Sample records for dissolved fe dfe
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Distal transport of dissolved hydrothermal iron in the deep South Pacific Ocean
Fitzsimmons, Jessica N.; Boyle, Edward A.; Jenkins, William J.
2014-01-01
Until recently, hydrothermal vents were not considered to be an important source to the marine dissolved Fe (dFe) inventory because hydrothermal Fe was believed to precipitate quantitatively near the vent site. Based on recent abyssal dFe enrichments near hydrothermal vents, however, the leaky vent hypothesis [Toner BM, et al. (2012) Oceanography 25(1):209–212] argues that some hydrothermal Fe persists in the dissolved phase and contributes a significant flux of dFe to the global ocean. We show here the first, to our knowledge, dFe (<0.4 µm) measurements from the abyssal southeast and southwest Pacific Ocean, where dFe of 1.0–1.5 nmol/kg near 2,000 m depth (0.4–0.9 nmol/kg above typical deep-sea dFe concentrations) was determined to be hydrothermally derived based on its correlation with primordial 3He and dissolved Mn (dFe:3He of 0.9–2.7 × 106). Given the known sites of hydrothermal venting in these regions, this dFe must have been transported thousands of kilometers away from its vent site to reach our sampling stations. Additionally, changes in the size partitioning of the hydrothermal dFe between soluble (<0.02 µm) and colloidal (0.02–0.4 µm) phases with increasing distance from the vents indicate that dFe transformations continue to occur far from the vent source. This study confirms that although the southern East Pacific Rise only leaks 0.02–1% of total Fe vented into the abyssal Pacific, this dFe persists thousands of kilometers away from the vent source with sufficient magnitude that hydrothermal vents can have far-field effects on global dFe distributions and inventories (≥3% of global aerosol dFe input). PMID:25349389
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Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes
NASA Astrophysics Data System (ADS)
Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.
2017-04-01
Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.
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NASA Astrophysics Data System (ADS)
Sherrell, R. M.; Fitzsimmons, J. N.; Roccanova, J.; Schofield, O.; Meredith, M. P.
2016-02-01
The Western Antarctic Peninsula (WAP) shelf region is is a natural Fe fertilization zone where primary production exceeds that of the adjacent open Southern Ocean. Until recently, however, distributions of Fe and of other bioactive metals were completely lacking for the WAP, and the sources and delivery mechanisms of Fe to the euphotic zone were only speculated upon. We have previously presented surface water (2m) dissolved (dTM, <0.2µm) and particulate (pTM, >0.45µm) distributions for Fe and a suite of other bioactive metals over the WAP shelf, covering the Palmer LTER sampling grid for Jan. 2010, 2011 and 2012. We now report the first complete 3D distribution of dissolved and colloidal Fe (and Mn, Zn, Cu, Ni, Cd and Pb) over the LTER grid in Jan. 2015, allowing assessment of dFe size speciation, sources and transport pathways in this dynamic shelf system. Dissolved metals were analyzed by automated offline preconcentration (seaFAST-pico, ESI) followed by sector-field ICP-MS. We confirm previous findings of low ( 0.1nM) dFe in surface waters on the mid-outer shelf in the northern portion of the grid, and now find that concentrations at this level or below persist through the euphotic zone. However, dFe increases rapidly with depth, with low surface values underlain by substantially higher concentrations even at 50m. Inner shelf surface waters are generally substantially > 0.1nM, suggesting Fe replete conditions in this region. Vertical profiles reveal that dFe generally increases with depth, much moreso in the inner shelf (dFe up to 5.0nM) than the outer shelf. A general N-S gradient in dFe is also evident, with concentrations higher in the southern WAP, especially in Marguerite Bay. In addition, shelf stations often show a dFe maximum suggesting remineralization from sinking biogenic particles. These findings for dFe and for the other metals, will be used to help unravel the biogeochemical workings of natural Fe fertilization in this region.
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NASA Astrophysics Data System (ADS)
Schallenberg, Christina; van der Merwe, Pier; Chever, Fanny; Cullen, Jay T.; Lannuzel, Delphine; Bowie, Andrew R.
2016-09-01
Distributions of dissolved iron (dFe) and its reduced form, Fe(II), to a depth of 1000 m were investigated under the seasonal pack ice off East Antarctica during the Sea Ice Physics and Ecosystem experiment (SIPEX-2) sea-ice voyage in September-October 2012. Concentrations of dFe were elevated up to five-fold relative to Southern Ocean background concentrations and were spatially variable. The mean dFe concentration was 0.44±0.4 nM, with a range from 0.09 to 3.05 nM. Profiles of dFe were more variable within and among stations than were macronutrients, suggesting that coupling between these biologically-essential elements was weak at the time of the study. Brine rejection and drainage from sea ice are estimated to be the dominant contributors to elevated dFe concentrations in the mixed layer, but mass budget considerations indicate that estimated dFe fluxes from brine input alone are insufficient to account for all observed dFe. Melting icebergs and shelf sediments are suspected to provide the additional dFe. Fe(II) was mostly below the detection limit but elevated at depth near the continental shelf, implying that benthic processes are a source of reduced Fe in bottom waters. The data indicate that dFe builds up under the seasonal sea-ice cover during winter and that reduction of Fe may be hampered in early spring by several factors such as lack of electron donors, low biological productivity and inadequate light below the sea ice. The accumulated dFe pool in the mixed layer is expected to contribute to the formation of the spring bloom as the ice retreats.
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Pathways and supply of dissolved iron in the Amundsen Sea (Antarctica)
NASA Astrophysics Data System (ADS)
St-Laurent, P.; Yager, P. L.; Sherrell, R. M.; Stammerjohn, S. E.; Dinniman, M. S.
2017-09-01
Numerous coastal polynyas fringe the Antarctic continent and strongly influence the productivity of Antarctic shelf systems. Of the 46 Antarctic coastal polynyas documented in a recent study, the Amundsen Sea Polynya (ASP) stands out as having the highest net primary production per unit area. Incubation experiments suggest that this productivity is partly controlled by the availability of dissolved iron (dFe). As a first step toward understanding the iron supply of the ASP, we introduce four plausible sources of dFe and simulate their steady spatial distribution using conservative numerical tracers. The modeled distributions replicate important features from observations including dFe maxima at the bottom of deep troughs and enhanced concentrations near the ice shelf fronts. A perturbation experiment with an idealized drawdown mimicking summertime biological uptake and subsequent resupply suggests that glacial meltwater and sediment-derived dFe are the main contributors to the prebloom dFe inventory in the top 100 m of the ASP. The sediment-derived dFe depends strongly on the buoyancy-driven overturning circulation associated with the melting ice shelves (the "meltwater pump") to add dFe to the upper 300 m of the water column. The results support the view that ice shelf melting plays an important direct and indirect role in the dFe supply and delivery to polynyas such as the ASP.
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Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; ...
2017-05-19
Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.
Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less
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NASA Astrophysics Data System (ADS)
Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.
2017-08-01
Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.
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Temporal variability of dissolved iron species in the mesopelagic zone at Ocean Station PAPA
NASA Astrophysics Data System (ADS)
Schallenberg, Christina; Ross, Andrew R. S.; Davidson, Ashley B.; Stewart, Gillian M.; Cullen, Jay T.
2017-08-01
Deposition of atmospheric aerosols to the surface ocean is considered an important mechanism for the supply of iron (Fe) to remote ocean regions, but direct observations of the oceanic response to aerosol deposition are sparse. In the high nutrient, low chlorophyll (HNLC) subarctic Pacific Ocean we observed a dissolved Fe and Fe(II) anomaly at depth that is best explained as the result of aerosol deposition from Siberian forest fires in May 2012. Interestingly, there was no evidence of enhanced dFe concentrations in surface waters, nor was there a detectable phytoplankton bloom in response to the suspected aerosol deposition. Dissolved Fe (dFe) and Fe(II) showed the strongest enhancement in the subsurface oxygen deficient zone (ODZ), where oxygen concentrations <50 μmol kg-1 are prevalent. In the upper 200 m, dFe concentrations were at or below historic background levels, consistent with a short residence time of aerosol particles in surface waters and possible scavenging loss of dFe. Aerosol toxicity and/or dominance of particle scavenging over dissolution of Fe in the upper water column may have contributed to the lack of a strong phytoplankton response.
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NASA Astrophysics Data System (ADS)
Nakanowatari, Takuya; Nakamura, Tomohiro; Uchimoto, Keisuke; Nishioka, Jun; Mitsudera, Humio; Wakatsuchi, Masaaki
2017-05-01
Iron (Fe) is an essential nutrient for marine phytoplankton and it constitutes an important element in the marine carbon cycle in the ocean. This study examined the mechanisms controlling seasonal variation of dissolved Fe (dFe) in the western subarctic North Pacific (WSNP), using an ocean general circulation model coupled with a simple biogeochemical model incorporating a dFe cycle fed by two major sources (atmospheric dust and continental shelf sediment). The model reproduced the seasonal cycle of observed concentrations of dFe and macronutrients at the surface in the Oyashio region with maxima in winter (February-March) and minima in summer (July-September), although the simulated seasonal amplitudes are a half of the observed values. Analysis of the mixed-layer dFe budget indicated that both local vertical entrainment and lateral advection are primary contributors to the wintertime increase in dFe concentration. In early winter, strengthened northwesterly winds excite southward Ekman transport and Ekman upwelling over the western subarctic gyre, transporting dFe-rich water southward. In mid to late winter, the southward western boundary current of the subarctic gyre and the outflow from the Sea of Okhotsk also bring dFe-rich water to the Oyashio region. The contribution of atmospheric dust to the dFe budget is several times smaller than these ocean transport processes in winter. These results suggest that the westerly wind-induced Ekman transport and gyre circulation systematically influence the seasonal cycle of WSNP surface dFe concentration.
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The Distribution of Dissolved Iron in the West Atlantic Ocean
Rijkenberg, Micha J. A.; Middag, Rob; Laan, Patrick; Gerringa, Loes J. A.; van Aken, Hendrik M.; Schoemann, Véronique; de Jong, Jeroen T. M.; de Baar, Hein J. W.
2014-01-01
Iron (Fe) is an essential trace element for marine life. Extremely low Fe concentrations limit primary production and nitrogen fixation in large parts of the oceans and consequently influence ocean ecosystem functioning. The importance of Fe for ocean ecosystems makes Fe one of the core chemical trace elements in the international GEOTRACES program. Despite the recognized importance of Fe, our present knowledge of its supply and biogeochemical cycle has been limited by mostly fragmentary datasets. Here, we present highly accurate dissolved Fe (DFe) values measured at an unprecedented high intensity (1407 samples) along the longest full ocean depth transect (17500 kilometers) covering the entire western Atlantic Ocean. DFe measurements along this transect unveiled details about the supply and cycling of Fe. External sources of Fe identified included off-shelf and river supply, hydrothermal vents and aeolian dust. Nevertheless, vertical processes such as the recycling of Fe resulting from the remineralization of sinking organic matter and the removal of Fe by scavenging still dominated the distribution of DFe. In the northern West Atlantic Ocean, Fe recycling and lateral transport from the eastern tropical North Atlantic Oxygen Minimum Zone (OMZ) dominated the DFe-distribution. Finally, our measurements showed that the North Atlantic Deep Water (NADW), the major driver of the so-called ocean conveyor belt, contains excess DFe relative to phosphate after full biological utilization and is therefore an important source of Fe for biological production in the global ocean. PMID:24978190
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Iron Biogeochemistry in the High Latitude North Atlantic Ocean.
