impact of the treatment resulting in misbalance in essential micronutrients. Altogether, this study highlights the sensitivity of the sunflower to a polymetallic pollution and indicates that its use as a remediative tool of trace element polluted soils is limited. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

INAA Application for Trace Element Determination in Biological Reference Material

NASA Astrophysics Data System (ADS)

Atmodjo, D. P. D.; Kurniawati, S.; Lestiani, D. D.; Adventini, N.

2017-06-01

Trace element determination in biological samples is often used in the study of health and toxicology. Determination change to its essentiality and toxicity of trace element require an accurate determination method, which implies that a good Quality Control (QC) procedure should be performed. In this study, QC for trace element determination in biological samples was applied by analyzing the Standard Reference Material (SRM) Bovine muscle 8414 NIST using Instrumental Neutron Activation Analysis (INAA). Three selected trace element such as Fe, Zn, and Se were determined. Accuracy of the elements showed as %recovery and precision as %coefficient of variance (%CV). The result showed that %recovery of Fe, Zn, and Se were in the range between 99.4-107%, 92.7-103%, and 91.9-112%, respectively, whereas %CV were 2.92, 3.70, and 5.37%, respectively. These results showed that INAA method is precise and accurate for trace element determination in biological matrices.

Elemental weathering fluxes and saprolite production rate in a Central African lateritic terrain (Nsimi, South Cameroon)

NASA Astrophysics Data System (ADS)

Braun, Jean-Jacques; Marechal, Jean-Christophe; Riotte, Jean; Boeglin, Jean-Loup; Bedimo Bedimo, Jean-Pierre; Ndam Ngoupayou, Jules Remy; Nyeck, Brunot; Robain, Henri; Sekhar, M.; Audry, Stéphane; Viers, Jérôme

2012-12-01

The comparison between contemporary and long-term weathering has been carried out in the Small Experimental Watershed (SEW) of Nsimi, South Cameroon in order to quantify the export fluxes of major and trace elements and the residence time of the lateritic weathering cover. We focus on the hillside system composed of a thick lateritic weathering cover topped by a soil layer. This study is built on the recent improvements of the hillside hydrological functioning and on the analyses of major and trace elements. The mass balance calculation at the weathering horizon scale performed with the parent rock as reference indicates (i) strong depletion profiles for alkalis (Na, K, Rb) and alkaline earths (Mg, Ca, Sr, Ba), (ii) moderate depletion profiles for Si, P, Cd, Cu, Zn, Ni and Co, (iii) depletion/enrichment profiles for Al, Ga, Ge, Sn, Pb, LREE, HREE, Y, U, Fe, V, Cr, Mn. It is noteworthy that (i) Mn and Ce are not significantly redistributed according to oxidative processes as it is the case for Fe, V and Cr, and (ii) Ge is fractionated compared to silica with enrichment in Fe-rich horizons. The calculations performed for the topsoil with iron crust as parent material reference reveal that the degradation of the iron crust is accompanied by the loss of most of the constituting elements, among which are those specifically accumulated as the redox sensitive elements (Fe, V, Cr) and iron oxide related elements like Th. The overall current elemental fluxes from the hillside system at the springs and the seepage zones are extremely low due to the inert lateritic mineralogy. Ninety-four percent of the whole Na flux generated from the hillside corrected from atmospheric deposits (77 mol/ha/yr) represents the current weathering rates of plagioclase (oligoclase) in the system, the other remaining 6% may be attributed to the dissolution of hornblende. The silica hillside flux is 300 mol/ha/yr and can be mostly attributed to the plagioclase and kaolinite dissolution. Al and Ga are exported from the lateritic regolith and maybe due to the dissolution of kaolinite crystals. Compared to the other immobile elements (Zr, Hf, Nb and Th), Ti is significantly exported. Among redox-sensitive elements (Fe, V, Cr, Mn, Ce), only Ce and Mn are exported out of the hillside system. The other elements (Fe, V, Cr) are likely able to be mobilized but over a short distance only. Rb, Sr, Ba, Ni, Cu, Zn are affected by export processes. LREE and Y are exported but in very low amounts (in the range from μmol/ha/yr to mmol/ha/yr) while HREE and U are exported in negligible quantities. A first attempt is carried out to compare the mature ridge top profile from Nsimi SEW with the immature ridge top weathering profile from the Mule Hole SEW (South India), developed on similar granodioritic basement, in order to get deeper insight into (i) the contemporary saprolite production rates and (ii) the combined effect of precipitation (in terms of Mean Annual Rainfall, MAR) and evapotranspiration on the aggressiveness of the draining solutions. Considering (i) the contemporary Na flux as representative of the dissolution of plagioclase crystals and conservative during saprolitization processes and (ii) steady state of the inter-annual recharge (R) over a 10 years period, the current saprolite production rates (σr) are of 22 mm/kyr for Mule Hole SEW and 2 mm/kyr for Nsimi SEW, respectively. Even with a very low R/MAR ratio (0.04) compared to Nsimi, the chemical weathering at Mule Hole is active and related to the groundwater exports. At Mule Hole, plagioclase crystals are still present in the saprolite and the soil cover leading to a diffuse weathering front. The high Nsimi R/MAR ratio (0.2) allows the solution to be still aggressive with respect to the plagioclase and other weatherable minerals at the bedrock interface resulting in their complete breakdown in a few centimetres (sharp weathering front) leading to a mature saprolite. For the Nsimi SEW, if we consider (i) the low contemporary saprolite production rate (2 mm/kyr), (ii) the Miocene age (average 15 Myr) of the South Cameron Plateau landscape and (ii) the limited movement of Africa continent since Eocene, the long term saprolite production rate should have remained in its lower range, from 2 to 10 m/Myr. This suggests that, for thick weathering profiles the migration of the weathering front into the bedrock occurs at a relatively uniform rate regardless of present-day climatic conditions. Climate variation leading to the alternation of setup of savanna or humid forest will have an effect on physical erosion rather than chemical erosion for such deep weathering profiles.

ICPMS analysis of proteins separated by Native-PAGE: Evaluation of metaloprotein profiles in human synovial fluid with acute and chronic arthritis.

PubMed

Moyano, Mario F; Mariño-Repizo, Leonardo; Tamashiro, Héctor; Villegas, Liliana; Acosta, Mariano; Gil, Raúl A

2016-07-01

The role of trace elements bound to proteins in the etiology and pathogenesis of rheumatoid arthritis (RA) remains unclear. In this sense, the identification and detection of metalloproteins has a strong and growing interest. Metalloprotein studies are currently carried out by polyacrylamide gel electrophoresis (PAGE) associated to inductively coupled plasma mass spectrometry (ICPMS), and despite that complete information can be obtained for metals such as Fe, Cu and Zn, difficulties due to poor sensitivity for other trace elements such as Sn, As, etc, are currently faced. In the present work, a simple and fast method for the determination of trace metals bound to synovial fluid (SF) proteins was optimized. Proteins from SF (long and short-term RA) were separated in ten fractions by native PAGE, then dissolved in nitric acid and peroxide hydrogen, and analyzed by ICPMS. Fifteen metals were determined in each separated protein fraction (band). Adequate calibration of proteins molecular weight allowed stablishing which protein type were bound to different metals. Copyright © 2016 Elsevier GmbH. All rights reserved.

New insights into trace element wet deposition in the Himalayas: amounts, seasonal patterns, and implications.

PubMed

Cong, Zhiyuan; Kang, Shichang; Zhang, Yulan; Gao, Shaopeng; Wang, Zhongyan; Liu, Bin; Wan, Xin

2015-02-01

Our research provides the first complete year-long dataset of wet deposition of trace elements in the high Himalayas based on a total of 42 wet deposition events on the northern slope of Mt. Qomolangma (Everest). Except for typical crustal elements (Al, Fe, and Mn), the concentration level of most trace elements (Sc, V, Cr, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Cs, Pb, Bi, and U) are generally comparable to those preserved in snow pits and ice cores from the nearby East Rongbuk Glacier. Cadmium was the element most affected by anthropogenic emissions. No pronounced seasonal variations are observed for most trace elements despite different transport pathways. In our study, the composition of wet precipitation reflects a regional background condition and is not clearly related to specific source regions. For the trace element record from ice cores and snow pits in the Himalayas, it could be deduced that the pronounced seasonal patterns were caused by the dry deposition of trace elements (aerosols) during their long exposure to the atmosphere after precipitation events. Our findings are of value for the understanding of the trace element deposition mechanisms in the Himalayas.

NASA Redox system development project status

NASA Technical Reports Server (NTRS)

Nice, A. W.

1981-01-01

NASA-Redox energy storage systems developed for solar power applications and utility load leveling applications are discussed. The major objective of the project is to establish the technology readiness of Redox energy storage for transfer to industry for product development and commercialization by industry. The approach is to competitively contract to design, build, and test Redox systems progressively from preprototype to prototype multi-kW and megawatt systems and conduct supporting technology advancement tasks. The Redox electrode and membrane are fully adequate for multi-kW solar related applications and the viability of the Redox system technology as demonstrated for multi-kW solar related applications. The status of the NASA Redox Storage System Project is described along with the goals and objectives of the project elements.

Linking major and trace element headwater stream concentrations to DOC release and hydrologic conditions in a bog and peaty riparian zone

NASA Astrophysics Data System (ADS)

Broder, Tanja; Biester, Harald

2017-04-01

Peatlands and organic-rich riparian zones are known to export large amounts of dissolved organic carbon (DOC) to surface water. In organic-rich, acidic headwater streams main carriers for element export are dissolved organic matter (DOM) and organic-iron complexes. In this environment DOM might also act as major carrier for metals, which otherwise may have a low solubility. This study examines annual and short term event-based variations of major and trace elements in a headwater catchment. Patterns are used to trace hydrological pathways and element sources under different hydrologic preconditions. Furthermore, it elucidates the importance of DOC as carrier of different elements in a bog and a peaty riparian catchment. The study was conducted in a small headwater stream draining an ombrotrophic peatland with an adjacent forested area with peaty riparian soils in the Harz Mountains (Germany). Discharge sampling was conducted weekly at two sites from snowmelt to begin of snowfall and in high resolution during selected discharge events in 2013 and 2014. Element concentrations were measured by means of ICP-MS and ICP-OES. A PCA was performed for each site and for annual and event datasets. Results show that a large number of element concentrations strongly correlate with DOC concentrations at the bog site. Even elements like Ca and Mg, which are known to have a low affinity to DOC. Congruently, the first principal component integrates the DOC pattern (element loadings > 0.8: Ca, Fe, Mg, Mn, Zn, As, Sr, Cd, DOC) and explained about 35 % of total variance and even 50 % during rain events (loadings > 0.8: Al, Ca, Fe, Mg, Mn, Zn, Li, Co, As, Sr, Cd, Pb, DOC). The study cannot verify that all correlating elements bind to DOC. It is likely that also a common mobilization pattern in the upper peat layer by plant decomposition causes the same response to changes in hydrologic pathways. Additionally, a low mineral content and an enrichment of elements like Fe and Mn in the upper peat layers due to prevailing redox conditions might play a major role in a bog environment. At the peaty riparian zone only Ca, Fe, and Sr strongly correlated with DOC over the annual record. The PCA of the annual record display no clear DOC component here, but indicates that DOC is influenced by Component one (element loadings > 0.8: Ca, Mg, Zn, Co, Sr) and two (Al, V, La, Pb, U) suggesting different DOC sources in the peaty riparian zone. A large number of elements correlate with DOC during rain event sampling at the riparian zone. In contrast to the bog site the event-based riparian zone PCA distinguished a clear discharge related component with mineral, groundwater related elements (K, Rb, In, Cs, NO3- and SO42-). Pattern of the mineral and DOC components prove that during base flow discharge is generated in a shallow groundwater layer and successively increases upward to the organic-rich upper soil layer with increasing discharge. Contrarily, bog element pattern confirm a dominating surface-near discharge, due to high hydraulic conductivities.

Thiol-based Redox Proteins in Brassica napus Guard Cell Abscisic Acid and Methyl Jasmonate Signaling

PubMed Central

Zhu, Mengmeng; Zhu, Ning; Song, Wen-yuan; Harmon, Alice C.; Assmann, Sarah M.; Chen, Sixue

2014-01-01

SUMMARY Reversibly oxidized cysteine sulfhydryl groups serve as redox sensors or targets of redox sensing that are important in different physiological processes. Little is known, however, about redox sensitive proteins in guard cells and how they function in stomatal signaling. In this study, Brassica napus guard cell proteins altered by redox in response to abscisic acid (ABA) or methyl jasmonate (MeJA) were identified by complementary proteomics approaches, saturation differential in-gel electrophoresis (DIGE) and isotope-coded affinity tag (ICAT). In total, 65 and 118 potential redox responsive proteins were identified in ABA and MeJA treated guard cells, respectively. All the proteins contain at least one cysteine, and over half of them are predicted to form intra-molecular disulfide bonds. Most of the proteins fall into the functional groups of energy, stress and defense, and metabolism. Based on the peptide sequences identified by mass spectrometry, 30 proteins were common to ABA and MeJA treated samples. A total of 44 cysteines was mapped in all the identified proteins, and their levels of redox sensitivity were quantified. Two of the proteins, a SNRK2 kinase and an isopropylmalate dehydrogenase were confirmed to be redox regulated and involved in stomatal movement. This study creates an inventory of potential redox switches, and highlights a protein redox regulatory mechanism in guard cell ABA and MeJA signal transduction. PMID:24580573

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.

Redox Regulation of Neuronal Voltage-Gated Calcium Channels

PubMed Central

Jevtovic-Todorovic, Vesna

2014-01-01

Abstract Significance: Voltage-gated calcium channels are ubiquitously expressed in neurons and are key regulators of cellular excitability and synaptic transmitter release. There is accumulating evidence that multiple subtypes of voltage-gated calcium channels may be regulated by oxidation and reduction. However, the redox mechanisms involved in the regulation of channel function are not well understood. Recent Advances: Several studies have established that both T-type and high-voltage-activated subtypes of voltage-gated calcium channel can be redox-regulated. This article reviews different mechanisms that can be involved in redox regulation of calcium channel function and their implication in neuronal function, particularly in pain pathways and thalamic oscillation. Critical Issues: A current critical issue in the field is to decipher precise mechanisms of calcium channel modulation via redox reactions. In this review we discuss covalent post-translational modification via oxidation of cysteine molecules and chelation of trace metals, and reactions involving nitric oxide-related molecules and free radicals. Improved understanding of the roles of redox-based reactions in regulation of voltage-gated calcium channels may lead to improved understanding of novel redox mechanisms in physiological and pathological processes. Future Directions: Identification of redox mechanisms and sites on voltage-gated calcium channel may allow development of novel and specific ion channel therapies for unmet medical needs. Thus, it may be possible to regulate the redox state of these channels in treatment of pathological process such as epilepsy and neuropathic pain. Antioxid. Redox Signal. 21, 880–891. PMID:24161125

Hydrothermal Links Between the Caribbean Plateau and OAE2

NASA Astrophysics Data System (ADS)

Duncan, R. A.; Snow, L. J.

2003-12-01

A popular current model for the sporadic occurrence of ocean anoxic events (OAEs) in the Cretaceous ties hydrothermally-induced changes in ocean chemistry (bio-limiting trace metals) during ocean plateau (LIP) volcanism to increased surface productivity, followed by mid-to-deep water oxygen depletion and accumulation of organic-rich sediments. This proposed connection is far from accepted, and important unresolved aspects include the timing of events and yet-to-be-proved synchroneity of volcanism and OAEs, the sensitivity of phytoplankton to bio-limiting (and toxic) trace metals, the difference in biotic responses at various OAEs, and the source of the hydrothermal inputs (sea floor spreading centers or ocean plateaus). To test this hypothesis we have measured the distribution of major, minor and trace element abundances in five pelagic carbonate and black shale sequences that bracket the OAE2, defined by a prominent positive excursion in the global seawater d13C record. Sedimentary sections at Rock Creek Canyon (Pueblo, CO), ODP Site 1138 (Kerguelen Plateau), Bass River (NJ), Totuma well (Venezuela) and Baranca el Canyon (Mexico) were chosen to examine potential trace metal patterns and gradients around the proposed source of hydrothermal inputs - the Caribbean Plateau, whose initial volcanic activity has been dated at 93-89 Ma. ICP-AES and ICP-MS elemental abundances from whole rock samples are normalized to Zr to remove the effect of terrestrial inputs. We find prominent trace metal "spikes" (up to 50 times background) for elements known to be concentrated in volatile degassing of magmas and in hydrothermal plumes resulting from seawater-rock reactions. These anomalies begin at the onset and continue well into the d13C excusion at all five sites. Furthermore, the magnitude of the anomalies decreases with distance from the Caribbean region, and the pattern of elements shifts from a wide range of metals near-source to predominantly long residence time metals far "downstream".

The effect of tissue structure and soil chemistry on trace element uptake in fossils

NASA Astrophysics Data System (ADS)

Hinz, Emily A.; Kohn, Matthew J.

2010-06-01

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H 2O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO 3. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element "plumes" down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ˜5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients ( Kd's). Although acid leaches and bulk digestion of soils yield comparable fossil-soil Kd's among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H 2O leachates instead reveal radically different Kd's in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE Kd's and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading Kd's for many trace elements, especially the REE, and H 2O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.

A Global Overview of Exposure Levels and Biological Effects of Trace Elements in Penguins.

PubMed

Espejo, Winfred; Celis, José E; GonzÃlez-Acuña, Daniel; Banegas, Andiranel; Barra, Ricardo; Chiang, Gustavo

2018-01-01

Trace elements are chemical contaminants that can be present almost anywhere on the planet. The study of trace elements in biotic matrices is a topic of great relevance for the implications that it can have on wildlife and human health. Penguins are very useful, since they live exclusively in the Southern Hemisphere and represent about 90% of the biomass of birds of the Southern Ocean. The levels of trace elements (dry weight) in different biotic matrices of penguins were reviewed here. Maps of trace element records in penguins were included. Data on exposure and effects of trace elements in penguins were collected from the literature. The most reported trace elements in penguins are aluminum, arsenic, cadmium, lead, mercury, copper, zinc, and manganese. Trace elements have been measured in 11 of the 18 species of penguins. The most studied biotic matrices are feathers and excreta. Most of the studies have been performed in Antarctica and subantarctic Islands. Little is known about the interaction among metals, which could provide better knowledge about certain mechanisms of detoxification in penguins. Future studies of trace elements in penguins must incorporate other metals such as vanadium, cobalt, nickel, and chromium. Data of metals in the species such as Eudyptes pachyrhynchus, Eudyptes moseleyi, Eudyptes sclateri, Eudyptes robustus, Eudyptes schlegeli, Spheniscus demersus, Spheniscus mendiculus, and Megadyptes antipodes are urged. It is important to correlate levels of metals in different biotic matrices with the effects on different species and in different geographic locations.

Trace element supplementation in the biogas production from wheat stillage--optimization of metal dosing.

PubMed

Schmidt, Thomas; Nelles, Michael; Scholwin, Frank; Pröter, Jürgen

2014-09-01

A trace element dosing strategy for the anaerobic digestion of wheat stillage was developed in this study. Mesophilic CSTR reactors were operated with the sulfuric substrate wheat stillage in some cases under trace element deficiency. After supplementing trace elements during the start-up, one of the elements of Fe, Ni, Co, Mo, and W were depleted in one digester while still augmenting the other elements to determine minimum requirements for each element. The depletion of Fe and Ni resulted in a rapid accumulation of volatile fatty acids while Co and W seem to have a long-term effect. Based on the results it was possible to reduce the dosing of trace elements, which is positive with reference to economic and environmental aspects. Copyright © 2014 Elsevier Ltd. All rights reserved.

Redox storage systems for solar applications

NASA Technical Reports Server (NTRS)

Hagedorn, N. H.; Thaller, L. H.

1980-01-01

The NASA Redox energy storage system is described. The system is based on soluble aqueous iron and chromium chloride redox couples. The needed technology advances in the two elements (electrodes and membranes) that are key to its technological feasibility have been achieved and system development has begun. The design, construction, and test of a 1 kilowatt system integrated with a solar photovoltaic array is discussed.

Highly sensitive measurement of whole blood chromium by inductively coupled plasma mass spectrometry.

PubMed

Cieslak, Wendy; Pap, Kathleen; Bunch, Dustin R; Reineks, Edmunds; Jackson, Raymond; Steinle, Roxanne; Wang, Sihe

2013-02-01

Chromium (Cr), a trace metal element, is implicated in diabetes and cardiovascular disease. A hypochromic state has been associated with poor blood glucose control and unfavorable lipid metabolism. Sensitive and accurate measurement of blood chromium is very important to assess the chromium nutritional status. However, interferents in biological matrices and contamination make the sensitive analysis challenging. The primary goal of this study was to develop a highly sensitive method for quantification of total Cr in whole blood by inductively coupled plasma mass spectrometry (ICP-MS) and to validate the reference interval in a local healthy population. This method was developed on an ICP-MS with a collision/reaction cell. Interference was minimized using both kinetic energy discrimination between the quadrupole and hexapole and a selective collision gas (helium). Reference interval was validated in whole blood samples (n=51) collected in trace element free EDTA tubes from healthy adults (12 males, 39 females), aged 19-64 years (38.8±12.6), after a minimum of 8 h fasting. Blood samples were aliquoted into cryogenic vials and stored at -70 °C until analysis. The assay linearity was 3.42 to 1446.59 nmol/L with an accuracy of 87.7 to 99.8%. The high sensitivity was achieved by minimization of interference through selective kinetic energy discrimination and selective collision using helium. The reference interval for total Cr using a non-parametric method was verified to be 3.92 to 7.48 nmol/L. This validated ICP-MS methodology is highly sensitive and selective for measuring total Cr in whole blood. Copyright © 2012 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved. Published by Elsevier Inc. All rights reserved.

Electrode Reactions Coupled with Chemical Reactions of Oxygen, Water and Acetaldehyde in an Ionic Liquid: New Approaches for Sensing Volatile Organic Compounds.

PubMed

Chi, Xiaowei; Tang, Yongan; Zeng, Xiangqun

2016-10-20

Water and oxygen are ubiquitous present in ambient conditions. This work studies the unique oxygen, trace water and a volatile organic compound (VOC) acetaldehyde redox chemistry in a hydrophobic and aprotic ionic liquid (IL), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([Bmpy] [NTf 2 ]) by cyclic voltammetry and potential step methods. One electron oxygen reduction leads to superoxide radical formation in the IL. Trace water in the IL acts as a protic species that reacts with the superoxide radical. Acetaldehyde is a stronger protic species than water for reacting with the superoxide radical. The presence of trace water in the IL was also demonstrated to facilitate the electro-oxidation of acetaldehyde, with similar mechanism to that in the aqueous solutions. A multiple-step coupling reaction mechanism between water, superoxide radical and acetaldehyde has been described. The unique characteristics of redox chemistry of acetaldehyde in [Bmpy][NTf 2 ] in the presence of oxygen and trace water can be controlled by electrochemical potentials. By controlling the electrode potential windows, several methods including cyclic voltammetry, potential step methods (single-potential, double-potential and triple-potential step methods) were established for the quantification of acetaldehyde. Instead of treating water and oxygen as frustrating interferents to ILs, we found that oxygen and trace water chemistry in [Bmpy][NTf 2 ] can be utilized to develop innovative electrochemical methods for electroanalysis of acetaldehyde.

Electrode Reactions Coupled with Chemical Reactions of Oxygen, Water and Acetaldehyde in an Ionic Liquid: New Approaches for Sensing Volatile Organic Compounds

PubMed Central

Chi, Xiaowei; Tang, Yongan; Zeng, Xiangqun

2017-01-01

Water and oxygen are ubiquitous present in ambient conditions. This work studies the unique oxygen, trace water and a volatile organic compound (VOC) acetaldehyde redox chemistry in a hydrophobic and aprotic ionic liquid (IL), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([Bmpy] [NTf2]) by cyclic voltammetry and potential step methods. One electron oxygen reduction leads to superoxide radical formation in the IL. Trace water in the IL acts as a protic species that reacts with the superoxide radical. Acetaldehyde is a stronger protic species than water for reacting with the superoxide radical. The presence of trace water in the IL was also demonstrated to facilitate the electro-oxidation of acetaldehyde, with similar mechanism to that in the aqueous solutions. A multiple-step coupling reaction mechanism between water, superoxide radical and acetaldehyde has been described. The unique characteristics of redox chemistry of acetaldehyde in [Bmpy][NTf2] in the presence of oxygen and trace water can be controlled by electrochemical potentials. By controlling the electrode potential windows, several methods including cyclic voltammetry, potential step methods (single-potential, double-potential and triple-potential step methods) were established for the quantification of acetaldehyde. Instead of treating water and oxygen as frustrating interferents to ILs, we found that oxygen and trace water chemistry in [Bmpy][NTf2] can be utilized to develop innovative electrochemical methods for electroanalysis of acetaldehyde. PMID:29142331

Loess as an environmental archive of atmospheric trace element deposition

NASA Astrophysics Data System (ADS)

Blazina, T.; Winkel, L. H.

2013-12-01

Environmental archives such as ice cores, lake sediment cores, and peat cores have been used extensively to reconstruct past atmospheric deposition of trace elements. These records have provided information about how anthropogenic activities such as mining and fossil fuel combustion have disturbed the natural cycles of various atmospherically transported trace elements (e.g. Pb, Hg and Se). While these records are invaluable for tracing human impacts on such trace elements, they often provide limited information about the long term natural cycles of these elements. An assumption of these records is that the observed variations in trace element input, prior to any assumed anthropogenic perturbations, represent the full range of natural variations. However, records such as those mentioned above which extend back to a maximum of ~400kyr may not capture the potentially large variations of trace element input occurring over millions of years. Windblown loess sediments, often representing atmospheric deposition over time scales >1Ma, are the most widely distributed terrestrial sediments on Earth. These deposits have been used extensively to reconstruct continental climate variability throughout the Quaternary and late Neogene periods. In addition to being a valuable record of continental climate change, loess deposits may represent a long term environmental archive of atmospheric trace element deposition and may be combined with paleoclimate records to elucidate how fluctuations in climate have impacted the natural cycle of such elements. Our research uses the loess-paleosol deposits on the Chinese Loess Plateau (CLP) to quantify how atmospheric deposition of trace elements has fluctuated in central China over the past 6.8Ma. The CLP has been used extensively to reconstruct past changes of East Asian monsoon system (EAM). We present a suite of trace element concentration records (e.g. Pb, Hg, and Se) from the CLP which exemplifies how loess deposits can be used as an environmental archive to reconstruct long term natural variations in atmospheric trace element input. By comparing paleomonsoon proxy data with geochemical data we can directly correlate variations in atmospheric trace element input to fluctuations in the EAM. For example we are able to link Se input into the CLP to EAM derived precipitation. In interglacial climatic periods from 2.3-1.56Ma and 1.50-1.29Ma, we find very strong positive correlations between Se concentration and the summer monsoon index, a proxy for effective precipitation. In later interglacial periods from 1.26-0.83Ma and 0.78-0.16Ma, we find dust input plays a greater role. Our findings demonstrate that the CLP is a valuable environmental archive of atmospheric trace element deposition and suggest that other loess deposits worldwide may serve as useful records for investigating long term natural variations in atmospheric trace element cycling.