Achterberg, Eric P; Steigenberger, Sebastian; Marsay, Chris M; LeMoigne, Frédéric A C; Painter, Stuart C; Baker, Alex R; Connelly, Douglas P; Moore, C Mark; Tagliabue, Alessandro; Tanhua, Toste
2018-01-19
Iron (Fe) is an essential micronutrient for marine microbial organisms, and low supply controls productivity in large parts of the world's ocean. The high latitude North Atlantic is seasonally Fe limited, but Fe distributions and source strengths are poorly constrained. Surface ocean dissolved Fe (DFe) concentrations were low in the study region (<0.1 nM) in summer 2010, with significant perturbations during spring 2010 in the Iceland Basin as a result of an eruption of the Eyjafjallajökull volcano (up to 2.5 nM DFe near Iceland) with biogeochemical consequences. Deep water concentrations in the vicinity of the Reykjanes Ridge system were influenced by pronounced sediment resuspension, with indications for additional inputs by hydrothermal vents, with subsequent lateral transport of Fe and manganese plumes of up to 250-300 km. Particulate Fe formed the dominant pool, as evidenced by 4-17 fold higher total dissolvable Fe compared with DFe concentrations, and a dynamic exchange between the fractions appeared to buffer deep water DFe. Here we show that Fe supply associated with deep winter mixing (up to 103 nmol m -2 d -1 ) was at least ca. 4-10 times higher than atmospheric deposition, diffusive fluxes at the base of the summer mixed layer, and horizontal surface ocean fluxes.
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NASA Astrophysics Data System (ADS)
Crusius, John; Schroth, Andrew W.; Resing, Joseph A.; Cullen, Jay; Campbell, Robert W.
2017-06-01
Phytoplankton growth in the Gulf of Alaska (GoA) is limited by iron (Fe), yet Fe sources are poorly constrained. We examine the temporal and spatial distributions of Fe, and its sources in the GoA, based on data from three cruises carried out in 2010 from the Copper River (AK) mouth to beyond the shelf break. April data are the first to describe late winter Fe behavior before surface water nitrate depletion began. Sediment resuspension during winter and spring storms generated high "total dissolvable Fe" (TDFe) concentrations of 1000 nmol kg-1 along the entire continental shelf, which decreased beyond the shelf break. In July, high TDFe concentrations were similar on the shelf, but more spatially variable, and driven by low-salinity glacial meltwater. Conversely, dissolved Fe (DFe) concentrations in surface waters were far lower and more seasonally consistent, ranging from 4 nmol kg-1 in nearshore waters to 0.6-1.5 nmol kg-1 seaward of the shelf break during April and July, despite dramatic depletion of nitrate over that period. The reasonably constant DFe concentrations are likely maintained during the year across the shelf by complexation by strong organic ligands, coupled with ample supply of labile particulate Fe. The April DFe data can be simulated using a simple numerical model that assumes a DFe flux from shelf sediments, horizontal transport by eddy diffusion, and removal by scavenging. Given how global change is altering many processes impacting the Fe cycle, additional studies are needed to examine controls on DFe in the Gulf of Alaska.
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Yang, Rujun; Su, Han; Qu, Shenglu; Wang, Xuchen
2017-05-03
The iron binding capacities (IBC) of fulvic acid (FA) and humic acid (HA) were determined in the salinity range from 5 to 40. The results indicated that IBC decreased while salinity increased. In addition, dissolved iron (dFe), FA and HA were also determined along the Yangtze River estuary's increasing salinity gradient from 0.14 to 33. The loss rates of dFe, FA and HA in the Yangtze River estuary were up to 96%, 74%, and 67%, respectively. The decreases in dFe, FA and HA, as well as the change in IBC of humic substances (HS) along the salinity gradient in the Yangtze River estuary were all well described by a first-order exponential attenuation model: y(dFe/FA/HA, S) = a 0 × exp(kS) + y 0 . These results indicate that flocculation of FA and HA along the salinity gradient resulted in removal of dFe. Furthermore, the exponential attenuation model described in this paper can be applied in the major estuaries of the world where most of the removal of dFe and HS occurs where freshwater and seawater mix.
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Redox speciation of dissolved iron in the northeastern atlantic ocean.
NASA Astrophysics Data System (ADS)
Ussher, S. J.; Achterberg, E. P.; Worsfold, P. J.
2003-04-01
Dissolved iron (<0.2 micron) and iron(II) (<0.2 micron) distributions were determined during the Iron from Below and Iron from Above research cruises in the North Eastern Atlantic Ocean. The cruises were part of the EU Ironages project. Iron(II) was measured on-board ship using an iron(II) specific, automated flow injection analyser with luminol chemiluminescence detection [1]. Total dissolved iron (DFe) was determined in a land-based laboratory, using the same FI technique but with prior reduction of iron(III) to iron(II) [2]. The limits of detection for the methods were 5 -15 pM and 35 pM respectively, the analysis time was 8 - 10 minutes per sample (minimum of 3 replicates). The Iron from Below expedition took place over the European Continental Shelf, 200 km South West of Brittany (France) in March 2002. A transect between 47.61°N, 4.24°W and 46.00°N, 8.01°W was completed. Over the transect, the depth increased from 100 m to 5000 m. Iron(II) concentrations ranged between 10 and 100 pM and DFe between 0.2 and 1 nM, with the higher concentrations (Fe(II) ca. > 50 pM and DFe ca. > 0.8 nM) generally found in the shallow shelf waters. These observations imply that benthic inputs and sediment resuspension may form important inputs of dissolved iron and iron(II) in the shelf waters. Iron speciation measurements were also made for underway surface and shallow cast samples during the Iron from Above cruise October 2002. Fe(II) and DFe concentrations were typically 5 to 50 pM and 0.2 to 0.6 nM, respectively. Sampling was carried out within a grid in the Canary Basin around 5 degrees W of the Canary Islands, an area assumed to be strongly influenced by the Saharan dust plume. Observed Fe(II) concentrations are compared and ratioed to the DFe concentrations, and indicate that iron(II) forms an important fraction (between 5 and 15%) of the total dissolved iron concentration in the study areas. Data plots for surface samples are presented with the corresponding physical oceanographic and solar irradiance data. The concentrations of Fe(II) observed during our studies exceed the values predicted from thermodynamic equilibrium modelling. This indicates that there is a steady supply of Fe(II) (possibly from photoreduction and/or biological origins) and/or Fe(II) is prevented from oxidation through stabilisation mechanisms (possibly by organic ligands). [1] A. R. Bowie, E. P. Achterberg, P. N. Sedwick, S. Ussher, P. J. Worsfold, Environ. Sci. Technol., 36, (2002) 4600. [2] A. R. Bowie, E. P. Achterberg, R. F. C. Mantoura, P. J. Worsfold, Anal. Chim. Acta, 377, (1998) 113.
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Organic matter controls of iron incorporation in growing sea ice
NASA Astrophysics Data System (ADS)
Janssens, Julie; Meiners, Klaus M.; Townsend, Ashley T.; Lannuzel, Delphine
2018-03-01
This study presents the first laboratory-controlled sea-ice growth experiment conducted under trace metal clean conditions. The role played by organic matter, in the incorporation of iron (Fe) into sea ice was investigated by means of laboratory ice-growth experiments using a titanium cold-finger apparatus. Experiments were also conducted to understand the role of extracellular polymeric substances (EPS) in the enrichment of ammonium in sea ice. Sea ice was grown from several seawater solutions containing different quantities and qualities of particulate Fe (PFe), dissolved Fe (DFe) and organic matter. Sea ice and seawater were analyzed for particulate organic carbon and nitrogen, macro-nutrients, extracellular EPS, PFe and DFe, and particulate aluminium. The experiments showed that biogenic PFe is preferentially incorporated into sea ice compared to lithogenic PFe. Furthermore, sea ice grown from ultra-violet (UV) and non-UV treated seawaters exhibits contrasting incorporation rates of organic matter and Fe. Whereas the effects of UV-treatments were not always significant, we do find indications that the type or organic matter controls the enrichment of Fe in forming sea ice.. Specifically, we come to the conclusion that the incorporation of DFe is favored by the presence of organic ligands in the source solution.
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NASA Astrophysics Data System (ADS)
Shelley, Rachel U.; Wyatt, Neil J.; Tarran, Glenn A.; Rees, Andrew P.; Worsfold, Paul J.; Lohan, Maeve C.
2017-11-01
Cobalt (Co) and iron (Fe) are essential for phytoplankton nutrition, and as such constitute a vital link in the marine biological carbon pump. Atmospheric deposition is an important, and in some places the dominant, source of trace elements (TEs) to the global ocean. Dissolved cobalt (dCo) and iron (dFe) were determined along an Atlantic Meridional Transect (AMT-19; Oct/Nov 2009) between 50°N and 40°S in the upper 150 m in order to investigate the behaviour and distribution of these two essential, bioactive TEs. During AMT-19, large differences in the distributions of dCo and dFe were observed. In the North Atlantic gyre provinces, extremely low mixed layer dCo concentrations (23 ± 9 pM) were observed, which contrasts with the relatively high mixed layer dFe concentrations (up to 1.0 nM) coincident with the band of highest atmospheric deposition (∼5-30°N). In the South Atlantic gyre, the opposite trend was observed, with relatively high dCo (55 ± 18 pM) observed throughout the water column, but low dFe concentrations (0.29 ± 0.08 nM). Given that annual dust supply is an order of magnitude greater in the North than the South Atlantic, the dCo distribution was somewhat unexpected. However, the distribution of dCo shows similarities with the distribution of phosphate (PO43-) in the euphotic zone of the Atlantic Ocean, where the North Atlantic gyre is characterised by chronically low PO4, and higher concentrations are observed in the South Atlantic gyre (Mather et al., 2008), suggesting the potential for a similar biological control of dCo distributions. Inverse correlations between dCo and Prochlorococcus abundance in the North Atlantic gyre provinces, combined with extremely low dCo where nitrogen fixation rates were highest (∼20-28°N), suggests the dominance of biological controls on dCo distributions. The contrasting dCo and dFe distributions in the North and South Atlantic gyres provides insights into the differences between the dominant controls on the distribution of these two bioactive trace metals in the central Atlantic Ocean.
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Factors Influencing the Diversity of Iron Uptake Systems in Aquatic Microorganisms
Desai, Dhwani K.; Desai, Falguni D.; LaRoche, Julie
2012-01-01
Iron (Fe) is an essential micronutrient for many processes in all living cells. Dissolved Fe (dFe) concentrations in the ocean are of the order of a few nM, and Fe is often a factor limiting primary production. Bioavailability of Fe in aquatic environments is believed to be primarily controlled through chelation by Fe-binding ligands. Marine microbes have evolved different mechanisms to cope with the scarcity of bioavailable dFe. Gradients in dFe concentrations and diversity of the Fe-ligand pool from coastal to open ocean waters have presumably imposed selection pressures that should be reflected in the genomes of microbial communities inhabiting the pelagic realm. We applied a hidden Markov model (HMM)-based search for proteins related to cellular iron metabolism, and in particular those involved in Fe uptake mechanisms in 164 microbial genomes belonging to diverse taxa and occupying different aquatic niches. A multivariate statistical approach demonstrated that in phototrophic organisms, there is a clear influence of the ecological niche on the diversity of Fe uptake systems. Extending the analyses to the metagenome database from the Global Ocean Sampling expedition, we demonstrated that the Fe uptake and homeostasis mechanisms differed significantly across marine niches defined by temperatures and dFe concentrations, and that this difference was linked to the distribution of microbial taxa in these niches. Using the dN/dS ratios (which signify the rate of non-synonymous mutations) of the nucleotide sequences, we identified that genes encoding for TonB, Ferritin, Ferric reductase, IdiA, ZupT, and Fe2+ transport proteins FeoA and FeoB were evolving at a faster rate (positive selection pressure) while genes encoding ferrisiderophore, heme and Vitamin B12 uptake systems, siderophore biosynthesis, and IsiA and IsiB were under purifying selection pressure (evolving slowly). PMID:23087680
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Iron Supply and Demand in an Antarctic Shelf Ecosystem
NASA Astrophysics Data System (ADS)
McGillicuddy, D. J., Jr.; Sedwick, P.; Dinniman, M. S.; Arrigo, K. R.; Bibby, T. S.; Greenan, B. J. W.; Hofmann, E. E.; Klinck, J. M., II; Smith, W.; Mack, S. L.; Marsay, C. M.; Sohst, B. M.; van Dijken, G.
2016-02-01
The Ross Sea sustains a rich ecosystem and is the most productive sector of the Southern Ocean. Most of this production occurs within a polynya during the November-February period, when the availability of dissolved iron (dFe) is thought to exert the major control on phytoplankton growth. Here we combine new data on the distribution of dFe, high-resolution model simulations of ice melt and regional circulation, and satellite-based estimates of primary production to quantify iron supply and demand over the Ross Sea continental shelf. Our analysis suggests that the largest sources of dFe to the euphotic zone are wintertime mixing and melting sea ice, with a lesser input from intrusions of Circumpolar Deep Water, and a small amount from melting glacial ice. Together these sources are in approximate balance with the annual biological dFe demand inferred from satellite-based productivity algorithms, although both the supply and demand estimates have large uncertainties. Our findings illustrate the complexities of iron cycling in the Southern Ocean, highlighting the heterogeneity of the underlying processes along the Antarctic continental margin. Explicit representation of these complexities, and the temporal variability in both proximate and ultimate sources of iron, will be necessary to understand how a changing climate will affect this important ecosystem and its influence on biogeochemical cycles. Reduction of the present uncertainties in iron supply and demand will require coupled observational and modeling systems capable of resolving the wide range of physical, biological, and chemical processes involved.
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Revisiting Mn and Fe removal in humic rich estuaries
NASA Astrophysics Data System (ADS)
Oldham, Véronique E.; Miller, Megan T.; Jensen, Laramie T.; Luther, George W.
2017-07-01
Metal removal by estuarine mixing has been studied for several decades, but few studies emphasize dissolved metal speciation and organic ligand complexation. Findings from the last decade indicate that metal-humic complexation can be significant for dissolved metals including Cu(II), Al(III) and Fe(III), but little consideration is given to the precipitation of these complexes with humic material at pH < 2. Given that total soluble metal analysis involves an acidification step for sample preservation, we show that Mn and other metal concentrations may have been underestimated in estuaries, especially when humic substance concentrations are high. A competitive ligand assay of selected samples from our study site, a coastal waterway bordered by wetlands (Broadkill River, DE), showed that Mn(III)-humic complexation is significant, and that some Mn(III)-L complexes precipitate during acidification. In the oxygenated surface waters of the Broadkill River, total dissolved Mn (dMnT) was up to 100% complexed to ambient ligands as Mn(III)-L, and we present evidence for humic-type Mn(III)-L complexes. The Mn(III) complexes were kinetically stabilized against Fe(II) reduction, even when [Fe(II)] was 17 times higher than [dMnT]. Unlike typical oceanic surface waters, [Fe(II)] > [Fe(III)-L] in surface waters, which may be attributed to high rates of photoreduction of Fe(III)-L complexes. Total [Mn(III)-L] ranged from 0.22 to 8.4 μM, in excess of solid MnOx (below 0.28 μM in all samples). Filtration of samples through 0.02 μm filters indicated that all Mn(III)-L complexes pass through the filters and were not colloidal species in contrast to dissolved Fe. Incubation experiments indicated that the reductive dissolution of solid MnOx by ambient ligands may be responsible for Mn(III) formation in this system. Unlike previous studies of estuarine mixing, which demonstrated metal removal during mixing, we show significant export of dMn and dissolved Fe (dFe) in the summer and fall of 2015. Thus, we propose that estuarine removal should be considered seasonal for dMn and dFe, with export in the summer and fall and removal during the winter.
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de Jong, Jeroen; Schoemann, Véronique; Lannuzel, Delphine; Tison, Jean-Louis; Mattielli, Nadine
2008-08-15
In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L(-1) level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a (54)Fe spike and measuring the (57)Fe/(54)Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045+/-0.020 nmol L(-1), n=21, 3 x S.D. limit of detection per session 0.020-0.069 nmol L(-1) range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H(2)O(2), and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097+/-0.043 nmol L(-1)) and Deep-2 (0.91+/-0.17 nmol L(-1)) and obtained results that were in excellent agreement with their DFe consensus values: 0.118+/-0.028 nmol L(-1) (n=7) for Surface-1 and 0.932+/-0.059 nmol L(-1) (n=9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004-January 2005. The profile shows near-surface DFe concentrations of approximately 0.6 nmol L(-1) and bottom water enrichment up to 23 nmol L(-1) DFe.
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de Jong, Jeroen; Schoemann, Véronique; Tison, Jean-Louis; Becquevort, Sylvie; Masson, Florence; Lannuzel, Delphine; Petit, Jérôme; Chou, Lei; Weis, Dominique; Mattielli, Nadine
2007-04-18
A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.
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NASA Astrophysics Data System (ADS)
Ye, Y.; Völker, C.; Wolf-Gladrow, D. A.
2009-10-01
A one-dimensional model of Fe speciation and biogeochemistry, coupled with the General Ocean Turbulence Model (GOTM) and a NPZD-type ecosystem model, is applied for the Tropical Eastern North Atlantic Time-Series Observatory (TENATSO) site. Among diverse processes affecting Fe speciation, this study is focusing on investigating the role of dust particles in removing dissolved iron (DFe) by a more complex description of particle aggregation and sinking, and explaining the abundance of organic Fe-binding ligands by modelling their origin and fate. The vertical distribution of different particle classes in the model shows high sensitivity to changing aggregation rates. Using the aggregation rates from the sensitivity study in this work, modelled particle fluxes are close to observations, with dust particles dominating near the surface and aggregates deeper in the water column. POC export at 1000 m is a little higher than regional sediment trap measurements, suggesting further improvement of modelling particle aggregation, sinking or remineralisation. Modelled strong ligands have a high abundance near the surface and decline rapidly below the deep chlorophyll maximum, showing qualitative similarity to observations. Without production of strong ligands, phytoplankton concentration falls to 0 within the first 2 years in the model integration, caused by strong Fe-limitation. A nudging of total weak ligands towards a constant value is required for reproducing the observed nutrient-like profiles, assuming a decay time of 7 years for weak ligands. This indicates that weak ligands have a longer decay time and therefore cannot be modelled adequately in a one-dimensional model. The modelled DFe profile is strongly influenced by particle concentration and vertical distribution, because the most important removal of DFe in deeper waters is colloid formation and aggregation. Redissolution of particulate iron is required to reproduce an observed DFe profile at TENATSO site. Assuming colloidal iron is mainly composed of inorganic colloids, the modelled colloidal to soluble iron ratio is lower that observations, indicating the importance of organic colloids.
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Pantoja, M L; Jones, H; Garelick, H; Mohamedbakr, H G; Burkitbayev, M
2014-01-01
Iron hydroxide supported onto porous diatomite (D-Fe) is a low-cost material with potential to remove arsenic from contaminated water due to its affinity for the arsenate ion. This affinity was tested under varying conditions of pH, contact time, iron content in D-Fe and the presence of competitive ions, silicate and phosphate. Batch and column experiments were conducted to derive adsorption isotherms and breakthrough behaviours (50 μg L(-1)) for an initial concentration of 1,000 μg L(-1). Maximum capacity at pH 4 and 17% iron was 18.12-40.82 mg of arsenic/g of D-Fe and at pH 4 and 10% iron was 18.48-29.07 mg of arsenic/g of D-Fe. Adsorption decreased in the presence of phosphate and silicate ions. The difference in column adsorption behaviour between 10% and 17% iron was very pronounced, outweighing the impact of all other measured parameters. There was insufficient evidence of a correlation between iron content and arsenic content in isotherm experiments, suggesting that ion exchange is a negligible process occurring in arsenate adsorption using D-Fe nor is there co-precipitation of arsenate by rising iron content of the solute above saturation.
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The Irony of Iron – Biogenic Iron Oxides as an Iron Source to the Ocean
Emerson, David
2016-01-01
Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity. PMID:26779157
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NASA Astrophysics Data System (ADS)
Ślezak, M.; Ślezak, T.; Matlak, K.; DróŻdŻ, P.; Korecki, J.
2018-05-01
A study of in-plane magnetic anisotropy (MA) in epitaxial bcc Co films and Fe/Co bilayers on a Fe(110) surface is reported. Surface MA of as-deposited Co films and Fe/Co bilayers strongly depends on the Co (dCo) and Fe (dFe) thickness. Adsorption of residual gases drastically modifies in-plane MA of both Co films and Fe/Co bilayers. We present two dimensional MA maps in the (dCo, dFe) space for both as grown and adsorption-modified films. Our results indicate how to precisely engineer in-plane MA that can be controlled by dCo, dFe and is sensitive to the residual gas adsorption.
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Lee, Soon Chang; Jeong, Yesul; Kim, Youn Jung; Kim, Hyeran; Lee, Hyun Uk; Lee, Young-Chul; Lee, Sang Moon; Kim, Hae Jin; An, Ha-Rim; Ha, Myoung Gyu; Lee, Go-Woon; Lee, Young-Seak; Lee, Gaehang
2018-04-23
In this study, hierarchically three-dimensional (3D) nanotubular sea urchin-shaped iron oxide nanostructures (3D-Fe 2 O 3 ) were synthesized by a facile and rapid ultrasound irradiation method. Additives, templates, inert gas atmosphere, pH regulation, and other complicated procedures were not required. Dense 3D-Fe 2 O 3 with a relatively large Brunauer-Emmett-Teller (BET) surface area of 129.4 m 2 /g was synthesized within 23 min, and the BET surface area was further improved to 282.7 m 2 /g by a post heat-treatment process. In addition, this post processing led to phase changes from maghemite (γ phase) to hematite (α phase) Fe 2 O 3 . Subsequent characterization suggested that the growth mechanism of the 3D-Fe 2 O 3 follows self-assembly and oriented attachment. The prepared 3D-Fe 2 O 3 was applied to wastewater purification. Ultrasound-irradiated 3D-Fe 2 O 3 can eliminate a As(V) and Cr(VI) from water with 25 times faster removal rate by using a one third smaller amount than commercial α-Fe 2 O 3 . This was attributed to the inter-particle pores and relatively positively charged surface of the nanostructure. In addition, post heat treatment on ultrasound-irradiated 3D-Fe 2 O 3 significantly influenced the photocatalytic degradation of methylene blue and phenol, with a 25 times higher removal efficiency than that of commercial α-Fe 2 O 3 , because of both high BET surface area and good crystallization of the prepared samples. Copyright © 2018 Elsevier B.V. All rights reserved.