Serum Concentrations of Trace Elements in Patients with Tuberculosis and Its Association with Treatment Outcome

PubMed Central

Choi, Rihwa; Kim, Hyoung-Tae; Lim, Yaeji; Kim, Min-Ji; Kwon, O Jung; Jeon, Kyeongman; Park, Hye Yun; Jeong, Byeong-Ho; Koh, Won-Jung; Lee, Soo-Youn

2015-01-01

Deficiencies in essential trace elements are associated with impaired immunity in tuberculosis infection. However, the trace element concentrations in the serum of Korean patients with tuberculosis have not yet been investigated. This study aimed to compare the serum trace element concentrations of Korean adult patients with tuberculosis with noninfected controls and to assess the impact of serum trace element concentration on clinical outcome after antituberculosis treatment. The serum concentrations of four trace elements in 141 consecutively recruited patients with tuberculosis and 79 controls were analyzed by inductively coupled plasma-mass spectrometry. Demographic characteristics were also analyzed. Serum cobalt and copper concentrations were significantly higher in patients with tuberculosis compared with controls, while zinc and selenium concentrations were significantly lower (p < 0.01). Moreover, serum selenium and zinc concentrations were positively correlated (ρ = 0.41, p < 0.05). A high serum copper concentration was associated with a worse clinical outcome, as assessed after one month of antituberculosis therapy. Specifically, culture-positive patients had higher serum copper concentrations than culture-negative patients (p < 0.05). Patients with tuberculosis had altered serum trace element concentrations. Further research is needed to elucidate the roles of individual trace elements and to determine their clinical impact on patients with tuberculosis. PMID:26197334

Understanding the evolution of S- and I-type granitic plutons through analysis of apatite.

NASA Astrophysics Data System (ADS)

Hess, B. L.; Fiege, A.; Tailby, N.

2017-12-01

The major and trace element composition of apatites from the Lachlan fold belt (LFB) S- and I-type granitoids (Australia) and the Central French Massif (CFM) S-type leucogranites (France) were analyzed to investigate their compositional and redox variation. Apatite is a common accessory mineral in magmatic systems that can incorporate a variety of trace elements, including the polyvalent elements sulfur (S), iron (Fe), and manganese (Mn). It was recently discovered that apatite can incorporate three oxidation states of S (S6+, S4+, S2-) into its structure as a function of oxygen fugacity [1]. However, the oxidation states of Mn and Fe in apatite are essentially unknown (2+ and/or 3+). In this study, we collected many electron probe line transects across apatites in several different host phases from a variety of S- and I-type plutons. The F-H-Cl contents of the S- and I-type LFB samples were similar ( 2.9 wt% F, 0.4 wt% Cl, 0.5 wt% OH). The CFM S-types contained virtually no Cl and ranged from near-endmember OH-apatite to near-endmember F-apatite. The apatites of all studied the S- and I-type plutons are characterized by similar ranges of Fe content (<1.5 wt% Fe), while Mn reaches much higher concentrations in the S-type when compared to I-type apatites (<6.5 wt% Mn). The S content of the apatites varies significantly, from <50 ppm S in the LFB S-types, up to 2,000 ppm S in the LFB I-types, and reaching 1,650 ppm S in the CFM S-types. The elevated S contents in the LFB I-type and CFM S-type apatites allowed us to measure the S oxidation states by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra show variability in S oxidation states ranging from mostly sulfate down to nearly equal S6+/S2- ratios, indicating redox variations during apatite formation. The S-type Mn + Fe content plots in a 1:1 ratio against calcium (Ca) in atoms per formula unit, while the I-type apatites have too low Mn and Fe to show a clear trend. Thus, divalent Mn and Fe probably replace Ca2+ in the S-types' apatite structure, while the incorporation of trivalent Mn or Fe in apatite is rather unlikely. We suggest that Mn and Fe contents in apatite may become a useful tracer of melt evolution once the distributions coefficients are experimentally calibrated. [1] Konecke et al. (2017), Am Mineral

Separate effects of flooding and anaerobiosis on soil greenhouse gas emissions and redox sensitive biogeochemistry

Treesearch

Gavin McNicol; Whendee L. Silver

2014-01-01

Soils are large sources of atmospheric greenhouse gases, and both the magnitude and composition of soil gas emissions are strongly controlled by redox conditions. Though the effect of redox dynamics on greenhouse gas emissions has been well studied in flooded soils, less research has focused on redox dynamics without total soil inundation. For the latter, all that is...

[Contents of ten trace elements in Epimedium acuminatum Franch. and its different processed products].

PubMed

Chen, H L; Wang, J K; Ren, Y Q; Wu, Z Y

2001-03-01

Determine and compare the contents of ten trace elements in crude E. acuminatum and its three different processed products. Using flame atomic absorption spectrometry. The ten trace elements were found in both the crude drug and its three processed products, and in terms of contents some of the trace elements in all the three processed products are higher than those in the crude drug. According to the trace element contents, the three processed products of E. acuminatum have their own advantages. It is thus suggested that thoroughgoing clinical and experimental researches be performed anew for the long-shelved processing methods.

Oceanic oxygenation events in the anoxic Ediacaran ocean.

PubMed

Sahoo, S K; Planavsky, N J; Jiang, G; Kendall, B; Owens, J D; Wang, X; Shi, X; Anbar, A D; Lyons, T W

2016-09-01

The ocean-atmosphere system is typically envisioned to have gone through a unidirectional oxygenation with significant oxygen increases in the earliest (ca. 635 Ma), middle (ca. 580 Ma), or late (ca. 560 Ma) Ediacaran Period. However, temporally discontinuous geochemical data and the patchy metazoan fossil record have been inadequate to chart the details of Ediacaran ocean oxygenation, raising fundamental debates about the timing of ocean oxygenation, its purported unidirectional rise, and its causal relationship, if any, with the evolution of early animal life. To better understand the Ediacaran ocean redox evolution, we have conducted a multi-proxy paleoredox study of a relatively continuous, deep-water section in South China that was paleogeographically connected with the open ocean. Iron speciation and pyrite morphology indicate locally euxinic (anoxic and sulfidic) environments throughout the Ediacaran in this section. In the same rocks, redox sensitive element enrichments and sulfur isotope data provide evidence for multiple oceanic oxygenation events (OOEs) in a predominantly anoxic global Ediacaran-early Cambrian ocean. This dynamic redox landscape contrasts with a recent view of a redox-static Ediacaran ocean without significant change in oxygen content. The duration of the Ediacaran OOEs may be comparable to those of the oceanic anoxic events (OAEs) in otherwise well-oxygenated Phanerozoic oceans. Anoxic events caused mass extinctions followed by fast recovery in biologically diversified Phanerozoic oceans. In contrast, oxygenation events in otherwise ecologically monotonous anoxic Ediacaran-early Cambrian oceans may have stimulated biotic innovations followed by prolonged evolutionary stasis. © 2016 John Wiley & Sons Ltd.

Sulfur redox chemistry governs diurnal antimony and arsenic cycles at Champagne Pool, Waiotapu, New Zealand

NASA Astrophysics Data System (ADS)

Ullrich, Maria K.; Pope, James G.; Seward, Terry M.; Wilson, Nathaniel; Planer-Friedrich, Britta

2013-07-01

Champagne Pool, a sulfidic hot spring in New Zealand, exhibits distinct diurnal variations in antimony (Sb) and arsenic (As) concentrations, with daytime high and night-time low concentrations. To identify the underlying mobilization mechanisms, five sites along the drainage channel of Champagne Pool were sampled every 2 h during a 24 h period. Temporal variations in elemental concentrations and Sb, As, and sulfur (S) speciation were monitored in the discharging fluid. Total trace element concentrations in filtered and unfiltered samples were analyzed using ICP-MS, and Sb, As and S species were determined by IC-ICP-MS. Sulfur speciation in the drainage channel was dominated by thiosulfate and sulfide at night, while sulfate dominated during the day. The distinct diurnal changes suggest that the transformations are caused by phototrophic sulfur-oxidizing bacteria. These bacteria metabolize thiosulfate and sulfide in daylight to form sulfate and, as suggested by modeling with PhreeqC, elemental sulfur. Sulfide consumption during the day results in undersaturation of antimony sulfides, which triggers the additional release of dissolved Sb. For As, diurnal cycles were much more pronounced in speciation than in total concentrations, with di- and trithioarsenate forming at night due to excess sulfide, and monothioarsenate forming from arsenite and elemental sulfur during the day. Sulfur speciation was thus found to control Sb and As in terms of both solubility and speciation.

Highly sensitive fiber grating chemical sensors: An effective alternative to atomic absorption spectroscopy

NASA Astrophysics Data System (ADS)

Laxmeshwar, Lata. S.; Jadhav, Mangesh S.; Akki, Jyoti. F.; Raikar, Prasad; Kumar, Jitendra; prakash, Om; Raikar, U. S.

2017-06-01

Accuracy in quantitative determination of trace elements like Zinc, present in drinking water in ppm level, is a big challenge and optical fiber gratings as chemical sensors may provide a promising solution to overcome the same. This paper presents design of two simple chemical sensors based on the principle of shift in characteristic wavelength of gratings with change in their effective refractive index, to measure the concentration of Zinc in drinking water using etched short period grating (FBG) and Long period grating (LPG) respectively. Three samples of drinking water from different places have been examined for presence of Zinc. Further, the results obtained by our sensors have also been verified with the results obtained by a standard method, Atomic absorption spectroscopy (AAS). The whole experiment has been performed by fixing the fibers in a horizontal position with the sensor regions at the center of the fibers, making it less prone to disturbance and breaking. The sensitivity of LPG sensor is about 205 times that of the FBG sensor. A few advantages of Fiber grating sensors, besides their regular features, over AAS have also been discussed, that make our sensors potential alternatives for existing techniques in determination of trace elements in drinking water.

The Effects of Various Amendments on Trace Element Stabilization in Acidic, Neutral, and Alkali Soil with Similar Pollution Index

PubMed Central

Kim, Min-Suk; Min, Hyun-Gi; Lee, Sang-Hwan; Kim, Jeong-Gyu

2016-01-01

Many studies have examined the application of soil amendments, including pH change-induced immobilizers, adsorbents, and organic materials, for soil remediation. This study evaluated the effects of various amendments on trace element stabilization and phytotoxicity, depending on the initial soil pH in acid, neutral, and alkali conditions. As in all types of soils, Fe and Ca were well stabilized on adsorption sites. There was an effect from pH control or adsorption mechanisms on the stabilization of cationic trace elements from inorganic amendments in acidic and neutral soil. Furthermore, acid mine drainage sludge has shown great potential for stabilizing most trace elements. In a phytotoxicity test, the ratio of the bioavailable fraction to the pseudo-total fraction significantly affected the uptake of trace elements by bok choy. While inorganic amendments efficiently decreased the bioavailability of trace elements, significant effects from organic amendments were not noticeable due to the short-term cultivation period. Therefore, the application of organic amendments for stabilizing trace elements in agricultural soil requires further study. PMID:27835687

Assessment of trace element contamination of urban surface soil at informal industrial sites in a low-income country.

PubMed

Kanda, Artwell; Ncube, France; Hwende, Tamuka; Makumbe, Peter

2018-05-29

Trace elements released by human activity are ubiquitously detected in surface soil. The trace element contamination statuses of 20 sampling stations at two busy informal industrial sites of Harare city, Zimbabwe, were evaluated using geochemical indices. Spectrophotometric determinations of concentrations of trace elements in surface soil indicated generally higher values than the reference site and the average upper earth's crust. High contamination factors were observed for trace elements across sampling stations at Gazaland and Siyaso informal industrial sites. Concentrations exhibited heterogeneous distribution of trace elements in surface soil varying with the nature of activity at a sampling station. The pollution load index and degree of contamination suggested highly contaminated surface soil with Cd, Cu and Pb particularly where the following activities were done: (1) welding, (2) automobile maintenance and (3) waste dumping. These results may be very important to reduce soil contamination. Paving surfaces may help to reduce dispersal of trace elements deposited on surface soil to other stations and minimise human exposure via inhalation and contact.

Risk assessment of trace elements in cultured freshwater fishes from Jiangxi province, China.

PubMed

Zhang, Li; Zhang, Dawen; Wei, Yihua; Luo, Linguan; Dai, Tingcan

2014-04-01

The levels of trace elements (As, Cd, Cr, Cu, Fe, Ni, Pb, Se, and Zn) in eight species of cultured freshwater fishes from Jiangxi province were determined by inductively coupled plasma-mass spectroscopy. All the studied trace element levels in fish muscles from Jiangxi province did not exceed Chinese national standard and European Union standard, and they were often lower than previous studies. The calculated target hazard quotient values for all the studied trace elements in fish samples were much less than 1, suggesting that the studied trace elements in fish muscles from Jiangxi province had not pose obvious health hazards to consumers. As and Cd concentrations in northern snakehead were much higher than that in other fishes, demonstrating that this fish species could be valuable as a bioindicator of As and Cd in environmental surveys. In addition, the highest concentrations of Fe, Zn, and moderate contents of other essential trace elements in crucian carp indicated that crucian carp could be a good nutrient source of essential trace elements for human health.

The Effects of Various Amendments on Trace Element Stabilization in Acidic, Neutral, and Alkali Soil with Similar Pollution Index.