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Meltwater Pathways and Iron Delivery to the Antarctic Coastal Ocean
NASA Astrophysics Data System (ADS)
Null, K. A.; Corbett, D. R.; Crenshaw, J.; Peterson, R. N.; Peterson, L.; Buck, C. S.; Lyons, W. B.
2016-02-01
Freshwater inputs to the Antarctic coastal ocean can occur through multiple pathways including calving, streams, and groundwater discharge. The impacts of submarine groundwater discharge on polar ecosystems are generally poorly understood and, until recently, had not been considered as an important physical process along the coast of the Antarctic continent. Here, we present a study utilizing multiple tracers (radium, radon, and stable water isotopes) to quantify freshwater inputs and chemical constituent fluxes associated with multiple discharge pathways, including submarine groundwater discharge, along the Western Antarctic Peninsula. Previous research has shown that primary production in iron-limited waters offshore of the Antarctic Peninsula is fueled in part by continentally-derived sediments, and our work demonstrates that subglacial/submarine groundwater discharge (SSGD) to continental shelf waters in the region is also an important source of dissolved iron (6.4 Gg yr-1; dFe). For reference, this flux equates to approximately 25 times the iron flux from calving in the study area. SSGD also contributed a significantly higher macronutrient flux than calving, although calving contributed more than twice as much freshwater. Thus, SSGD is likely a much more important source of macronutrients and dFe to the nearshore coastal ocean along the Western Antarctic Peninsula, and potentially to the continental shelf and offshore waters of the entire continent than previously recognized. If we assume similar discharge rates along the entire Antarctic coastline ( 45,000 km), the delivery of dFe via SSGD ( 216 Gg yr-1) is comparable to the other fluxes of Fe to the Southern Ocean via dust, icebergs, and glacial runoff from the Antarctic Ice Sheet, and should be considered in future geochemical budgets.
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NASA Astrophysics Data System (ADS)
Rahman, N.; Alam, M. N.
2018-02-01
Vibration response analysis of a hybrid beam with surface mounted patch piezoelectric layer is presented in this work. A one dimensional finite element (1D-FE) model based on efficient layerwise (zigzag) theory is used for the analysis. The beam element has eight mechanical and a variable number of electrical degrees of freedom. The beams are also modelled in 2D-FE (ABAQUS) using a plane stress piezoelectric quadrilateral element for piezo layers and a plane stress quadrilateral element for the elastic layers of hybrid beams. Results are presented to assess the effect of size of piezoelectric patch layer on the free and forced vibration responses of thin and moderately thick beams under clamped-free and clamped-clamped configurations. The beams are subjected to unit step loading and harmonic loading to obtain the forced vibration responses. The vibration control using in phase actuation potential on piezoelectric patches is also studied. The 1D-FE results are compared with the 2D-FE results.
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Diverse stoichiometry of dissolved trace metals in the Indian Ocean
Thi Dieu Vu, Huong; Sohrin, Yoshiki
2013-01-01
Trace metals in seawater are essential to organisms and important as tracers of various processes in the ocean. However, we do not have a good understanding of the global distribution and cycling of trace metals, especially in the Indian Ocean. Here we report the first simultaneous, full-depth, and basin-scale section-distribution of dissolved (D) Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the Indian Ocean. Our data reveal widespread co-limitation for phytoplankton production by DFe and occurrence of redox-related processes. The stoichiometry of the DM/phosphorus ratio agrees within a factor of 5 between deep waters in the Indian and Pacific, whereas it shows variability up to a factor of 300 among water masses within the Indian Ocean. This indicates that a consistent mechanism controls the stoichiometry in the deep waters, which are significantly depleted in Mn, Fe, and Co compared to requirements for phytoplankton.
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Wang, Dong; Yang, Zhuang-qun; Hu, Xiao-yi
2007-08-01
To analyze the stress and displacement distribution of 3D-FE models in three conjunctive methods of vascularized iliac bone graft for established mandibular body defects. Using computer image process technique, a series of spiral CT images were put into Ansys preprocess programe to establish three 3D-FE models of different conjunctions. The three 3D-FE models of established mandibular body defects by vascularized iliac bone graft were built up. The distribution of Von Mises stress and displacement around mandibular segment, grafted ilium, plates and screws was obtained. It may be determined successfully that the optimal conjunctive shape be the on-lay conjunction.
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Volcanic ash as an oceanic iron source and sink
NASA Astrophysics Data System (ADS)
Rogan, Nicholas; Achterberg, Eric P.; Le Moigne, Frédéric A. C.; Marsay, Chris M.; Tagliabue, Alessandro; Williams, Richard G.
2016-03-01
Volcanic ash deposition to the ocean forms a natural source of iron (Fe) to surface water microbial communities. Inputs of lithogenic material may also facilitate Fe removal through scavenging. Combining dissolved Fe (dFe) and thorium-234 observations alongside modeling, we investigate scavenging of Fe in the North Atlantic following the Eyjafjallajökull volcanic eruption. Under typical conditions biogenic particles dominate scavenging, whereas ash particles dominate during the eruption. The size of particles is important as smaller scavenging particles can become saturated with surface-associated ions. Model simulations indicate that ash deposition associated with Eyjafjallajökull likely led to net Fe removal. Our model suggests a threefold greater stimulation of biological activity if ash deposition had occurred later in the growing season when the region was Fe limited. The implications of ash particle scavenging, eruption timing, and particle saturation need to be considered when assessing the impact of ash deposition on the ocean Fe cycle and productivity.
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NASA Astrophysics Data System (ADS)
Borrione, I.; Aumont, O.; Nielsdóttir, M. C.; Schlitzer, R.
2013-07-01
In high-nutrient low-chlorophyll waters of the western Atlantic sector of the Southern Ocean, an intense phytoplankton bloom is observed annually north of South Georgia, most likely due to an enhanced supply of the limiting micronutrient iron. Shallow sediments and atmospheric dust deposition are believed to be the main iron sources. However, their relative importance is still unclear and in the South Georgia region have yet not been ascertained because iron measurements are very few. In this study, we use austral summer dissolved iron (dFe) data around South Georgia (January and February 2008) with a coupled regional hydrodynamic and biogeochemical model to investigate natural iron fertilization around the island. The biogeochemical component of the model includes an iron cycle, where sediments and dust deposition are the sources of iron to the ocean. The model captures the characteristic flow patterns around South Georgia, hence simulating a large phytoplankton bloom to the north, i.e., downstream, of the island. Modelled dFe concentrations agree well with observations (mean difference and root mean square errors of ~0.02 nM and ~0.81 nM) and form a large plume to the north of the island that extends eastwards for more than 800 km. In agreement with observations, highest dFe concentrations are located along the coast and decrease with distance from the island. Sensitivity tests indicate that most of the iron measured in the main bloom area originates from the coast and the very shallow shelf-sediments (depths < 20 m) while dust deposition plays a minor role, with almost no effects on surface chlorophyll a concentrations. Iron sources such as run-off not represented explicitly in the model, but that likely contribute to the iron plumes observed around South Georgia, are also discussed together with the potential effects their temporal variability may have on the system.
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NASA Astrophysics Data System (ADS)
Sedwick, P.; Mulholland, M. R.; Najjar, R.; Bernhardt, P. W.; Price, L. M.; Sohst, B. M.; Sookhdeo, C.; Widner, B.
2016-02-01
The role of iron supply in regulating phytoplankton production in high-nutrient, low-chlorophyll ocean regions has been well established. Less clear, however, is the importance of iron for phytoplankton processes in other oceanic settings, such as coastal and oligotrophic waters, where differential changes in the supply and removal of dissolved iron (dFe) can result in limitation or co-limitation of growth due to iron deficiency. One such region of interest is the Mid-Atlantic Bight (MAB), where previous field experiments have provided some evidence of co-limitation of algal growth by nitrogen and iron. In summer 2014 we conducted field sampling and shipboard experiments to assess the role of iron and macronutrient availability in controlling primary production in seasonally oligotrophic waters over the MAB continental slope, with a focus on the the impacts of wet deposition. Our results indicate that nitrogen was the proximate limiting nutrient, with a secondary limitation imposed by availability of phosphorus; we found no evidence for a deficiency in dFe, which was present at concentrations in the range 0.3-0.9 nM. Phytoplankton growth was clearly stimulated by the addition of natural rainwater, suggesting that summer rain events stimulate primary production in the MAB by contributing new nitrogen (primarily as ammonium) and phosphorus, whilst maintaining iron-replete conditions.
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NASA Astrophysics Data System (ADS)
Kurisu, M.; Iizuka, T.; Sakata, K.; Uematsu, M.; Takahashi, Y.
2015-12-01
It has been reported that phytoplankton growth in the High Nutrient-Low Chlorophyll (HNLC) regions is limited by dissolved iron (DFe) concentration (e.g., Martin and Fitzwater, 1988). Aerosol is known as one of the dominant sources of DFe to the ocean and classified into two origins such as anthropogenic and natural. A series of recent studies showed that Fe in anthropogenic aerosols is more soluble than that in natural aerosols (Takahashi et al., 2013) and has lower isotopic ratio (Mead et al., 2013). However, the difference between Fe isotopic ratio (δ56Fe: [(56Fe/54Fe)sample/(56Fe/54Fe)IRMM-14]-1) of two origins reported in Mead et al. (2013) is not so large compared with the standard deviation. Therefore, the aim of this study is to determine Fe species and δ56Fe in anthropogenic aerosols more accurately and to evaluate its contribution to the ocean surface. Iron species were determined by X-ray absorption fine structure (XAFS) analysis, while δ56Fe in size-fractionated aerosols were measured by MC-ICP-MS (NEPTUNE Plus) after chemical separation using anion exchange resin. Dominant Fe species in the samples were, ferrihydrite, hematite, and biotite. It was also revealed that coarse particles contained a larger amount of biotite and that fine particles contained a larger amount of hematite, which suggested that anthropogenic aerosols were emitted during combustion processes. In addition, results of Fe isotopic ratio analysis suggested that δ56Fe of coarse particles were around +0.25‰, whereas that of fine particles were -0.5 ˜ -2‰, which was lower than the δ56Fe in anthropogenic aerosol by Mead et al. (2013). The size-fractionated sampling made it possible to determine the δ56Fe in anthropogenic aerosol. Soluble component in fine particles extracted by simulated rain water also showed much lower δ56Fe (δ56Fe = -3.9±0.12‰), suggesting that anthropogenic Fe has much lower isotopic ratio. The remarkably low δ56Fe may be caused by the anthropogenic combustion process. The δ56Fe in anthropogenic aerosols measured here is important to model the budget of iron in the surface ocean.