PubMed

Kim, Min-Suk; Min, Hyun-Gi; Lee, Sang-Hwan; Kim, Jeong-Gyu

2016-01-01

Many studies have examined the application of soil amendments, including pH change-induced immobilizers, adsorbents, and organic materials, for soil remediation. This study evaluated the effects of various amendments on trace element stabilization and phytotoxicity, depending on the initial soil pH in acid, neutral, and alkali conditions. As in all types of soils, Fe and Ca were well stabilized on adsorption sites. There was an effect from pH control or adsorption mechanisms on the stabilization of cationic trace elements from inorganic amendments in acidic and neutral soil. Furthermore, acid mine drainage sludge has shown great potential for stabilizing most trace elements. In a phytotoxicity test, the ratio of the bioavailable fraction to the pseudo-total fraction significantly affected the uptake of trace elements by bok choy. While inorganic amendments efficiently decreased the bioavailability of trace elements, significant effects from organic amendments were not noticeable due to the short-term cultivation period. Therefore, the application of organic amendments for stabilizing trace elements in agricultural soil requires further study.

Determination of trace/ultratrace rare earth elements in environmental samples by ICP-MS after magnetic solid phase extraction with Fe3O4@SiO2@polyaniline-graphene oxide composite.

PubMed

Su, Shaowei; Chen, Beibei; He, Man; Hu, Bin; Xiao, Zuowei

2014-02-01

A novel Fe3O4@SiO2@polyaniline-graphene oxide composite (MPANI-GO) was prepared through a simple noncovalent method and applied to magnetic solid phase extraction (MSPE) of trace rare earth elements (REEs) in tea leaves and environmental water samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection. The prepared MPANI-GO was characterized by transmission electron microscopy and vibrating sample magnetometer. Various parameters affecting MPANI-GO MSPE of REEs have been investigated. Under the optimized conditions, the limits of detection (LODs, 3σ) for REEs were in the range of 0.04-1.49 ng L(-1) and the relative standard deviations (RSDs, c=20 ng L(-1), n=7) were 1.7-6.5%. The accuracy of the proposed method was validated by analyzing a Certified Reference Material of GBW 07605 tea leaves. The method was also successfully applied for the determination of trace REEs in tea leaves and environmental water samples. The developed MPANI-GO MSPE-ICP-MS method has the advantages of simplicity, rapidity, high sensitivity, high enrichment factor and is suitable for the analysis of trace REEs in samples with complex matrix. © 2013 Elsevier B.V. All rights reserved.

Methods for detecting the mobility of trace elements during medium-temperature pyrolysis

USGS Publications Warehouse

Shiley, R.H.; Konopka, K.L.; Cahill, R.A.; Hinckley, C.C.; Smith, Gerard V.; Twardowska, H.; Saporoschenko, Mykola

1983-01-01

The mobility (volatility) of trace elements in coal during pyrolysis has been studied for distances of up to 40 cm between the coal and the trace element collector, which was graphite or a baffled solvent trap. Nineteen elements not previously recorded as mobile were detected. ?? 1983.

The NASA Redox Storage System Development project, 1980

NASA Technical Reports Server (NTRS)

1982-01-01

The technical accomplishments pertaining to the development of Redox systems and related technology are outlined in terms of the task elements: prototype systems development, application analyses, and supporting technology. Prototype systems development provides for a major procurement to develop an industrial capability to take the current NASA Lewis technology and go on to the design, development, and commercialization of iron-chromium Redox storage systems. Application analyses provides for the definition of application concepts and technology requirements, specific definition studies, and the identification of market sectors and their penetration potential. Supporting technology includes both in house and contractual efforts that encompass implementation of technology improvements in membranes, electrodes, reactant processing, and system design. The status of all elements is discussed.

The NASA Redox Storage System Development project, 1980

NASA Astrophysics Data System (ADS)

1982-12-01

The technical accomplishments pertaining to the development of Redox systems and related technology are outlined in terms of the task elements: prototype systems development, application analyses, and supporting technology. Prototype systems development provides for a major procurement to develop an industrial capability to take the current NASA Lewis technology and go on to the design, development, and commercialization of iron-chromium Redox storage systems. Application analyses provides for the definition of application concepts and technology requirements, specific definition studies, and the identification of market sectors and their penetration potential. Supporting technology includes both in house and contractual efforts that encompass implementation of technology improvements in membranes, electrodes, reactant processing, and system design. The status of all elements is discussed.

The role of high-energy synchrotron radiation in biomedical trace element research

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

Pounds, J.G.; Long, G.J.; Kwiatek, W.M.

1987-01-01

This paper will present the results of an investigation of the distribution of essential elements in the normal hepatic lobule. the liver is the organ responsible for metabolism and storage of most trace elements. Although parenchymal hepatocytes are rather uniform histologically, morphometry, histochemistry, immunohistochemistry, and microdissection with microchemical investigations have revealed marked heterogeneity on a functional and biochemical level. Hepatocytes from the periportal and perivenous zones of the liver parrenchyma differ in oxidative energy metabolism, glucose uptake and output, unreagenesis, biotransformation, bile acid secretion, and palsma protein synthesis and secretion. Although trace elements are intimately involved in the regulation andmore » maintenance of these functions, little is known regarding the heterogeneity of trace element localization of the liver parenchyma. Histochemical techniques for trace elements generally give high spatial resolution, but lack specificity and stoichiometry. Microdissection has been of marginal usefulness for trace element analyses due to the very small size of the dissected parenchyma. The characteristics of the high-energy x-ray microscope provide an effective approach for elucidating the trace element content of these small biological structures or regions. 5 refs., 1 fig., 1 tab.« less

The influence of carbon, sulfur, and silicon on trace element partitioning in iron alloys

NASA Astrophysics Data System (ADS)

Han, J.; Van Orman, J. A.; Crispin, K. L.; Ash, R. D.

2014-12-01

Non-metallic light elements are important constituents of planetary cores and have a strong influence on the partitioning behavior of trace elements. Planetary cores may contain a wide range of non-metallic light elements, including H, N, S, P, Si, and C. Under highly reducing conditions, such as those that are thought to have pertained during the formation of Mercury's core, Si and C, in addition to sulfur, may be particularly important constituents. Each of these elements may strongly effect and have a different impact on the partitioning behavior of trace elements but their combined effects on trace element partitioning have not been quantified. We investigated the partitioning behavior of more than 25 siderophile trace elements within the Fe-S-C-Si system with varying concentrations of C, S, and Si. The experiments were performed under pressures varying from 1 atm to 2 GPa and temperatures ranging from 1200˚C to 1450˚C. All experiments produced immiscible liquids, one enriched in Si and C, and the other predominantly FeS. We found some highly siderophile elements including Os, Ru, Ir, and Re are much more enriched in Fe-Si-C phase than in Fe-S phase, whereas other trace elements like V, Co, Ag, Hf, and Pb are enriched in S-rich phase. However, not all the trace elements enriched in Fe-Si-C phase are repelled by sulfur. Elements like Re and Ru could have different partitioning trends if sulfur concentration in S-rich phase rises. The partitioning behavior of these trace elements could enhance our understanding of the differentiation of Mercury's core under oxygen-poor conditions.

Maternal transfer of trace elements in the Atlantic horseshoe crab (Limulus polyphemus).

PubMed

Bakker, Aaron K; Dutton, Jessica; Sclafani, Matthew; Santangelo, Nicholas

2017-01-01

The maternal transfer of trace elements is a process by which offspring may accumulate trace elements from their maternal parent. Although maternal transfer has been assessed in many vertebrates, there is little understanding of this process in invertebrate species. This study investigated the maternal transfer of 13 trace elements (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn) in Atlantic horseshoe crab (Limulus polyphemus) eggs and compared concentrations to those in adult leg and gill tissue. For the majority of individuals, all trace elements were transferred, with the exception of Cr, from the female to the eggs. The greatest concentrations on average transferred to egg tissue were Zn (140 µg/g), Cu (47.8 µg/g), and Fe (38.6 µg/g) for essential elements and As (10.9 µg/g) and Ag (1.23 µg/g) for nonessential elements. For elements that were maternally transferred, correlation analyses were run to assess if the concentration in the eggs were similar to that of adult tissue that is completely internalized (leg) or a boundary to the external environment (gill). Positive correlations between egg and leg tissue were found for As, Hg, Se, Mn, Pb, and Ni. Mercury, Mn, Ni, and Se were the only elements correlated between egg and gill tissue. Although, many trace elements were in low concentration in the eggs, we speculate that the higher transfer of essential elements is related to their potential benefit during early development versus nonessential trace elements, which are known to be toxic. We conclude that maternal transfer as a source of trace elements to horseshoe crabs should not be overlooked and warrants further investigation.

Correcting sensitivity drift during long-term multi-element signal measurements by solid sampling-ETV-ICP-MS.

PubMed

Martin-Esteban, A; Slowikowski, B; Grobecker, K H

2004-06-17

Solid sampling-electrothermal vaporisation-inductively coupled plasma-mass spectrometry (SS-ETV-ICP-MS) is an attractive technique for the direct simultaneous determination of trace elements in solid samples and especially in long-term studies (i.e. assessment of the homogeneity of reference materials). However, during these studies a downward drift in the instrument sensitivity has been observed due likely to deposits on the sampling and skimmer cones and on the ion lens of the mass spectrometer. Accordingly, in this paper, several means of correcting and/or suppressing sensitivity drift are proposed and evaluated for the monitoring of Cd, Cu, Hg, Mn, Pb, Sb, Se, Sn, Tl, U and V in different reference materials of inorganic and organic (biological) origin. From that studies, the combination of the use of the argon dimer as internal standard together with a modification in the ETV-ICP connection tube seems to be the best mean of getting stable sensitivity during at least 60 consecutive ETV runs.

Remediation using trace element humate surfactant

DOEpatents

Riddle, Catherine Lynn; Taylor, Steven Cheney; Bruhn, Debra Fox

2016-08-30

A method of remediation at a remediation site having one or more undesirable conditions in which one or more soil characteristics, preferably soil pH and/or elemental concentrations, are measured at a remediation site. A trace element humate surfactant composition is prepared comprising a humate solution, element solution and at least one surfactant. The prepared trace element humate surfactant composition is then dispensed onto the remediation site whereby the trace element humate surfactant composition will reduce the amount of undesirable compounds by promoting growth of native species activity. By promoting native species activity, remediation occurs quickly and environmental impact is minimal.

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.

Alternative model for the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Bekker, A.

2014-12-01

Transition from the Archean, largely anoxic atmosphere and ocean to the Proterozoic oxidizing surface conditions has been inferred in Zimbabwe from the geochemical and geological evidence as early as 1927. Subsequent studies provided additional support for this interpretation, bracketed the transition between 2.45 and 2.32 Ga, and suggested temporal and cause-and-effect relationship with a series of the early Paleoproterozoic ice ages (including 4 discrete events). Recently recognized transient oxidation events of the Archean add texture to this pattern, but do not change it. The rise of atmospheric oxygen requires a misbalance between oxygen sinks and sources and most attention was focused on sinks. In contrast, change in oxygen supply related to low organic productivity in Archean oceans with limited nutrient contents are considered here. Although carbon isotope values of carbonates and organic carbon indicate substantial relative burial rate of organic carbon during the Archean, most of the earlier buried organic matter at that time was recycled to sediments during continental weathering, implying very low productivity and burial of 'new' organic carbon. Low contents of redox-sensitive elements, such as Mo, Cu, Zn, and V, in Archean seawater could have kept organic productivity and oxygen production at low levels. The GOE was immediately preceded by deposition of giant iron formations, accounting for more than 70% of world iron resources, and worldwide emplacement of a number of LIPs between 2.5 and 2.45 Ga, indicating enhanced delivery of nutrients and redox-sensitive elements to the oceans via submarine hydrothermal processes and continental weathering under CO2- and SO2-rich atmosphere and associated terrestrial acidic runoff. This enhanced emplacement of LIPs has been linked with the growth of continental crust, emergence of the first supercontinent, and mantle overturn at the Archean-Proterozoic boundary. The GOE could have thus been triggered by enhanced nutrient supply to the oceans lifting the limit on biological productivity during a period with intensive mantle plume activity when the first supercontinent was assembled, emphasizing an underappreciated role of endogenic processes as a driver of redox fluctuations in the atmosphere-ocean system.

Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene.

PubMed

Burls, Natalie J; Fedorov, Alexey V; Sigman, Daniel M; Jaccard, Samuel L; Tiedemann, Ralf; Haug, Gerald H

2017-09-01

An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, the world's largest ocean, where relatively fresh surface waters inhibit North Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400-ppmv (parts per million by volume) CO 2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanying pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redox-sensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming.

Identification of Early Nuclear Target Genes of Plastidial Redox Signals that Trigger the Long-Term Response of Arabidopsis to Light Quality Shifts.

PubMed

Dietzel, Lars; Gläßer, Christine; Liebers, Monique; Hiekel, Stefan; Courtois, Florence; Czarnecki, Olaf; Schlicke, Hagen; Zubo, Yan; Börner, Thomas; Mayer, Klaus; Grimm, Bernhard; Pfannschmidt, Thomas

2015-08-01

Natural illumination conditions are highly variable and because of their sessile life style, plants are forced to acclimate to them at the cellular and molecular level. Changes in light intensity or quality induce changes in the reduction/oxidation (redox) state of the photosynthetic electron chain that acts as a trigger for compensatory acclimation responses comprising functional and structural adjustments of photosynthesis and metabolism. Such responses include redox-controlled changes in plant gene expression in the nucleus and organelles. Here we describe a strategy for the identification of early redox-regulated genes (ERGs) in the nucleus of the model organism Arabidopsis thaliana that respond significantly 30 or 60 min after the generation of a reduction signal in the photosynthetic electron transport chain. By comparing the response of wild-type plants with that of the acclimation mutant stn7, we could specifically identify ERGs. The results reveal a significant impact of chloroplast redox signals on distinct nuclear gene groups including genes for the mitochondrial electron transport chain, tetrapyrrole biosynthesis, carbohydrate metabolism, and signaling lipid synthesis. These expression profiles are clearly different from those observed in response to the reduction of photosynthetic electron transport by high light treatments. Thus, the ERGs identified are unique to redox imbalances in photosynthetic electron transport and were then used for analyzing potential redox-responsive cis-elements, trans-factors, and chromosomal regulatory hot spots. The data identify a novel redox-responsive element and indicate extensive redox control at transcriptional and chromosomal levels that point to an unprecedented impact of redox signals on epigenetic processes. Copyright © 2015 The Author. Published by Elsevier Inc. All rights reserved.