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NASA Astrophysics Data System (ADS)
Maranguit, Deejay
2017-04-01
The strong affinity of phosphorus (P) to iron (Fe) oxides and hydroxides in highly weathered tropical soils limits P availability and therefore plant productivity. In flooded soils, however, P fixed by Fe oxides and hydroxides can be released and transformed to a more available form because of Fe3+ reduction to Fe2+. These P dynamics in flooded soils are well documented for rice paddies. Such effects are much less studied in other land-use types under the influence of seasonal flooding, especially in the tropics during heavy monsoon rains. The aim of this study was to investigate the mobilization of P during flooding leading to anaerobic conditions in topsoil and subsoil horizons depending on land-use type. Samples were collected in highly weathered soils from four replicate sites under natural rainforest, jungle rubber, rubber and oil palm plantations in Sumatra, Indonesia. Topsoil and subsoil were taken to ensure a wide range of soil organic matter (SOM) and P contents. Soils were incubated under anaerobic, flooded conditions at 30 ± 1 oC for 60 days. Our results confirmed the hypothesis that soil flooding mobilizes P and increases P availability. Two distinct and opposite phases, however, were observed upon flooding. During the first three weeks of flooding, the dissolved P (DP) concentration peaked, simultaneously with a peak of dissolved Fe2+ (DFe2+) and dissolved organic carbon (DOC) in the soil solution. After three weeks, P availability in soils decreased, although Fe-P and available P did not reach initial, pre-flooding levels. Accordingly, Fe dissolution and P mobilization were reversible processes. Furthermore, land-use type influenced the impacts of flooding on P and Fe forms mainly in the topsoil, where P dissolution and availability were generally higher under forest and, to a lesser extent, under jungle rubber. A positive correlation between DOC and DFe2+ (R2 = 0.42) in topsoil indicates that the intensity of microbially-mediated Fe3+ reduction is limited by the amount of available carbon (C) as an energy source for microorganisms. Moreover, microbial mineralization of organic P from SOM also increases P availability, and this process requires available C. This interpretation was supported by the strong correlation (R2 = 0.58) between available P and DOC, as well as between DP and DOC (R2 = 0.56) in topsoil. The increasing soil solution pH in topsoil and subsoil after flooding of all land-use types may also influence the P release over time. In summary, the increase of available P and DP during flooding is due to three main mechanisms: (1) P release via the microbially-mediated reductive dissolution of Fe3+ oxides; (2) P release during SOM mineralization and (3) solubility of Fe phosphate due to increasing pH. These mechanisms are relevant not only in riparian areas, where flooding occurs, but also in well-drained soil that is partly waterlogged after regular heavy rainfalls during the wet season. Likewise, the P cycle turnover is faster in compacted, often anaerobic plantation soils. Here, more P is pumped by the vegetation and then removed from plantations due to yield export.
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NASA Technical Reports Server (NTRS)
Wang, Ren H.
1991-01-01
A method of combined use of magnetic vector potential (MVP) based finite element (FE) formulations and magnetic scalar potential (MSP) based FE formulations for computation of three-dimensional (3D) magnetostatic fields is developed. This combined MVP-MSP 3D-FE method leads to considerable reduction by nearly a factor of 3 in the number of unknowns in comparison to the number of unknowns which must be computed in global MVP based FE solutions. This method allows one to incorporate portions of iron cores sandwiched in between coils (conductors) in current-carrying regions. Thus, it greatly simplifies the geometries of current carrying regions (in comparison with the exclusive MSP based methods) in electric machinery applications. A unique feature of this approach is that the global MSP solution is single valued in nature, that is, no branch cut is needed. This is again a superiority over the exclusive MSP based methods. A Newton-Raphson procedure with a concept of an adaptive relaxation factor was developed and successfully used in solving the 3D-FE problem with magnetic material anisotropy and nonlinearity. Accordingly, this combined MVP-MSP 3D-FE method is most suited for solution of large scale global type magnetic field computations in rotating electric machinery with very complex magnetic circuit geometries, as well as nonlinear and anisotropic material properties.
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NASA Astrophysics Data System (ADS)
Blain, S.; Laes, A.; Laan, P.; Achterberg, E.; de Baar, H.
2002-12-01
In order to better understand and quantify the inputs of iron from below in the water column a detailed section from the coast to offshore has been studied in the eastern North Atlantic. The section, extended from 47°36 58 N, 4°14 51 W (depth 96 m) to 46°00 00 N, 8°00 00 W (depth 4912 m). The cruise took place in March 2002, on board R/V Pelagia, as part of the European Union project IRONAGES. Fifteen stations have been sampled for dissolved iron (DFe) and nutrients analysis. Go Flo bottles mounted on a kevlar cable were used for clean seawater sampling in the water column. A torpedo fish and trace metal clean bellows pump were used for surface sampling. Sample were filtered on-line through an 0.2 μm cartridge. The DFe concentrations were measured onboard using a FIA method with on line preconcentration (8-HQ resin) and chemiluminescence detection (mean blank = 28 pM, mean limit of detection= 39 pM). The coastal stations over the shelf showed the highest concentrations of DFe. In this part of the transect, the concentration decreased from the surface to the bottom. Maxima (1-2.4 nM) were associated with increase in turbidity demonstrating the DFe inputs associated with re-suspended sediments and/or pore waters. In the eastern part of the transect, water of the Loire river has been identified has a source of iron. Close to the shelf break the two dimensional iron distribution became more complex. A tidal front, internal waves and slope currents created a patchy distribution of DFe. Evertheless the input from below was always observable at depth between 500 and 1200 m. Finally, in the western part of the transect, off the plateau, the concentration of DFe was strongly correlated with the occurrence of different water masses (see abstract by A. Laës).
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Inverse-model estimates of the ocean's coupled phosphorus, silicon, and iron cycles
NASA Astrophysics Data System (ADS)
Pasquier, Benoît; Holzer, Mark
2017-09-01
The ocean's nutrient cycles are important for the carbon balance of the climate system and for shaping the ocean's distribution of dissolved elements. Dissolved iron (dFe) is a key limiting micronutrient, but iron scavenging is observationally poorly constrained, leading to large uncertainties in the external sources of iron and hence in the state of the marine iron cycle. Here we build a steady-state model of the ocean's coupled phosphorus, silicon, and iron cycles embedded in a data-assimilated steady-state global ocean circulation. The model includes the redissolution of scavenged iron, parameterization of subgrid topography, and small, large, and diatom phytoplankton functional classes. Phytoplankton concentrations are implicitly represented in the parameterization of biological nutrient utilization through an equilibrium logistic model. Our formulation thus has only three coupled nutrient tracers, the three-dimensional distributions of which are found using a Newton solver. The very efficient numerics allow us to use the model in inverse mode to objectively constrain many biogeochemical parameters by minimizing the mismatch between modeled and observed nutrient and phytoplankton concentrations. Iron source and sink parameters cannot jointly be optimized because of local compensation between regeneration, recycling, and scavenging. We therefore consider a family of possible state estimates corresponding to a wide range of external iron source strengths. All state estimates have a similar mismatch with the observed nutrient concentrations and very similar large-scale dFe distributions. However, the relative contributions of aeolian, sedimentary, and hydrothermal iron to the total dFe concentration differ widely depending on the sources. Both the magnitude and pattern of the phosphorus and opal exports are well constrained, with global values of 8. 1 ± 0. 3 Tmol P yr-1 (or, in carbon units, 10. 3 ± 0. 4 Pg C yr-1) and 171. ± 3. Tmol Si yr-1. We diagnose the phosphorus and opal exports supported by aeolian, sedimentary, and hydrothermal iron. The geographic patterns of the export supported by each iron type are well constrained across the family of state estimates. Sedimentary-iron-supported export is important in shelf and large-scale upwelling regions, while hydrothermal iron contributes to export mostly in the Southern Ocean. The fraction of the global export supported by a given iron type varies systematically with its fractional contribution to the total iron source. Aeolian iron is most efficient in supporting export in the sense that its fractional contribution to export exceeds its fractional contribution to the total source. Per source-injected molecule, aeolian iron supports 3. 1 ± 0. 8 times more phosphorus export and 2. 0 ± 0. 5 times more opal export than the other iron types. Conversely, per injected molecule, sedimentary and hydrothermal iron support 2. 3 ± 0. 6 and 4. ± 2. times less phosphorus export, and 1. 9 ± 0. 5 and 2. ± 1. times less opal export than the other iron types.
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NASA Astrophysics Data System (ADS)
Medard, E.; Martin, A. M.; Collinet, M.; Righter, K.; Grove, T. L.; Newville, M.; Lanzirotti, A.
2014-12-01
The partitioning of Fe3+ between silicate melts and minerals is a key parameter to understand magmatic processes, as it is directly linked to oxygen fugacity (fO2). fO2 is, a priori, not a constant during magmatic processes, and its evolution depends on the compatibility of Fe3+. We have experimentally determined the partition coefficients of Fe3+ between augite, pigeonite, and silicate melt, and use them to constrain the fO2of the martian mantle and of differentiated martian basalts. A series of experiments on various martian basaltic compositions were performed under controlled fO2 in one-atmosphere gas-mixing furnaces. Fe3+/Fetotal ratios in silicate melts and pyroxenes were determined using synchrotron Fe K-edge XANES on the 13 IDE beamline at APS (Argonne). Fe3+ mineral/melt partition coefficients (DFe3+) for augite and pigeonite were obtained with a relative uncertainty of 10-15 %. Both are constant over a wide range of oxygen fugacity (FMQ-2.5 to FMQ+2.0). DFe3+ for augite and pigeonite are broadly consistent with previous data by [1], but DFe3+ for augite is significantly higher (by a factor of 2) than the indirect determinations of [2]. Since augites in [2] are extremely poor in iron compared to ours (0.18 wt% vs 13 wt% FeO), this strongly suggests that DFe3+ varies with Mg#, indicating that Fe3+is more compatible than previously thought in terrestrial mantle pyroxenes (3 wt% FeO) as well. Crystallization paths for shergottite parental melts have been calculated using the MELTS software, combined with our partition coefficients. fO2 in the residual melts is calculated from the models of [3] and [4]. It stays relatively constant at high temperatures, but increases very strongly during the latest stages of crystallization. These results explain the large range of fO2 determined in enriched shergottites. In order to estimate the fO2 of the martian mantle, only the highest temperature phases in the most primitive martian samples should be used. The most primitive shergottites record a mantle fO2 around FMQ-2.5, consistent with the lowest fO2estimated for surface basalts [5]. [1] McCanta et al. (2004) Am Min 89:1685-1693; [2] Mallmann and O'Neill (2009) J Petrol 50:1765-1794; [3] Righter et al. (2013) Am Min 98:616-628; [4] Kress and Carmichael (1991) CMP 108:82-92; [5] Schmidt ME et al. (2014) EPSL 384:198-208.