Trace element and stable isotope analysis of fourteen species of marine invertebrates from the Bay of Fundy, Canada.

PubMed

English, Matthew D; Robertson, Gregory J; Mallory, Mark L

2015-12-15

The Bay of Fundy, Canada, is a macrotidal bay with a highly productive intertidal zone, hosting a large abundance and diversity of marine invertebrates. We analysed trace element concentrations and stable isotopic values of δ(15)N and δ(13)C in 14 species of benthic marine invertebrates from the Bay of Fundy's intertidal zone to investigate bioaccumulation or biodilution of trace elements in the lower level of this marine food web. Barnacles (Balanus balanus) consistently had significantly greater concentrations of trace elements compared to the other species studied, but otherwise we found low concentrations of non-essential trace elements. In the range of trophic levels that we studied, we found limited evidence of bioaccumulation or biodilution of trace elements across species, likely due to the species examined occupying similar trophic levels in different food chains. Copyright © 2015 Elsevier Ltd. All rights reserved.

Trace metals in fluids lining the respiratory system of patients with idiopathic pulmonary fibrosis and diffuse lung diseases.

PubMed

Bargagli, Elena; Lavorini, Federico; Pistolesi, Massimo; Rosi, Elisabetta; Prasse, Antje; Rota, Emilia; Voltolini, Luca

2017-07-01

Idiopathic pulmonary fibrosis (IPF) is an interstitial lung disease with a poor prognosis and an undefined etiopathogenesis. Oxidative stress contributes to alveolar injury and fibrosis development and, because transition metals are essential to the functioning of most proteins involved in redox reactions, a better knowledge of metal concentrations and metabolism in the respiratory system of IPF patients may provide a valuable complementary approach to prevent and manage a disease which is often misdiagnosed or diagnosed in later stages. The present review summarizes and discusses literature data on the elemental composition of bronchoalveolar lavage (BAL), induced sputum and exhaled breath condensate (EBC) from patients affected by IPF and healthy subjects. Available data are scanty and the lack of consistent methods for the collection and analysis of lung and airways lining fluids makes it difficult to compare the results of different studies. However, the elemental composition of BAL samples from IPF patients seems to have a specific profile that can be distinguished from that of patients with other interstitial lung diseases (ILD) or control subjects. Suggestions are given towards standard sampling and analytical procedures of BAL samples, in the aim to assess typical element concentration patterns and their potential role as biomarkers of IPF. Copyright © 2017 Elsevier GmbH. All rights reserved.

Distribution and environmental assessment of trace elements contamination of water, sediments and flora from Douro River estuary, Portugal.

PubMed

Ribeiro, C; Couto, C; Ribeiro, A R; Maia, A S; Santos, M; Tiritan, M E; Pinto, E; Almeida, A A

2018-10-15

The present study evaluated the content and distribution of several trace elements (Li, Be, Al, V, Cr, Co, Ni, Cu, Zn, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, and U) in the Douro River estuary. For that, three matrices were collected (water, sediments and native local flora) to assess the extent of contamination by these elements in this estuarine ecosystem. Results showed their occurrence in estuarine water and sediments, but significant differences were recorded on the concentration levels and pattern of distribution among both matrices and sampling points. Generally, the levels of trace elements were higher in the sediments than in the respective estuarine water. Nonetheless, no correlation among trace elements was determined between water and sediments, except for Cd. Al was the trace element found at highest concentration at both sediments and water followed by Zn. Pollution indices such as geo-accumulation (I geo ), enrichment factor (EF) and contamination factor (CF) were determined to understand the levels and sources of trace elements pollution. I geo showed strong contamination by anthropogenic activities for Li, Al, V, Cr, Ni, Cu, Zn, Ba and Pb at all sampling points while EF and CF demonstrated severe enrichment and contamination by Se, Sb and Pb. Levels of trace elements were compared to acceptable values for aquatic organisms and Sediment Quality Guidelines. The concentration of some trace elements, namely Al, Pb and Cu, were higher than those considered acceptable, with potential negative impact on local living organisms. Nevertheless, permissible values for all trace elements are still not available, demonstrating that further studies are needed in order to have a complete assessment of environmental risk. Furthermore, the occurrence and possible accumulation of trace elements by local plant species and macroalgae were investigated as well as their potential use as bioindicators of local pollution and for phytoremediation purposes. Copyright © 2018 Elsevier B.V. All rights reserved.

Constraints on the bioavailability of trace elements to terrestrial fauna at mining and smelting sites

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

Pastorok, R.; Schoof, R.; LaTier, A.

1995-12-31

At mining and smelting sites, the bioavailability of waste-related trace elements to terrestrial wildlife is limited by mineralogy of the waste material and the geochemistry of the waste-soil mixture. For example, encapsulation of trace elements in inert mineral matrices limits the assimilation of particle-associated trace elements that are ingested by wildlife. The bioavailability of arsenic, cadmium, copper, lead, silver, and zinc at mining and smelting sites in Oklahoma and Montana was evaluated based on analysis of waste material, soil chemistry, and concentrations of trace elements in whole-body samples of key food web species. Concentrations of trace elements were generally elevatedmore » relative to reference area values for selected species of vegetation, insects, spiders, and small mammals. Soil-to-tissue bioconcentration factors derived from field data at these sites were generally low (< 1), with the exception of cadmium in vegetation. For all of the trace elements evaluated, wildlife exposure models indicate that the potential for transfer of contaminants to wildlife species of public concern and high trophic-level predators is limited. Moreover, laboratory feeding experiments conducted with cadmium and lead indicate that the assimilation of waste-related trace elements by mammals is relatively low (24--47 percent for lead in blood and bone; 22--44 percent for cadmium in kidney). The relatively low bioavailability of trace elements at mining and smelting sites should be considered when estimating exposure of ecological receptors and when deriving soil cleanup criteria based on measured or modeled ecological risk.« less

Assessment of serum trace elements and electrolytes in children with childhood and atypical autism.

PubMed

Skalny, Anatoly V; Simashkova, Natalia V; Klyushnik, Tatiana P; Grabeklis, Andrei R; Radysh, Ivan V; Skalnaya, Margarita G; Nikonorov, Alexandr A; Tinkov, Alexey A

2017-09-01

The existing data demonstrate a significant interrelation between ASD and essential and toxic trace elements status of the organism. However, data on trace element homeostasis in particular ASD forms are insufficient. Therefore, the objective of the present study was to assess the level of trace elements and electrolytes in serum of children with childhood and atypical autism. A total of 48 children with ASD (24 with childhood and 24 with atypical autism) and age- and sex-adjusted controls were examined. Serum trace elements and electrolytes were assessed using inductively-coupled plasma mass spectrometry. The obtained data demonstrate that children with ASD unspecified are characterized by significantly lower Ni, Cr, and Se levels as compared to the age- and sex-matched controls. At the same time, significantly decreased serum Ni and Se concentrations were detected in patients with childhood autism. In turn, children with atypical autism were characterized by more variable serum trace element spectrum. In particular, atypical autism is associated with lower serum Al, As, Ni, Cr, Mn, and Se levels in comparison to the control values. Moreover, Al and Mn concentration in this group was also lower than that in childhood autism patients. Generally, the obtained data demonstrate lower levels of both essential and toxic trace elements in atypical autism group, being indicative of profound alteration of trace elements metabolism. However, further detailed metabolic studies are required to reveal critical differences in metabolic pathways being responsible for difference in trace element status and clinical course of the disease. Copyright © 2016 Elsevier GmbH. All rights reserved.

Hypoxic Signaling and the Cellular Redox Tumor Environment Determine Sensitivity to MTH1 Inhibition.

PubMed

Bräutigam, Lars; Pudelko, Linda; Jemth, Ann-Sofie; Gad, Helge; Narwal, Mohit; Gustafsson, Robert; Karsten, Stella; Carreras Puigvert, Jordi; Homan, Evert; Berndt, Carsten; Berglund, Ulrika Warpman; Stenmark, Pål; Helleday, Thomas

2016-04-15

Cancer cells are commonly in a state of redox imbalance that drives their growth and survival. To compensate for oxidative stress induced by the tumor redox environment, cancer cells upregulate specific nononcogenic addiction enzymes, such as MTH1 (NUDT1), which detoxifies oxidized nucleotides. Here, we show that increasing oxidative stress in nonmalignant cells induced their sensitization to the effects of MTH1 inhibition, whereas decreasing oxidative pressure in cancer cells protected against inhibition. Furthermore, we purified zebrafish MTH1 and solved the crystal structure of MTH1 bound to its inhibitor, highlighting the zebrafish as a relevant tool to study MTH1 biology. Delivery of 8-oxo-dGTP and 2-OH-dATP to zebrafish embryos was highly toxic in the absence of MTH1 activity. Moreover, chemically or genetically mimicking activated hypoxia signaling in zebrafish revealed that pathologic upregulation of the HIF1α response, often observed in cancer and linked to poor prognosis, sensitized embryos to MTH1 inhibition. Using a transgenic zebrafish line, in which the cellular redox status can be monitored in vivo, we detected an increase in oxidative pressure upon activation of hypoxic signaling. Pretreatment with the antioxidant N-acetyl-L-cysteine protected embryos with activated hypoxia signaling against MTH1 inhibition, suggesting that the aberrant redox environment likely causes sensitization. In summary, MTH1 inhibition may offer a general approach to treat cancers characterized by deregulated hypoxia signaling or redox imbalance. Cancer Res; 76(8); 2366-75. ©2016 AACR. ©2016 American Association for Cancer Research.

Organic Carbon and Trace Element Cycling in a River-Dominated Tidal Coastal Wetland System (Tampa Bay, FL, USA)

NASA Astrophysics Data System (ADS)

Moyer, R. P.; Smoak, J. M.; Engelhart, S. E.; Powell, C. E.; Chappel, A. R.; Gerlach, M. J.; Kemp, A.; Breithaupt, J. L.

2016-02-01

Tampa Bay is the largest open water, river-fed estuary in Florida (USA), and is characterized by the presence of both mangrove and salt marsh ecosystems. Both coastal wetland systems, and small rivers such as the ones draining into Tampa Bay have historically been underestimated in terms of their role in the global carbon and elemental cycles. Climate change and sea-level rise (SLR) are major threats in Tampa Bay and stand to disrupt hydrologic cycles, compromising sediment accumulation and the rate of organic carbon (OC) burial. This study evaluates organic carbon content, sediment accumulation, and carbon burial rates in salt marsh and mangrove ecosystems, along with measurements of fluxes of dissolved OC (DOC) and trace elements in the water column of the Little Manatee River (LMR) in Tampa Bay. The characterization of OC and trace elements in tidal rivers and estuaries is critical for quantitatively constraining these systems in local-to-regional scale biogeochemical budgets, and provide insight into biogeochemical processes occurring with the estuary and adjacent tidal wetlands. Material fluxes of DOC and trace elements were tied to discharge irrespective of season, and the estuarine habitats removed 15-65% of DOC prior to export to Tampa Bay and the Gulf of Mexico. Thus, material is available for cycling and burial within marsh and mangrove peats, however, LMR mangrove peats have higher OC content and burial rates than adjacent salt marsh peats. Sedimentary accretion rates in LMR marshes are not currently keeping pace with SLR, thus furthering the rapid marsh-to-mangrove conversions that have been seen in Tampa Bay over the past half-century. Additionally, wetlands in Tampa Bay tend to have a lower rate of carbon burial than other Florida tidal wetlands, demonstrating their high sensitivity to climate change and SLR.

[Determination of Trace Elements in Marine Cetaceans by ICP-MS and Health Risk Assessment].

PubMed

Ding, Yu-long; Ning, Xi; Gui, Duan; Mo, Hui; Li, Yu-sen; Wu, Yu-ping

2015-09-01

The liver, kidney and muscle samples from seven cetaceans were digested by microwave digestion, and trace elements amounts of V, Cd, Cu, Zn, As, Cr, Ni, Mn, Se, Hg and Pb were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the health risk assessment for Zn, Cu, Cd, Hg, Se in the liver was conducted. The results of international lobster hepatopancreas standard (TORT-2) showed acceptable agreement with the certified values, and the relative standard deviation (RSD) of eleven kinds of trace elements were less than 3.54%, showing that the method is suitable for the determination of trace elements in cetaceans. The experimental results indicated that different tissues and organs of the dolphins had different trace elements, presenting the tissue specificity. There is a certain inter-species difference among different dolphins about the bioaccumulation ability of the trace elements. The distribution of trace elements in whales presented a certain regularity: the contents of most elements in liver, kidney were much higher than the contents of muscle tissues, Cu, Mn, Hg, Se, and Zn exhibit the higher concentrations in liver, while Cd was mainly accumulated in kidney. And according to the health risk assessment in liver, the exceeding standardrate of selenium and copper in seven kinds of whales was 100%, suggesting that these whales were suffering the contamination of trace elements. The experimental results is instructive to the study of trace elements in cetaceans, while this is the first report for the concentrations in organs of Striped dolphin, Bottlenose dolphin, Fraser's Dolphin and Risso's dolphin in China, it may provide us valuable data for the conservation of cetaceans.

Cost-driven materials selection criteria for redox flow battery electrolytes

NASA Astrophysics Data System (ADS)

Dmello, Rylan; Milshtein, Jarrod D.; Brushett, Fikile R.; Smith, Kyle C.

2016-10-01

Redox flow batteries show promise for grid-scale energy storage applications but are presently too expensive for widespread adoption. Electrolyte material costs constitute a sizeable fraction of the redox flow battery price. As such, this work develops a techno-economic model for redox flow batteries that accounts for redox-active material, salt, and solvent contributions to the electrolyte cost. Benchmark values for electrolyte constituent costs guide identification of design constraints. Nonaqueous battery design is sensitive to all electrolyte component costs, cell voltage, and area-specific resistance. Design challenges for nonaqueous batteries include minimizing salt content and dropping redox-active species concentration requirements. Aqueous battery design is sensitive to only redox-active material cost and cell voltage, due to low area-specific resistance and supporting electrolyte costs. Increasing cell voltage and decreasing redox-active material cost present major materials selection challenges for aqueous batteries. This work minimizes cost-constraining variables by mapping the battery design space with the techno-economic model, through which we highlight pathways towards low price and moderate concentration. Furthermore, the techno-economic model calculates quantitative iterations of battery designs to achieve the Department of Energy battery price target of 100 per kWh and highlights cost cutting strategies to drive battery prices down further.

Origin and distribution of trace elements in high-elevation precipitation in southern China.

PubMed

Zhou, Jie; Wang, Yan; Yue, Taixing; Li, Yuhua; Wai, Ka-Ming; Wang, Wenxing

2012-09-01

During a 2009 investigation of the transport and deposition of trace elements in southern China, 37 event-based precipitation samples were collected at an observatory on Mount Heng, China (1,269 m asl). Concentrations of trace elements were analyzed using inductively coupled plasma-mass spectrometry and the wet deposition fluxes were established. A combination of techniques including enrichment factor analysis, principal component analysis, and back trajectory models were used to identify pollutant sources. Trace element concentrations at Mount Heng were among the highest with respect to measured values reported elsewhere. All elements were of non-marine origin. The elements Pb, As, Cu, Se, and Cd were anthropogenic, while Fe, Cr, V, Ba, Mn, and Ni were of mixed crustal/anthropogenic origin. The crustal and anthropogenic contributions of trace elements were 12.8 % (0.9 ~ 17.4 %) and 87.2 % (82.6 ~ 99.1 %), with the maximum crustal fraction being 17.4 % for Fe. Coal combustion, soil and road dust, metallurgical processes, and industrial activities contributed to the element composition. Summit precipitation events were primarily distant in origin. Medium- to long-range transport of trace elements from the Yangtze River Delta and northern China played an important role in wet deposition at Mount Heng, while air masses from south or southeast of the station were generally low in trace element concentrations.

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Rumble, D., III

2006-01-01

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

Trends in Trace Element Fractionation Between Foraminiferal Species and the Role of Biomineralization

NASA Astrophysics Data System (ADS)

Reichart, G. J.; Nooijer, L. D.; Geerken, E.; Mezger, E.; van Dijk, I. V.; Daemmer, L. K.

2017-12-01

Reconstructions of past climate and environments are largely based on stable isotopes and trace element concentrations measured on fossil foraminiferal calcite. Their element and isotope composition roughly reflects seawater composition and physical conditions, which in turn, are related to paleoceanographic parameters. More recently, attempts are being made to infer ranges in environmental parameters using the observed differences in the composition within individual tests. Remarkably, inter-species differences in trace element incorporation are well-correlated over a wide range of environmental conditions. This is particularly remarkable knowing that different environmental factors influence incorporation of these elements at various magnitudes. Most likely the complex biomineralization of foraminifera potentially offsets trace elements similarly at all these scales and also between different species. This suggests that at least parts of the mechanisms underlying foraminiferal biomineralization are similar for all species, which in turn provides important clues on the cellular mechanisms operating during calcification. Moreover, the systematics in trace element partitioning between species could potentially provide important clues for unravelling past changes in trace element composition of the ancient ocean.

Thiol-based redox proteins in abscisic acid and methyl jasmonate signaling in Brassica napus guard cells.

PubMed

Zhu, Mengmeng; Zhu, Ning; Song, Wen-yuan; Harmon, Alice C; Assmann, Sarah M; Chen, Sixue

2014-05-01

Reversibly oxidized cysteine sulfhydryl groups serve as redox sensors or targets of redox sensing that are important in various physiological processes. However, little is known about redox-sensitive proteins in guard cells and how they function in stomatal signaling. In this study, Brassica napus guard-cell proteins altered by redox in response to abscisic acid (ABA) or methyl jasmonate (MeJA) were identified by complementary proteomics approaches, saturation differential in-gel electrophoresis and isotope-coded affinity tagging. In total, 65 and 118 potential redox-responsive proteins were identified in ABA- and MeJA-treated guard cells, respectively. All the proteins contain at least one cysteine, and over half of them are predicted to form intra-molecular disulfide bonds. Most of the proteins fall into the functional groups of 'energy', 'stress and defense' and 'metabolism'. Based on the peptide sequences identified by mass spectrometry, 30 proteins were common to ABA- and MeJA-treated samples. A total of 44 cysteines were mapped in the identified proteins, and their levels of redox sensitivity were quantified. Two of the proteins, a sucrose non-fermenting 1-related protein kinase and an isopropylmalate dehydrogenase, were confirmed to be redox-regulated and involved in stomatal movement. This study creates an inventory of potential redox switches, and highlights a protein redox regulatory mechanism in ABA and MeJA signal transduction in guard cells. © 2014 The Authors The Plant Journal © 2014 John Wiley & Sons Ltd.

Glutathione reductase mediates drug resistance in glioblastoma cells by regulating redox homeostasis.

PubMed

Zhu, Zhongling; Du, Shuangshuang; Du, Yibo; Ren, Jing; Ying, Guoguang; Yan, Zhao

2018-01-01

Glutathione (GSH) and GSH-related enzymes constitute the most important defense system that protects cells from free radical, radiotherapy, and chemotherapy attacks. In this study, we aim to explore the potential role and regulatory mechanism of the GSH redox cycle in drug resistance in glioblastoma multiforme (GBM) cells. We found that temozolomide (TMZ)-resistant glioma cells displayed lower levels of endogenous reactive oxygen species and higher levels of total antioxidant capacity and GSH than sensitive cells. Moreover, the expression of glutathione reductase (GSR), the key enzyme of the GSH redox cycle, was higher in TMZ-resistant cells than in sensitive cells. Furthermore, silencing GSR in drug-resistant cells improved the sensitivity of cells to TMZ or cisplatin. Conversely, the over-expression of GSR in sensitive cells resulted in resistance to chemotherapy. In addition, the GSR enzyme partially prevented the oxidative stress caused by pro-oxidant L-buthionine -sulfoximine. The modulation of redox state by GSH or L-buthionine -sulfoximine regulated GSR-mediated drug resistance, suggesting that the action of GSR in drug resistance is associated with the modulation of redox homeostasis. Intriguingly, a trend toward shorter progress-free survival was observed among GBM patients with high GSR expression. These results indicated that GSR is involved in mediating drug resistance and is a potential target for improving GBM treatment. © 2017 International Society for Neurochemistry.

Perturbations of Amino Acid Metabolism Associated with Glyphosate-Dependent Inhibition of Shikimic Acid Metabolism Affect Cellular Redox Homeostasis and Alter the Abundance of Proteins Involved in Photosynthesis and Photorespiration1[W][OA

PubMed Central

Vivancos, Pedro Diaz; Driscoll, Simon P.; Bulman, Christopher A.; Ying, Liu; Emami, Kaveh; Treumann, Achim; Mauve, Caroline; Noctor, Graham; Foyer, Christine H.

2011-01-01

The herbicide glyphosate inhibits the shikimate pathway of the synthesis of amino acids such as phenylalanine, tyrosine, and tryptophan. However, much uncertainty remains concerning precisely how glyphosate kills plants or affects cellular redox homeostasis and related processes in glyphosate-sensitive and glyphosate-resistant crop plants. To address this issue, we performed an integrated study of photosynthesis, leaf proteomes, amino acid profiles, and redox profiles in the glyphosate-sensitive soybean (Glycine max) genotype PAN809 and glyphosate-resistant Roundup Ready Soybean (RRS). RRS leaves accumulated much more glyphosate than the sensitive line but showed relatively few changes in amino acid metabolism. Photosynthesis was unaffected by glyphosate in RRS leaves, but decreased abundance of photosynthesis/photorespiratory pathway proteins was observed together with oxidation of major redox pools. While treatment of a sensitive genotype with glyphosate rapidly inhibited photosynthesis and triggered the appearance of a nitrogen-rich amino acid profile, there was no evidence of oxidation of the redox pools. There was, however, an increase in starvation-associated and defense proteins. We conclude that glyphosate-dependent inhibition of soybean leaf metabolism leads to the induction of defense proteins without sustained oxidation. Conversely, the accumulation of high levels of glyphosate in RRS enhances cellular oxidation, possibly through mechanisms involving stimulation of the photorespiratory pathway. PMID:21757634

Responses of trace elements to aerobic maximal exercise in elite sportsmen.

PubMed

Otag, Aynur; Hazar, Muhsin; Otag, Ilhan; Gürkan, Alper Cenk; Okan, Ilyas

2014-02-21

Trace elements are chemical elements needed in minute quantities for the proper growth, development, and physiology of the organism. In biochemistry, a trace element is also referred to as a micronutrient. Trace elements, such as nickel, cadmium, aluminum, silver, chromium, molybdenum, germanium, tin, titanium, tungsten, scandium, are found naturally in the environment and human exposure derives from a variety of sources, including air, drinking water and food. The Purpose of this study was investigated the effect of aerobic maximal intensity endurance exercise on serum trace elements as well-trained individuals of 28 wrestlers (age (year) 19.64±1.13, weight (Kg) 70.07 ± 15.69, height (cm) 176.97 ± 6.69) during and after a 2000 meter Ergometer test protocol was used to perform aerobic (75 %) maximal endurance exercise. Trace element serum levels were analyzed from blood samples taken before, immediately after and one hour after the exercise. While an increase was detected in Chromium (Cr), Nickel (Ni), Molybdenum (Mo) and Titanium (Ti) serum levels immediately after the exercise, a decrease was detected in Aluminum (Al), Scandium (Sc) and Tungsten (W) serum levels. Except for aluminum, the trace elements we worked on showed statistically meaningful responses (P < 0.05 and P < 0.001). According to the responses of trace elements to the exercise showed us the selection and application of the convenient sport is important not only in terms of sportsman performance but also in terms of future healthy life plans and clinically.

A Redox-Nucleophilic Dual-Reactable Probe for Highly Selective and Sensitive Detection of H2S: Synthesis, Spectra and Bioimaging

NASA Astrophysics Data System (ADS)

Zhang, Changyu; Wang, Runyu; Cheng, Longhuai; Li, Bingjie; Xi, Zhen; Yi, Long

2016-07-01

Hydrogen sulfide (H2S) is an important signalling molecule with multiple biological functions. The reported H2S fluorescent probes are majorly based on redox or nucleophilic reactions. The combination usage of both redox and nucleophilic reactions could improve the probe’s selectivity, sensitivity and stability. Herein we report a new dual-reactable probe with yellow turn-on fluorescence for H2S detection. The sensing mechanism of the dual-reactable probe was based on thiolysis of NBD (7-nitro-1,2,3-benzoxadiazole) amine (a nucleophilic reaction) and reduction of azide to amine (a redox reaction). Compared with its corresponding single-reactable probes, the dual-reactable probe has higher selectivity and fluorescence turn-on fold with magnitude of multiplication from that of each single-reactable probe. The highly selective and sensitive properties enabled the dual-reactable probe as a useful tool for efficiently sensing H2S in aqueous buffer and in living cells.

Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion

DOE PAGES

Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; ...

2016-02-01

We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN) 3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

Removal of bulk dissolved organic carbon (DOC) and trace organic compounds by bank filtration and artificial recharge.

PubMed

Grünheid, Steffen; Amy, Gary; Jekel, Martin

2005-09-01

Bank filtration and artificial recharge provide an important drinking water source to the city of Berlin. Due to the practice of water recycling through a semi-closed urban water cycle, the introduction of effluent organic matter (EfOM) and persistent trace organic pollutants in the drinking water is of potential concern. In the work reported herein, the research objectives are to study the removal of bulk and trace organics at bank filtration and artificial recharge sites and to assess important factors of influence for the Berlin area. The monthly analytical program is comprised of dissolved organic carbon (DOC), UV absorbance (UVA254), liquid chromatography with organic carbon detection (LC-OCD), differentiated adsorbable organic halogens (AOX) and single organic compound analysis of a few model compounds. More than 1 year of monitoring was conducted on observation wells located along the flowpaths of the infiltrating water at two field sites that have different characteristics regarding redox conditions, travel time, and travel distance. Two transects are highlighted: one associated with a bank filtration site dominated by anoxic/anaerobic conditions with a travel time of up to 4-5 months, and another with an artificial recharge site dominated by aerobic conditions with a travel time of up to 50 days. It was found that redox conditions and travel time significantly influence the DOC degradation kinetics and the efficiency of AOX and trace compound removal.

Optical-fiber strain sensors with asymmetric etched structures.