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Rijkenberg, Micha J A; Langlois, Rebecca J; Mills, Matthew M; Patey, Matthew D; Hill, Polly G; Nielsdóttir, Maria C; Compton, Tanya J; Laroche, Julie; Achterberg, Eric P
2011-01-01
During the winter of 2006 we measured nifH gene abundances, dinitrogen (N(2)) fixation rates and carbon fixation rates in the eastern tropical and sub-tropical North Atlantic Ocean. The dominant diazotrophic phylotypes were filamentous cyanobacteria, which may include Trichodesmium and Katagnymene, with up to 10(6) L(-1)nifH gene copies, unicellular group A cyanobacteria with up to 10(5) L(-1)nifH gene copies and gamma A proteobacteria with up to 10(4) L(-1)nifH gene copies. N(2) fixation rates were low and ranged between 0.032-1.28 nmol N L(-1) d(-1) with a mean of 0.30 ± 0.29 nmol N L(-1) d(-1) (1σ, n = 65). CO(2)-fixation rates, representing primary production, appeared to be nitrogen limited as suggested by low dissolved inorganic nitrogen to phosphate ratios (DIN:DIP) of about 2 ± 3.2 in surface waters. Nevertheless, N(2) fixation rates contributed only 0.55 ± 0.87% (range 0.03-5.24%) of the N required for primary production. Boosted regression trees analysis (BRT) showed that the distribution of the gamma A proteobacteria and filamentous cyanobacteria nifH genes was mainly predicted by the distribution of Prochlorococcus, Synechococcus, picoeukaryotes and heterotrophic bacteria. In addition, BRT indicated that multiple a-biotic environmental variables including nutrients DIN, dissolved organic nitrogen (DON) and DIP, trace metals like dissolved aluminum (DAl), as a proxy of dust inputs, dissolved iron (DFe) and Fe-binding ligands as well as oxygen and temperature influenced N(2) fixation rates and the distribution of the dominant diazotrophic phylotypes. Our results suggest that lower predicted oxygen concentrations and higher temperatures due to climate warming may increase N(2) fixation rates. However, the balance between a decreased supply of DIP and DFe from deep waters as a result of more pronounced stratification and an enhanced supply of these nutrients with a predicted increase in deposition of Saharan dust may ultimately determine the consequences of climate warming for N(2) fixation in the North Atlantic.
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Guieu, Cécile; Bonnet, Sophie; Petrenko, Anne; Menkes, Christophe; Chavagnac, Valérie; Desboeufs, Karine; Maes, Christophe; Moutin, Thierry
2018-06-13
In the Western Tropical South Pacific, patches of high chlorophyll concentrations linked to the occurrence of N 2 -fixing organisms are found in the vicinity of volcanic islands. The survival of these organisms relies on a high bioavailable iron supply whose origin and fluxes remain unknown. Here, we measured high dissolved iron (DFe) concentrations (up to 66 nM) in the euphotic layer, extending zonally over 10 degrees longitude (174 E-175 W) at ∼20°S latitude. DFe atmospheric fluxes were at the lower end of reported values of the remote ocean and could not explain the high DFe concentrations measured in the water column in the vicinity of Tonga. We argue that the high DFe concentrations may be sustained by a submarine source, also characterized by freshwater input and recorded as salinity anomalies by Argo float in situ measurements and atlas data. The observed negative salinity anomalies are reproduced by simulations from a general ocean circulation model. Submarine iron sources reaching the euphotic layer may impact nitrogen fixation across the whole region.
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NASA Astrophysics Data System (ADS)
Mork, Steven Wayne
High resolution infrared spectroscopy was used to examine intramolecular vibrational interactions in 2 -fluoroethanol (2FE) and 1,2-difluoroethane (DFE). A high resolution infrared spectrophotometer capable of better than 10 MHz spectral resolution was designed and constructed. The excitation source consists of three lasers: an argon-ion pumped dye laser which pumps a color -center laser. The infrared beam from the color-center laser is used to excite sample molecules which are rotationally and vibrationally cooled in a supersonic molecular beam. Rovibrational excitation of the sample molecules is detected by monitoring the kinetic energy of the molecular beam with a bolometer. The high resolution infrared spectrum of 2FE was collected and analyzed over the 2977-2990 cm^ {-1}^ectral region. This region contains the asymmetric CH stretch on the fluorinated carbon. The spectrum revealed extensive perturbations in the rotational fine structure. Analysis of these perturbations has provided a quantitative measure of selective vibrational mode coupling between the C-H stretch and its many neighboring dark vibrational modes. Interestingly, excitation of the C-H stretch is known to induce a photoisomerization reaction between 2FE's Gg^' and Tt conformers. Implications of the role of mode coupling in the reaction mechanism are also addressed. Similarly, the high resolution infrared spectrum of DFE was collected and analyzed over the 2978-2996 cm ^{-1}^ectral region. This region contains the symmetric combination of asymmetric C-H stretches in DFE. Perturbations in the rotational fine structure indicate vibrational mode coupling to a single dark vibrational state. The dark state is split by approximately 19 cm^{-1} due to tunneling between two identical gauche conformers. The coupling mechanism is largely anharmonic with a minor component of B/C-plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. The coupled vibrational mode has been identified as containing C-C torsion, CCF bend and CH_2 rock. As in 2FE, DFE undergoes an isomerization reaction upon excitation of the C-H stretch. Coupling between the C-H stretch and C-C torsion is addressed with respect to the reaction mechanism.
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Food matrix and cooking process affect mineral bioaccessibility of enteral nutrition formulas.
Galán, María Gimena; Drago, Silvina Rosa
2014-02-01
When enteral formulas (EF) are administered orally as a supplement to the normal diet, they are often mixed with conventional foods or included in recipes in order to seek new flavors and textures and avoid monotony. The aims of this work were to study the bioaccessibility of Fe, Zn and Ca from commercial EF and the impact upon their incorporation into sweet preparations. Twenty commercial EF, before and after inclusion in sweet food (rice pudding, RP; banana smoothie, BS; tea, T; chocolate dessert, CD) were evaluated regarding Fe, Zn and Ca dialyzability (%DFe , %DZn , %DCa ) as an estimator of mineral bioaccessibility. Fe, Zn and Ca dialyzability from EF was variable and generally low. Heating during EF-sweet food preparation (T and CD) lowered values to 44.1 %DFe , possibly due to degradation of vitamin C, and 52.7 %DZn and 25.3 %DCa , due to the interaction with food components. EF and EF-sweet foods did not represent a good supply of Fe, Zn and Ca as recommended. This study demonstrated how the bioaccessibility of these minerals is affected by the food matrix in which EF is included as well as heating during food preparation. © 2013 Society of Chemical Industry.
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Improved analysis tool for concrete pavement : [project summary].
DOT National Transportation Integrated Search
2017-10-01
University of Florida researchers developed 3D-FE models to more accurately predict the behavior of concrete slabs. They also followed up on a project to characterize strain gauge performance for a Florida Department of Transportation (FDOT) concrete...
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Sherman, David M.
1989-01-01
The pressure and temperature-induced metallization of FeO discovered by Knittle et al (1986) is here argued to result from a Mott transition associated with increased Fe(3d)-Fe(3d) orbital overlap at high pressures. Consequently, it is here argued that a lower mantle containing only these phases should be electrically insulating. Finally, the formation of itinerant d-electrons in FeO may be a necessary, if not sufficient, condition for the apparent alloying of FeO with Fe. Such alloying may allow oxygen to be incorporated into the outer core. -from Author
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Bioactive trace metal time series during Austral summer in Ryder Bay, Western Antarctic Peninsula
NASA Astrophysics Data System (ADS)
Bown, Johann; Laan, Patrick; Ossebaar, Sharyn; Bakker, Karel; Rozema, Patrick; de Baar, Hein J. W.
2017-05-01
The Western Antarctic Peninsula, one of the most productive regions of the Southern Ocean, is currently affected by the increasing of atmospheric and oceanic temperatures. For several decades, the Rothera Time Series (RaTS) site located in Ryder Bay has been monitored by the British Antarctic Survey and has shown long lasting phytoplankton summer blooms (over a month) that are likely driven by the length of the sea ice season. The dynamics of phytoplankton blooms in Ryder Bay may just as well be influenced by natural fertilization of iron and other bioactive trace metals due to the proximity of land, islands and glaciers. For the first time, temporal distributions in the surface layer (0-75 m depth) of six bioactive trace metals (dissolved: Fe, Mn, Zn, Cd, Cu and dissolved labile Co) have been investigated with high temporal and spatial resolution at the RaTS site during a total of 2 and 3.5 months respectively, over two consecutive summers. Most of the studied trace elements showed wide ranges of concentrations and this dynamics appears to be driven by phytoplankton uptake, remineralization and occasional vertical mixing associated with storm episodes. The biological uptake of DMn, DZn, DCd, DCoL and DCu was proportional to uptake of phosphate and silicate, which was associated with weak to strong linear relationships depending on which phytoplankton bloom events was considered. This further suggests that the surface water distributions of these studied bio-active trace metals were mainly driven by biological uptake and remineralization during austral spring and summer in Ryder Bay. Even though DFe did not show any strong relationship with phosphate, DFe decreasing concentrations during each bloom event suggest that Fe is a key essential element for phytoplankton in the area of study. The consistency of trace metals/nutrient ratios during two consecutive summers indicates that over-winter scavenging removal was slow relative to mixing. The increase of DCd/P and DCoL/P drawdown ratios during the two consecutive blooms monitored during the second season could reflect the substitution of DZn by trace metals DCd and DCoL due to lowered DZn concentrations after the first bloom. Relationships of trace elements versus silicate appear to be dominated by diatoms abundances which tend to vary both at the season and bloom time scale. Simultaneous short-term events of depletions of both nutrients and bio-active trace metals might induce stress in the growth of the phytoplankton assemblage.
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U.S. EPA, Pesticide Product Label, , 11/14/1991
2011-04-21
... 0. i~jS-"lu j~!:-;l.)licQt.ivl.1~ uat,.t;;;(.l nUSlUc.t. .:t~, .l~~l ilUu uctowr ~j, 1~~..L 4:"<.(H.iu(.:stih'.,;: dn I'\\lt~rr,~l~' O£lJuu L'i
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Effects of Fe2O3 addition on the nitridation of silicon powder
NASA Technical Reports Server (NTRS)
Hasegawa, Y.; Inomata, Y.; Kijima, K.; Matsuyama, T.
1977-01-01
The reaction of silicon powder and nitrogen was studied in the range of 1300-1400 C. When an addition of Fe2O3 was more than 0.8wt%, the reaction was linear and compared to samples with no Fe2O3, the reaction velocity increased 5 to 10 times. The reactions were mediated by the process of peeling and cracking in a thin layer of Si2N4 formed on the silicon particles or on the surface of the Fe-Si melts. As the addition of Fe2O3 increased, the reaction activation energy for highly pure samples decreased. Fe2O3 which exceeded the Si3N4 solubility limits was finally converted to d-Fe.
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NASA Astrophysics Data System (ADS)
Joubert, W. R.; Swart, S.; Tagliabue, A.; Thomalla, S. J.; Monteiro, P. M. S.
2014-03-01
The seasonal cycle of primary productivity is impacted by seasonal and intra-seasonal dynamics of the mixed layer through the changing balance between mixing and buoyancy forcing, which regulates nutrient supply and light availability. Of particular recent interest is the role of synoptic scale events in supplying nutrients, particularly iron, to the euphotic zone in the Sub Antarctic Zone (SAZ), where phytoplankton blooms occur throughout summer. In this study, we present high resolution measurements of net community production (NCP) constrained by ΔO2/Ar ratios, and mixed layer depth (MLD) in the Atlantic SAZ. We found a non-linear relationship between NCP and MLD, with the highest and most variable NCP observed in shallow MLDs (< 45 m). We propose that NCP variability in the SAZ may be driven by alternating states of synoptic-scale deepening of the mixed layer, leading to the entrainment of iron (dFe), followed by restratification, allowing rapid growth in an iron replete, high light environment. Synoptic iron fluxes into the euphotic zone based on water column dFe profiles and high resolution glider MLD data, reveal a potentially significant contribution of "new iron" which could sustain NCP throughout summer. Future process studies will help elaborate these findings further.
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Data Analysis for Rotationally Resolved Spectra: A Simulated Annealing Approach
1992-05-29
Table V. Expe rimental Data PSA was used to analyze high resolution infrared spectra of 2- fluoroethanol (2FE) and difluoroethane (DFE). Although the...does not inhere in the model used to calculate spectra, so the match to the experimental spectrum is not ideal. 8. PSA optimization of Difluoroethane ...A) The experimental spectrum of Difluoroethane . B) The spectrum generated from the starting state given to PSA. C) The spectrum generated from the
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Joshi, Kaushal; Barletta, Michael; Wurpel, John
2017-06-01
Inhalant abuse is the intentional inhalation of chemical vapors to attain euphoric effects. Many common household products are abused by inhalation and one is 1,1-difluoroethane (DFE), which is a halogenated hydrocarbon used in refrigeration, dust-off spray, and airbrush painting. Although many human DFE abuse cases have been studied, the etiology and mechanism of sudden death is still unknown. In this study, an animal model was used to simulate the human conditions of DFE inhalation abuse that results in sudden death.Current research targets mechanistic studies involving electrolyte changes and cardiomyocyte damage after DFE administration in vivo. To investigate these changes, Sprague Dawley rats (N = 6) were exposed to 30 seconds of 20 L/min of DFE in multiple doses. Isoflurane acted as a control. Two additional groups, epinephrine and epinephrine + DFE, were included to simulate the clinical condition of DFE abuse. Plasma sodium, potassium, calcium, and magnesium levels were measured, followed by lactate dehydrogenase, creatine kinase, and cardiac troponin I levels. In addition, oxidative stress markers were also evaluated in all animal groups. Electrolyte levels showed a significant rise in plasma potassium and magnesium levels for the treated groups. In addition, lactate dehydrogenase, creatine kinase, and cardiac troponin I levels in DFE and epinephrine + DFE administered rats were significantly elevated as compared with control. Some oxidative stress makers were also elevated significantly in treatment groups. Furthermore, histopathological analysis showed hyperemia/congestion in treated rats.These results support cardiotoxic effects indicating that DFE results in fatal arrhythmias, and the study can be important during clinical cases involving inhalant abuse.
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Numerical fatigue 3D-FE modeling of indirect composite-restored posterior teeth.
Ausiello, Pietro; Franciosa, Pasquale; Martorelli, Massimo; Watts, David C
2011-05-01
In restored teeth, stresses at the tooth-restoration interface during masticatory processes may fracture the teeth or the restoration and cracks may grow and propagate. The aim was to apply numerical methodologies to simulate the behavior of a restored tooth and to evaluate fatigue lifetimes before crack failure. Using a CAD-FEM procedure and fatigue mechanic laws, the fatigue damage of a restored molar was numerically estimated. Tessellated surfaces of enamel and dentin were extracted by applying segmentation and classification algorithms, to sets of 2D image data. A user-friendly GUI, which enables selection and visualization of 3D tessellated surfaces, was developed in a MatLab(®) environment. The tooth-boundary surfaces of enamel and dentin were then created by sweeping operations through cross-sections. A class II MOD cavity preparation was then added into the 3D model and tetrahedral mesh elements were generated. Fatigue simulation was performed by combining a preliminary static FEA simulation with classical fatigue mechanical laws. Regions with the shortest fatigue-life were located around the fillets of the class II MOD cavity, where the static stress was highest. The described method can be successfully adopted to generate detailed 3D-FE models of molar teeth, with different cavities and restorative materials. This method could be quickly implemented for other dental or biomechanical applications. Copyright © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
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The distribution and stabilisation of dissolved Fe in deep-sea hydrothermal plumes
NASA Astrophysics Data System (ADS)
Bennett, Sarah A.; Achterberg, Eric P.; Connelly, Douglas P.; Statham, Peter J.; Fones, Gary R.; German, Christopher R.
2008-06-01
We have conducted a study of hydrothermal plumes overlying the Mid-Atlantic Ridge near 5° S to investigate whether there is a significant export flux of dissolved Fe from hydrothermal venting to the oceans. Our study combined measurements of plume-height Fe concentrations from a series of 6 CTD stations together with studies of dissolved Fe speciation in a subset of those samples. At 2.5 km down plume from the nearest known vent site dissolved Fe concentrations were ˜ 20 nM. This is much higher than would be predicted from a combination of plume dilution and dissolved Fe(II) oxidation rates, but consistent with stabilisation due to the presence of organic Fe complexes and Fe colloids. Using Competitive Ligand Exchange-Cathodic Stripping Voltammetry (CLE-CSV), stabilised dissolved Fe complexes were detected within the dissolved Fe fraction on the edges of one non-buoyant hydrothermal plume with observed ligand concentrations high enough to account for stabilisation of ˜ 4% of the total Fe emitted from the 5° S vent sites. If these results were representative of all hydrothermal systems, submarine venting could provide 12-22% of the global deep-ocean dissolved Fe budget.
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Dairy farm effluent effects on urine patch nitrous oxide and carbon dioxide emissions.
Clough, Tim J; Kelliher, Francis M
2005-01-01
Dairy farm effluent (DFE) comprises animal feces, urine, and wash-down water collected at the milking shed. This is collected daily during the milking season and sprayed onto grazed dairy pastures. Urine patches in grazed pastures make a significant contribution to anthropogenic N(2)O emissions. The DFE could potentially mitigate N(2)O emissions by influencing the N(2)O to dinitrogen (N(2)) ratio, since it contains water-soluble carbon (WSC). Alternatively, DFE may enhance N(2)O emissions from urine patches. The application of DFE may also provide a substrate for the production of CO(2) in pasture soils. The effects of DFE on the CO(2) and N(2)O emissions from urine patches are unknown. Thus a laboratory experiment was performed where repeated DFE applications were made to repacked soil cores. Dairy farm effluent was applied at 0, 7, or 14 d after urine deposition. The urine was applied once on Day 0. Urine contained (15)N-enriched urea. Measurements of N(2)O, N(2), and carbon dioxide (CO(2)) fluxes, soil pH, and soil inorganic N concentrations were made. After 43 d the DFE had not mitigated N(2)O fluxes from urine patches. A small increase in the N(2)O flux occurred from the urine-treated soils where DFE was applied 1 wk after urine deposition. The amount of WSC applied in the DFE proved to be insignificant compared with the amount of soil C released as CO(2) following urine application. The priming of soil C in urine patches has implications for the understanding of soil C processes in grazed pasture ecosystems and the budgeting of C within these ecosystems.
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Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China.
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.
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Design for the Environment Products (Raw Data)
This dataset contains a list of products that carry the Design for the Environment (DfE) label. This mark enables consumers to quickly identify and choose products that can help protect the environment and are safer for families. When you see the DfE logo on a product it means that the DfE scientific review team has screened each ingredient for potential human health and environmental effects and that-based on currently available information, EPA predictive models, and expert judgment-the product contains only those ingredients that pose the least concern among chemicals in their class. Product manufacturers who become DfE partners, and earn the right to display the DfE logo on recognized products, have invested heavily in research, development and reformulation to ensure that their ingredients and finished product line up on the green end of the health and environmental spectrum while maintaining or improving product performance. EPA's Design for the Environment Program (DfE) has allowed use of their logo on over 2500 products. These products are formulated from the safest possible ingredients and have reduced the use of chemicals of concern by hundreds of millions of pounds. A Spanish version of this dataset is available for download at http://www.epa.gov/dfe/pubs/products/list_of_labeled_products.html
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NASA Astrophysics Data System (ADS)
Badía-Romano, L.; Rubín, J.; Magén, C.; Bürgler, D. E.; Bartolomé, J.
2014-07-01
The morphology and the quantitative composition of the Fe-Si interface layer forming at each Fe layer of a (Fe/Si)3 multilayer have been determined by means of conversion electron Mössbauer spectroscopy (CEMS) and high-resolution transmission electron microscopy (HRTEM). For the CEMS measurements, each layer was selected by depositing the Mössbauer active 57Fe isotope with 95% enrichment. Samples with Fe layers of nominal thickness dFe = 2.6 nm and Si spacers of dSi = 1.5 nm were prepared by thermal evaporation onto a GaAs(001) substrate with an intermediate Ag(001) buffer layer. HRTEM images showed that Si layers grow amorphous and the epitaxial growth of the Fe is good only for the first deposited layer. The CEMS spectra show that at all Fe/Si and Si/Fe interfaces a paramagnetic c-Fe1-xSi phase is formed, which contains 16% of the nominal Fe deposited in the Fe layer. The bottom Fe layer, which is in contact with the Ag buffer, also contains α-Fe and an Fe1-xSix alloy that cannot be attributed to a single phase. In contrast, the other two layers only comprise an Fe1-xSix alloy with a Si concentration of ≃0.15, but no α-Fe.
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Sung, Yoon-Young; Kim, Dong-Seon; Yang, Won-Kyung; Nho, Kyoung Jin; Seo, Hyeong Seok; Kim, Young Sang; Kim, Ho Kyoung
2012-10-31
Drynaria fortunei (Kunze) J. Sm has been widely used in traditional medicine for the treatment of inflammation, hyperlipidemia, arteriosclerosis, rheumatism, and bone healing. We investigated the anti-inflammatory effects of a 70% ethanol extract of Drynaria fortunei (DFE). We evaluated the anti-inflammatory effects of topically applied DFE on house dust mite Dermatophargoides farinae-induced atopic dermatitis-like skin lesions in NC/Nga mice. Treatment of NC/Nga mice with DFE reduced the dermatitis score, ear thickness, and serum levels of IgE, IgG1, and IL-6. Histopathological analyses of ear and skin lesions showed inhibition of the thickening of the epidermis and reduced epidermal/dermal infiltration of inflammatory cells. In ear lesions, mRNA expression levels of IL-4, IL-6, and tumor necrosis factor-α were reduced by DFE treatment. DFE inhibited the development of dermatitis-like skin lesions in NC/Nga mice. These results suggest that DFE may be a therapeutic candidate for the treatment of AD. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.
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Fatal cardiac arrhythmia after repeated exposure to 1,1-difluoroethane (DFE).