PubMed

Vaziri, M; Chen, C L

1993-11-01

Optical-fiber strain gauges with asymmetric etched structures have been analyzed, fabricated, and tested. These sensors are very sensitive with a gauge factor as high as 170 and a flat frequency response to at least 2.7 kHz. The gauge factor depends on the asymmetry of the etched structures and the number of etched sections. To understand the physical principles involved, researchers have used structural analysis programs based on a finite-element method to analyze fibers with asymmetric etched structures under tensile stress. The results show that lateral bends are induced on the etched fibers when they are stretched axially. To relate the lateral bending to the optical attenuation, we have also employed a ray-tracing technique to investigate the dependence of the attenuation on the structural deformation. Based on the structural analysis and the ray-tracing study parameters affecting the sensitivity have been studied. These results agree with the results of experimental investigations.

Chemical Sample Processing for Combined Selenium Isotope and Selenium-Tellurium Elemental Investigation of the Earth's Igneous Reservoirs

NASA Astrophysics Data System (ADS)

Yierpan, Aierken; König, Stephan; Labidi, Jabrane; Kurzawa, Timon; Babechuk, Michael G.; Schoenberg, Ronny

2018-02-01

The redox-sensitive, chalcophile, and volatile Se stable isotope system offers new perspectives to investigate the origin and evolution of terrestrial volatiles and the roles of magmatic and recycling processes in the development of the redox contrast between Earth's reservoirs. Selenium isotope systematics become more robust in a well-constrained petrogenetic context as can be inferred from Se-Te elemental signatures of sulfides and igneous rocks. In this study, we present a high-yield chemical sample processing method that allows the determination of Se-Te concentrations and Se isotope composition from the same sample digest of silicate rocks by hydride generation isotope dilution (ID) quadrupole inductively coupled plasma mass spectrometry (ICP-MS) and double spike (DS) multicollector (MC)-ICP-MS, respectively. Our procedure yields ˜80% Se-Te recoveries with quantitative separation of relevant interfering elements such as Ge and HG-buffering metals. Replicate analyses of selected international reference materials yield uncertainties better than 0.11‰ (2 s.d.) on δ82/76Se and 3% (r.s.d.) on Se concentration for DS MC-ICP-MS determinations for as low as ˜10 ng sample Se. The precision of Se-Te concentration measurements by ID ICP-MS is better than 3% and 5% (r.s.d.) for total amounts of ˜0.5-1 ng Se and ˜0.2-0.5 ng Te, respectively. The basaltic reference materials have variable Se-Te contents, but their δ82/76Se values are rather uniform (on average 0.23 ± 0.14‰; 2 s.d.) and different from the chondritic value. This altogether provides the methodology and potential to extend the limited data set of coupled Se isotope and Se-Te elemental systematics of samples relevant to study the terrestrial igneous inventory.

Novel insights into redox system and the mechanism of redox regulation.

PubMed

Wang, Xin; Hai, Chunxu

2016-07-01

In view of the critical role of redox system in numerous physiological and pathophysiological processes, it is important to clearly understand the family members and regulatory mechanism of redox system. In this work, we will systematically review the current data detailing the reactive oxygen species (ROS), enzymatic and non-enzymatic antioxidants and redox sensitive transcription factors and we give a brief description of redox-mediated epigenetic and post-translational regulation. We propose that the redox system functions as a "Redox Chain", consisting of "ROS-generating Enzyme Chain", "Combined Antioxidant Chain" and "Transcription Factor Chain". We suggest that an individualized assessment of the redox status in the body should be conducted for the redox intervention of a patient. The strategy of intervention is to maintain redox homeostasis via either facilitation of ROS signaling or enhancement of antioxidant defense. These findings provide valuable new insights into redox system and open up new paths for the control of redox-related disorders.

Roles and potential mechanisms of selenium in countering thyrotoxicity of DEHP.

PubMed

Zhang, Pei; Guan, Xie; Yang, Min; Zeng, Li; Liu, Changjiang

2018-04-01

Di-(2-ethylhexyl) phthalate (DEHP) as a ubiquitous environmental contaminant could disturb thyroid hormone (TH) homeostasis. Selenium as an essential trace element has protective effects on thyroids. To verify roles of selenium in countering thyrotoxicity of DEHP and elucidate potential mechanisms, Sprague-Dawley rats and Nthy-ori 3-1 cells were treated with DEHP or/and selenomethionine (SeMet). Results showed that selenium supplementation elevated plasma free thyroxine (FT4) that was decreased by DEHP, and free triiodothyronine (FT3) and thyroid stimulating hormone (TSH) levels were also partially recovered. DEHP-caused histopathologic changes were ameliorated after selenium supplementation, as indicated by recovered thyroid follicular epithelial cell numbers and cavity diameters. DEHP disrupted the redox equilibrium, causing depletions of SOD, GPx1, GPx3, and TxnRd, and accumulations of MDA. Nevertheless, selenium supplementation effectively improved the redox status. DEHP affected biosynthesis, biotransformation, biotransport, and metabolism of THs, as well as thyrotropin releasing hormone receptor (TRHr) levels. Plasma selenium, thyroid peroxidase (TPO), deiodinase 1 (Dio1), and transthyretin (TTR) were downregulated, while Dio3, Ugt1a1, Sult1e1, CYP2b1, CYP3a1, and TRHr were upregulated by DEHP. However, selenium supplementation led to elevations of selenium, Dio1 and TTR, and reductions of Ugt1a1, Sult1e1, CYP2b1, and TRHr. TPO, Dio3, and CYP3a1 were not significantly affected by selenium supplementation. Taken together, selenium could ameliorate DEHP-caused TH dyshomeostasis via modulations of the redox status, Dio1, TTR, TRHr, and hepatic enzymes. Copyright © 2017 Elsevier B.V. All rights reserved.

Mobility and phytoavailability of As and Pb in a contaminated soil using pine sawdust biochar under systematic change of redox conditions.

PubMed

Beiyuan, Jingzi; Awad, Yasser M; Beckers, Felix; Tsang, Daniel C W; Ok, Yong Sik; Rinklebe, Jörg

2017-07-01

Biochar has been adopted to control the mobility and phytoavailability of trace elements (TEs) in soils. To date, no attempt has been made to determine the mobility and phytoavailability of arsenic (As) and lead (Pb) in a contaminated soil with biochars as amendments under predefined redox potentials (E H ). Thus, in this study, a soil contaminated with As and Pb (2047 and 1677 mg kg -1 , respectively) was pre-incubated for 105 days with three amendments (pine sawdust biomass (BM) and two biochars produced from the same feedstock at 300 °C (BC300) and 550 °C (BC550)). The aged samples were then exposed to dynamic E H conditions to evaluate the mobility and phytoavailability of As and Pb after immobilization. The BM amendment significantly decreased and the BC300 slightly reduced the mobility and phytoavailability of As and Pb, which may be related to the oxygen-containing functional groups on the surface of BM and BC300. In contrast, BC550 increased the mobility of As at -300 to -100 mV and 100 mV, enhanced the phytoavailability of As under oxidizing condition (>100 mV), but reduced the phytoavailability of Pb, which might be caused by the properties of amendments and redox chemistry of the TEs. The effectiveness of BM and biochars for the stabilization of As and Pb varied under dynamic E H conditions, which indicates that detailed investigations should be conducted before the applications of biochar as soil amendment under variable environmental conditions, especially for contaminated paddy soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Diurnal hydrological physicochemical controls and sampling methods for minor and trace elements in an Alpine glacial hydrological system

NASA Astrophysics Data System (ADS)

Mitchell, Andrew C.; Brown, Giles H.

2007-01-01

SummaryWe present diurnal (i) 0.45 and 0.1 μm pore-size filtered and (ii) operationally defined labile particulate-associated major, minor and trace element concentrations and fluxes in glacial outflow waters draining Haut Glacier d'Arolla, Switzerland. We use speciation modelling (PHREEQCi) and water-suspended sediment interaction experiments are utilised under conditions analogous to the subglacial channellised hydrological system, in order to assess controls on, and the most suitable sampling methods to investigate short-term variations in the mode of major, minor and trace element species export from a glacierised headwater catchment. 0.45 μm pore-size filtered major ions, Sr and U are exported in glacial outflow waters predominately as mobile monovalent or divalent ions or as carbonate complexes, and are controlled by hydrological variations over diurnal cycles, exhibiting an inverse concentration with increasing meltwater discharge. Conversely, 0.45 μm pore-size filtered concentrations of most minor and trace elements ( e.g. Fe, Mn, Co, Ba and Pb) exhibit variations that are not strongly inter-correlated with meltwater discharge or suspended sediment concentrations (SSC) over diurnal periods. The use of 0.45 and 0.1 μm pore-size filter membranes indicates that significant colloidal material is not passing through the 0.45 μm pore-size filters, and these unsystematic variations are not a result of colloid measurement. Speciation modelling applied to meltwaters and observations during water-rock interaction experiments suggest that these unsystematic temporal variations reflect physicochemical controls. This includes sorption, and the oversaturation and precipitation of Fe and Al (oxi)hydroxides, and the co-precipitation of other species. Diurnal pH variations appear important in controlling such short-term physicochemical controls, which limits such species use for hydrological investigations. The percentage of total elemental fluxes exported as the labile particulate-associated flux (%PAF) for each minor and trace element changes dramatically between and during the diurnal cycles, reflecting species-specific sensitivity to hydrological and physicochemical controls. Hydrological interpretations of hydrochemical data must be made carefully when using chemical determinations by ICP-MS, since we demonstrate that measurements will comprise of any material that passes through the filter. This can lead to higher concentration measurements than if determined by ion chromatography, which measures truly ionic dissolved species.

Assessing the risks of trace elements in environmental materials under selected greenhouse vegetable production systems of China.

PubMed

Chen, Yong; Huang, Biao; Hu, Wenyou; Weindorf, David C; Liu, Xiaoxiao; Niedermann, Silvana

2014-02-01

The risk assessment of trace elements of different environmental media in conventional and organic greenhouse vegetable production systems (CGVPS and OGVPS) can reveal the influence of different farming philosophy on the trace element accumulations and their effects on human health. These provide important basic data for the environmental protection and human health. This paper presents trace element accumulation characteristics of different land uses; reveals the difference of soil trace element accumulation both with and without consideration of background levels; compares the trace element uptake by main vegetables; and assesses the trace element risks of soils, vegetables, waters and agricultural inputs, using two selected greenhouse vegetable systems in Nanjing, China as examples. Results showed that greenhouse vegetable fields contained significant accumulations of Zn in CGVPS relative to rice-wheat rotation fields, open vegetable fields, and geochemical background levels, and this was the case for organic matter in OGVPS. The comparative analysis of the soil medium in two systems with consideration of geochemical background levels and evaluation of the geo-accumulation pollution index achieved a more reasonable comparison and accurate assessment relative to the direct comparison analysis and the evaluation of the Nemerow pollution index, respectively. According to the Chinese food safety standards and the value of the target hazard quotient or hazard index, trace element contents of vegetables were safe for local residents in both systems. However, the spatial distribution of the estimated hazard index for producers still presented certain specific hotspots which may cause potential risk for human health in CGVPS. The water was mainly influenced by nitrogen, especially for CGVPS, while the potential risk of Cd and Cu pollution came from sediments in OGVPS. The main inputs for trace elements were fertilizers which were relatively safe based on relevant standards; but excess application caused trace element accumulations in the environmental media. Copyright © 2013 Elsevier B.V. All rights reserved.

Sufficient oxygen for animal respiration 1,400 million years ago

PubMed Central

Zhang, Shuichang; Wang, Xiaomei; Wang, Huajian; Bjerrum, Christian J.; Hammarlund, Emma U.; Costa, M. Mafalda; Connelly, James N.; Zhang, Baomin; Su, Jin; Canfield, Donald E.

2016-01-01

The Mesoproterozoic Eon [1,600–1,000 million years ago (Ma)] is emerging as a key interval in Earth history, with a unique geochemical history that might have influenced the course of biological evolution on Earth. Indeed, although this time interval is rather poorly understood, recent chromium isotope results suggest that atmospheric oxygen levels were <0.1% of present levels, sufficiently low to have inhibited the evolution of animal life. In contrast, using a different approach, we explore the distribution and enrichments of redox-sensitive trace metals in the 1,400 Ma sediments of Unit 3 of the Xiamaling Formation, North China Block. Patterns of trace metal enrichments reveal oxygenated bottom waters during deposition of the sediments, and biomarker results demonstrate the presence of green sulfur bacteria in the water column. Thus, we document an ancient oxygen minimum zone. We develop a simple, yet comprehensive, model of marine carbon−oxygen cycle dynamics to show that our geochemical results are consistent with atmospheric oxygen levels >4% of present-day levels. Therefore, in contrast to previous suggestions, we show that there was sufficient oxygen to fuel animal respiration long before the evolution of animals themselves. PMID:26729865

Trace elements in natural azurite pigments found in illuminated manuscript leaves investigated by synchrotron x-ray fluorescence and diffraction mapping

NASA Astrophysics Data System (ADS)

Smieska, Louisa M.; Mullett, Ruth; Ferri, Laurent; Woll, Arthur R.

2017-07-01

We present trace-element and composition analysis of azurite pigments in six illuminated manuscript leaves, dating from the thirteenth to sixteenth century, using synchrotron-based, large-area x-ray fluorescence (SR-XRF) and diffraction (SR-XRD) mapping. SR-XRF mapping reveals several trace elements correlated with azurite, including arsenic, zirconium, antimony, barium, and bismuth, that appear in multiple manuscripts but were not always detected by point XRF. Within some manuscript leaves, variations in the concentration of trace elements associated with azurite coincide with distinct regions of the illuminations, suggesting systematic differences in azurite preparation or purification. Variations of the trace element concentrations in azurite are greater among different manuscript leaves than the variations within each individual leaf, suggesting the possibility that such impurities reflect distinct mineralogical/geologic sources. SR-XRD maps collected simultaneously with the SR-XRF maps confirm the identification of azurite regions and are consistent with impurities found in natural mineral sources of azurite. In general, our results suggest the feasibility of using azurite trace element analysis for provenance studies of illuminated manuscript fragments, and demonstrate the value of XRF mapping in non-destructive determination of trace element concentrations within a single pigment.

Co-digestion of manure and industrial waste--The effects of trace element addition.

PubMed

Nordell, Erik; Nilsson, Britt; Nilsson Påledal, Sören; Karisalmi, Kaisa; Moestedt, Jan

2016-01-01

Manure is one of the most common substrates for biogas production. Manure from dairy- and swine animals are often considered to stabilize the biogas process by contributing nutrients and trace elements needed for the biogas process. In this study two lab-scale reactors were used to evaluate the effects of trace element addition during co-digestion of manure from swine- and dairy animals with industrial waste. The substrate used contained high background concentrations of both cobalt and nickel, which are considered to be the most important trace elements. In the reactor receiving additional trace elements, the volatile fatty acids (VFA) concentration was 89% lower than in the control reactor. The lower VFA concentration contributed to a more digested digestate, and thus lower methane emissions in the subsequent storage. Also, the biogas production rate increased with 24% and the biogas production yield with 10%, both as a result of the additional trace elements at high organic loading rates. All in all, even though 50% of the feedstock consisted of manure, trace element addition resulted in multiple positive effects and a more reliable process with stable and high yield. Copyright © 2015 Elsevier Ltd. All rights reserved.

Trace elements in dialysis.

PubMed

Filler, Guido; Felder, Sarah

2014-08-01

In end-stage chronic kidney disease (CKD), pediatric nephrologists must consider the homeostasis of the multiple water-soluble ions that are influenced by renal replacement therapy (RRT). While certain ions such as potassium and calcium are closely monitored, little is known about the handling of trace elements in pediatric dialysis. RRT may lead to accumulation of toxic trace elements, either due to insufficient elimination or due to contamination, or to excessive removal of essential trace elements. However, trace elements are not routinely monitored in dialysis patients and no mechanism for these deficits or toxicities has been established. This review summarizes the handling of trace elements, with particular attention to pediatric data. The best data describe lead and indicate that there is a higher prevalence of elevated lead (Pb, atomic number 82) levels in children on RRT when compared to adults. Lead is particularly toxic in neurodevelopment and lead levels should therefore be monitored. Monitoring of zinc (Zn, atomic number 30) and selenium (Se, atomic number 34) may be indicated in the monitoring of all pediatric dialysis patients to reduce morbidity from deficiency. Prospective studies evaluating the impact of abnormal trace elements and the possible therapeutic value of intervention are required.

Determination of trace elements and their concentrations in clay balls: problem of geophagia practice in Ghana.

PubMed

Arhin, Emmanuel; Zango, Musah S

2017-02-01

Ten samples of 100 g weight were subsampled from 1400 g of the clay balls from which the contained trace element levels were determined by X-ray fluorescence technique. The results of trace elements in the clay balls were calibrated using certified reference materials "MAJMON" and "BH-1." The results showed elevated concentrations but with different concentration levels in the regions, particularly with arsenic, chromium, cobalt, Cs, Zr and La. These trace elements contained in the clay balls are known to be hazardous to human health. Thence the relatively high concentrations of these listed trace elements in clay balls in the three regions, namely Ashanti, Upper East and Volta, which are widely sold in markets in Ghana, could present negative health impact on consumers if consumed at 70 g per day or more and on regular basis. On the basis of these, the study concludes an investigation to establish breakeven range for trace element concentrations in the clay balls as it has been able to demonstrate the uneven and elevated values in them. The standardized safe ranges of trace elements will make the practice safer for the people that ingest clay balls in Ghana.

Trace-element concentrations in streambed sediment across the conterminous United States

USGS Publications Warehouse

Rice, Karen C.

1999-01-01

Trace-element concentrations in 541 streambed-sediment samples collected from 20 study areas across the conterminous United States were examined as part of the National Water-Quality Assessment Program of the U.S. Geological Survey. Sediment samples were sieved and the <63-μm fraction was retained for determination of total concentrations of trace elements. Aluminum, iron, titanium, and organic carbon were weakly or not at all correlated with the nine trace elements examined:  arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc. Four different methods of accounting for background/baseline concentrations were examined; however, normalization was not required because field sieving removed most of the background differences between samples. The sum of concentrations of trace elements characteristic of urban settings - copper, mercury, lead, and zinc - was well correlated with population density, nationwide. Median concentrations of seven trace elements (all nine examined except arsenic and selenium) were enriched in samples collected from urban settings relative to agricultural or forested settings. Forty-nine percent of the sites sampled in urban settings had concentrations of one or more trace elements that exceeded levels at which adverse biological effects could occur in aquatic biota.

Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Herrin, J. S.

2010-01-01

Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected

Rare earth element abundances in presolar SiC

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Ávila, J. N.; Lugaro, M.; Cristallo, S.; Holden, P.; Lanc, P.; Nittler, L.; Alexander, C. M. O'D.; Gyngard, F.; Amari, S.

2018-01-01

Individual isotope abundances of Ba, lanthanides of the rare earth element (REE) group, and Hf have been determined in bulk samples of fine-grained silicon carbide (SiC) from the Murchison CM2 chondrite. The analytical protocol involved secondary ion mass spectrometry with combined high mass resolution and energy filtering to exclude REE oxide isobars and Si-C-O clusters from the peaks of interest. Relative sensitivity factors were determined through analysis of NIST SRM reference glasses (610 and 612) as well as a trace-element enriched SiC ceramic. When normalised to chondrite abundances, the presolar SiC REE pattern shows significant deficits at Eu and Yb, which are the most volatile of the REE. The pattern is very similar to that observed for Group III refractory inclusions. The SiC abundances were also normalised to s-process model predictions for the envelope compositions of low-mass (1.5-3 M⊙) AGB stars with close-to-solar metallicities (Z = 0.014 and 0.02). The overall trace element abundances (excluding Eu and Yb) appear consistent with the predicted s-process patterns. The depletions of Eu and Yb suggest that these elements remained in the gas phase during the condensation of SiC. The lack of depletion in some other moderately refractory elements (like Ba), and the presence of volatile elements (e.g. Xe) indicates that these elements were incorporated into SiC by other mechanisms, most likely ion implantation.

Microfluidic Experiments Studying Pore Scale Interactions of Microbes and Geochemistry

NASA Astrophysics Data System (ADS)

Chen, M.; Kocar, B. D.

2016-12-01

Understanding how physical phenomena, chemical reactions, and microbial behavior interact at the pore-scale is crucial to understanding larger scale trends in groundwater chemistry. Recent studies illustrate the utility of microfluidic devices for illuminating pore-scale physical-biogeochemical processes and their control(s) on the cycling of iron, uranium, and other important elements 1-3. These experimental systems are ideal for examining geochemical reactions mediated by microbes, which include processes governed by complex biological phenomenon (e.g. biofilm formation, etc.)4. We present results of microfluidic experiments using a model metal reducing bacteria and varying pore geometries, exploring the limitations of the microorganisms' ability to access tight pore spaces, and examining coupled biogeochemical-physical controls on the cycling of redox sensitive metals. Experimental results will provide an enhanced understanding of coupled physical-biogeochemical processes transpiring at the pore-scale, and will constrain and compliment continuum models used to predict and describe the subsurface cycling of redox-sensitive elements5. 1. Vrionis, H. A. et al. Microbiological and geochemical heterogeneity in an in situ uranium bioremediation field site. Appl. Environ. Microbiol. 71, 6308-6318 (2005). 2. Pearce, C. I. et al. Pore-scale characterization of biogeochemical controls on iron and uranium speciation under flow conditions. Environ. Sci. Technol. 46, 7992-8000 (2012). 3. Zhang, C., Liu, C. & Shi, Z. Micromodel investigation of transport effect on the kinetics of reductive dissolution of hematite. Environ. Sci. Technol. 47, 4131-4139 (2013). 4. Ginn, T. R. et al. Processes in microbial transport in the natural subsurface. Adv. Water Resour. 25, 1017-1042 (2002). 5. Scheibe, T. D. et al. Coupling a genome-scale metabolic model with a reactive transport model to describe in situ uranium bioremediation. Microb. Biotechnol. 2, 274-286 (2009).

Soluble trace elements and total mercury in Arctic Alaskan snow

USGS Publications Warehouse

Snyder-Conn, E.; Garbarino, J.R.; Hoffman, G.L.; Oelkers, A.

1997-01-01

Ultraclean field and laboratory procedures were used to examine trace element concentrations in northern Alaskan snow. Sixteen soluble trace elements and total mercury were determined in snow core samples representing the annual snowfall deposited during the 1993-94 season at two sites in the Prudhoe Bay oil field and nine sites in the Arctic National Wildlife Refuge (Arctic NWR). Results indicate there were two distinct point sources for trace elements in the Prudhoe Bay oil field - a source associated with oil and gas production and a source associated with municipal solid-waste incineration. Soluble trace element concentrations measured in snow from the Arctic NWR resembled concentrations of trace elements measured elsewhere in the Arctic using clean sample-collection and processing techniques and were consistent with deposition resulting from widespread arctic atmospheric contamination. With the exception of elements associated with sea salts, there were no orographic or east-west trends observed in the Arctic NWR data, nor were there any detectable influences from the Prudhoe Bay oil field, probably because of the predominant easterly and northeasterly winds on the North Slope of Alaska. However, regression analysis on latitude suggested significant south-to-north increases in selected trace element concentrations, many of which appear unrelated to the sea salt contribution.

The effects of trace element content on pyrite oxidation rates

NASA Astrophysics Data System (ADS)

Gregory, D. D.; Lyons, T.; Cliff, J. B.; Perea, D. E.; Johnson, A.; Romaniello, S. J.; Large, R. R.

2017-12-01

Pyrite acts as both an important source and sink for many different metals and metalloids in the environment, including many that are toxic. Oxidation of pyrite can release these elements while at the same time producing significant amounts of sulfuric acid. Such issues are common in the vicinity of abandoned mines and smelters, but, as pyrite is a common accessory mineral in many different lithologies, significant pyrite oxidation can occur whenever pyritic rocks are exposed to oxygenated water or the atmosphere. Accelerated exposure to oxygen can occur during deforestation, fracking for petroleum, and construction projects. Geochemical models for pyrite oxidation can help us develop strategies to mitigate these deleterious effects. An important component of these models is an accurate pyrite oxidation rate; however, current pyrite oxidation rates have been determined using relatively pure pyrite. Natural pyrite is rarely pure and has a wide range of trace element concentrations that may affect the oxidation rate. Furthermore, the position of trace elements within the mineral lattice can also affect the oxidation rate. For example, elements such as Ni and Co, which substitute into the pyrite lattice, are thought to stabilize the lattice and thus prevent pyrite oxidation. Alternatively, trace elements that are held within inclusions of other minerals could form a galvanic cell with the surrounding pyrite, thus enhancing pyrite oxidation rates. In this study, we present preliminary analyses from three different pyrite oxidation experiments each using natural pyrite with different trace element compositions. These results show that the pyrite with the highest trace element concentration has approximately an order of magnitude higher oxidation rate compared to the lowest trace element sample. To further elucidate the mechanisms, we employed microanalytical techniques to investigate how the trace elements are held within the pyrite. LA-ICPMS was used to determine the variability of trace element content from the pyrite samples. These data were then used to select areas of interest for NanoSIMS analyses, which in turn was used to select areas for TEM and APT. These analyses show that the trace element content of pyrite can be highly variable, which may significantly affect the rate of pyrite oxidation.

Concentrations of selected trace elements in fish tissue and streambed sediment in the Clark Fork-Pend Oreille and Spokane River basins, Washington, Idaho, and Montana, 1998

USGS Publications Warehouse

Maret, Terry R.; Skinner, K.D.

2000-01-01

Fish tissue and bed sediment samples were collected from 16 stream sites in the Northern Rockies Intermontane Basins study area in 1998 as part of the U.S. Geological Survey National Water-Quality Assessment Program. Bed sediment samples were analyzed for 45 trace elements, and fish livers and sportfish fillets were analyzed for 22 elements to characterize the occurrence and distribution of these elements in relation to stream characteristics and land use activities. Nine trace elements of environmental concern—arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc—were detected in bed sediment, but not all of these elements were detected in fish tissue. Trace-element concentrations were highest in bed sediment samples collected at sites downstream from significant natural mineral deposits and (or) mining activities. Arsenic, cadmium, copper, lead, mercury, and zinc in bed sediment at some sites were elevated relative to national median concentrations, and some concentrations were at levels that can adversely affect aquatic biota. Although trace-element concentrations in bed sediment exceeded various guidelines, no concentrations in sportfish fillets exceeded U.S. Environmental Protection Agency screening values for the protection of human health. Correlations between most trace-element concentrations in bed sediment and fish tissue (liver and fillet) were not significant (r0.05). Concentrations of arsenic, cadmium, copper, lead, mercury, nickel, selenium, and zinc in bed sediment were significantly correlated (r=0.53 to 0.88, p2=0.95 and 0.99, p<0.001) that corresponded to trace-element enrichment categories. These strong relations warrant further study using mine density as an explanatory variable to predict trace-element concentrations in bed sediment.

Trace Elements in Marine Sediment and Organisms in the Gulf of Thailand

PubMed Central

Worakhunpiset, Suwalee

2018-01-01

This review summarizes the findings from studies of trace element levels in marine sediment and organisms in the Gulf of Thailand. Spatial and temporal variations in trace element concentrations were observed. Although trace element contamination levels were low, the increased urbanization and agricultural and industrial activities may adversely affect ecosystems and human health. The periodic monitoring of marine environments is recommended in order to minimize human health risks from the consumption of contaminated marine organisms. PMID:29677146