Avella, Joseph; Wilson, James C; Lehrer, Michael
2006-03-01
A 42-year-old man was found dead after repeated exposure to 1,1-difluoroethane (DFE, Freon 152a), a propellant found in CRC Duster, a product intended for the removal of dust and lint. Toxicologic analysis detected DFE in femoral blood 136.3 mg/L, brain 117.5 mg/kg, liver 87.6 mg/kg, lung 60.3 mg/kg, adipose 235.7 mg/kg, and vitreous fluid 25.1 mg/L. The cause of death was determined to be a fatal cardiac arrhythmia due to intoxication with 1,1-difluoroethane. After comparison to previously published cases involving DFE, we suggest that analysis of adipose tissue for DFE and similar compounds, along with blood and other tissues, may be useful in distinguishing between acute versus chronic exposure. Adipose may also be a valuable alternate specimen for detection in cases where loss or elimination from blood is likely to have occurred.
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Federal Register 2010, 2011, 2012, 2013, 2014
2013-11-13
... Request Submitted to OMB for Review and Approval; Comment Request; EPA's Design for the Environment (DfE... Environment (DfE) Logo Redesign Consultations'' (EPA ICR No. 2487.01, OMB Control No. 2070-NEW) to the Office... (EPA) will select a revised logo and messaging for its Design for the Environment (DfE) program. A key...
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Federal Register 2010, 2011, 2012, 2013, 2014
2012-10-30
... Activities; Submission to OMB for Review and Approval; Comment Request; EPA's Design for the Environment (DfE... Budget (OMB) for review and approval: EPA's Design for the Environment (DfE) Partner of the Year Awards... . Title: EPA's Design for the Environment (DfE) Partner of the Year Awards Program. ICR Status: This is a...
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Design for the Environment Products (Online Search)
This dataset contains a list of products that carry the Design for the Environment (DfE) label. This mark enables consumers to quickly identify and choose products that can help protect the environment and are safer for families. When you see the DfE logo on a product it means that the DfE scientific review team has screened each ingredient for potential human health and environmental effects and that-based on currently available information, EPA predictive models, and expert judgment-the product contains only those ingredients that pose the least concern among chemicals in their class. Product manufacturers who become DfE partners, and earn the right to display the DfE logo on recognized products, have invested heavily in research, development and reformulation to ensure that their ingredients and finished product line up on the green end of the health and environmental spectrum while maintaining or improving product performance. EPA's Design for the Environment Program (DfE) has allowed use of their logo on over 2500 products. These products are formulated from the safest possible ingredients and have reduced the use of chemicals of concern by hundreds of millions of pounds.
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Kim, Bernard Y.; Huber, Christian D.; Lohmueller, Kirk E.
2017-01-01
The distribution of fitness effects (DFE) has considerable importance in population genetics. To date, estimates of the DFE come from studies using a small number of individuals. Thus, estimates of the proportion of moderately to strongly deleterious new mutations may be unreliable because such variants are unlikely to be segregating in the data. Additionally, the true functional form of the DFE is unknown, and estimates of the DFE differ significantly between studies. Here we present a flexible and computationally tractable method, called Fit∂a∂i, to estimate the DFE of new mutations using the site frequency spectrum from a large number of individuals. We apply our approach to the frequency spectrum of 1300 Europeans from the Exome Sequencing Project ESP6400 data set, 1298 Danes from the LuCamp data set, and 432 Europeans from the 1000 Genomes Project to estimate the DFE of deleterious nonsynonymous mutations. We infer significantly fewer (0.38–0.84 fold) strongly deleterious mutations with selection coefficient |s| > 0.01 and more (1.24–1.43 fold) weakly deleterious mutations with selection coefficient |s| < 0.001 compared to previous estimates. Furthermore, a DFE that is a mixture distribution of a point mass at neutrality plus a gamma distribution fits better than a gamma distribution in two of the three data sets. Our results suggest that nearly neutral forces play a larger role in human evolution than previously thought. PMID:28249985
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NASA Astrophysics Data System (ADS)
Oiwake, M.; Ootsuki, D.; Noji, T.; Hatakeda, T.; Koike, Y.; Horio, M.; Fujimori, A.; Saini, N. L.; Mizokawa, T.
2013-12-01
We have investigated the electronic structure of superconducting (SC) and nonsuperconducting (non-SC) KxFe2-ySe2 using x-ray photoemission spectroscopy (XPS). The spectral shape of the Fe 2p XPS is found to depend on the amount of Fe vacancies. The Fe 2p3/2 peak of the SC and non-SC Fe-rich samples is accompanied by a shoulder structure on the lower binding energy side, which can be attributed to the metallic phase embedded in the Fe2+ insulating phase. The absence of the shoulder structure in the non-SC Fe-poor sample allows us to analyze the Fe 2p spectra using a FeSe4 cluster model. The Fe 3d-Se 4p charge-transfer energy of the Fe2+ insulating phase is found to be ˜2.3 eV which is smaller than the Fe 3d-Fe 3d Coulomb interaction of ˜3.5 eV. This indicates that the Fe2+ insulating state is the charge-transfer type in the Zaanen-Sawatzky-Allen scheme. We also find a substantial change in the valence-band XPS as a function of Fe content and temperature. The metallic state at the Fermi level is seen in the SC and non-SC Fe-rich samples and tends to be enhanced with cooling in the SC sample.
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Improving Passive Time Reversal Underwater Acoustic Communications Using Subarray Processing.
He, Chengbing; Jing, Lianyou; Xi, Rui; Li, Qinyuan; Zhang, Qunfei
2017-04-24
Multichannel receivers are usually employed in high-rate underwater acoustic communication to achieve spatial diversity. In the context of multichannel underwater acoustic communications, passive time reversal (TR) combined with a single-channel adaptive decision feedback equalizer (TR-DFE) is a low-complexity solution to achieve both spatial and temporal focusing. In this paper, we present a novel receiver structure to combine passive time reversal with a low-order multichannel adaptive decision feedback equalizer (TR-MC-DFE) to improve the performance of the conventional TR-DFE. First, the proposed method divides the whole received array into several subarrays. Second, we conduct passive time reversal processing in each subarray. Third, the multiple subarray outputs are equalized with a low-order multichannel DFE. We also investigated different channel estimation methods, including least squares (LS), orthogonal matching pursuit (OMP), and improved proportionate normalized least mean squares (IPNLMS). The bit error rate (BER) and output signal-to-noise ratio (SNR) performances of the receiver algorithms are evaluated using simulation and real data collected in a lake experiment. The source-receiver range is 7.4 km, and the data rate with quadrature phase shift keying (QPSK) signal is 8 kbits/s. The uncoded BER of the single input multiple output (SIMO) systems varies between 1 × 10 - 1 and 2 × 10 - 2 for the conventional TR-DFE, and between 1 × 10 - 2 and 1 × 10 - 3 for the proposed TR-MC-DFE when eight hydrophones are utilized. Compared to conventional TR-DFE, the average output SNR of the experimental data is enhanced by 3 dB.
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Improving Passive Time Reversal Underwater Acoustic Communications Using Subarray Processing
He, Chengbing; Jing, Lianyou; Xi, Rui; Li, Qinyuan; Zhang, Qunfei
2017-01-01
Multichannel receivers are usually employed in high-rate underwater acoustic communication to achieve spatial diversity. In the context of multichannel underwater acoustic communications, passive time reversal (TR) combined with a single-channel adaptive decision feedback equalizer (TR-DFE) is a low-complexity solution to achieve both spatial and temporal focusing. In this paper, we present a novel receiver structure to combine passive time reversal with a low-order multichannel adaptive decision feedback equalizer (TR-MC-DFE) to improve the performance of the conventional TR-DFE. First, the proposed method divides the whole received array into several subarrays. Second, we conduct passive time reversal processing in each subarray. Third, the multiple subarray outputs are equalized with a low-order multichannel DFE. We also investigated different channel estimation methods, including least squares (LS), orthogonal matching pursuit (OMP), and improved proportionate normalized least mean squares (IPNLMS). The bit error rate (BER) and output signal-to-noise ratio (SNR) performances of the receiver algorithms are evaluated using simulation and real data collected in a lake experiment. The source-receiver range is 7.4 km, and the data rate with quadrature phase shift keying (QPSK) signal is 8 kbits/s. The uncoded BER of the single input multiple output (SIMO) systems varies between 1×10−1 and 2×10−2 for the conventional TR-DFE, and between 1×10−2 and 1×10−3 for the proposed TR-MC-DFE when eight hydrophones are utilized. Compared to conventional TR-DFE, the average output SNR of the experimental data is enhanced by 3 dB. PMID:28441763
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Avella, Joseph; Lehrer, Michael; Zito, S William
2008-10-01
1,1-Difluoroethane (DFE), also known as Freon 152A, is a member of a class of compounds known as halogenated hydrocarbons. A number of these compounds have gained notoriety because of their ability to induce rapid onset of intoxication after inhalation exposure. Abuse of DFE has necessitated development of methods for its detection and quantitation in postmortem and human performance specimens. Furthermore, methodologies applicable to research studies are required as there have been limited toxicokinetic and toxicodynamic reports published on DFE. This paper describes a method for the quantitation of DFE using a gas chromatography-flame-ionization headspace technique that employs solventless standards for calibration. Two calibration curves using 0.5 mL whole blood calibrators which ranged from A: 0.225-1.350 to B: 9.0-180.0 mg/L were developed. These were evaluated for linearity (0.9992 and 0.9995), limit of detection of 0.018 mg/L, limit of quantitation of 0.099 mg/L (recovery 111.9%, CV 9.92%), and upper limit of linearity of 27,000.0 mg/L. Combined curve recovery results of a 98.0 mg/L DFE control that was prepared using an alternate technique was 102.2% with CV of 3.09%. No matrix interference was observed in DFE enriched blood, urine or brain specimens nor did analysis of variance detect any significant differences (alpha = 0.01) in the area under the curve of blood, urine or brain specimens at three identical DFE concentrations. The method is suitable for use in forensic laboratories because validation was performed on instrumentation routinely used in forensic labs and due to the ease with which the calibration range can be adjusted. Perhaps more importantly it is also useful for research oriented studies because the removal of solvent from standard preparation eliminates the possibility for solvent induced changes to the gas/liquid partitioning of DFE or chromatographic interference due to the presence of solvent in specimens.
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Pizzi, Laura T; Zangalli, Camila S; Murchison, Ann P; Hale, Nicole; Hark, Lisa; Dai, Yang; Leiby, Benjamin E; Haller, Julia A
2015-04-01
Diabetic retinopathy is one of the leading causes of vision impairment among adults in the USA. While it is suggested that diabetics receive annual dilated fundus examinations (DFE), many patients do not adhere to these recommendations. This paper investigates the outcomes and costs of an educational and telephone intervention on DFE follow-up adherence in patients with diabetes. In a prospective trial, 356 diabetic patients due for a DFE at an urban eye clinic were randomly assigned to usual care (UC; reference case), mailed intervention (MI), or telephone intervention (TI). UC patients (n = 119) received a standard form letter. MI patients (n = 117) received a personalized letter encouraging scheduling of an eye examination with an educational brochure about diabetic eye disease. TI patients (n = 120) received personal calls (up to three attempts) to schedule a follow-up with standard form letter. The primary outcome was obtaining a DFE within 90 days of suggested return. Costs (US$ 2013) included time costs for staff, phone charges, supplies, and postage. Since TI involved greater cost components compared to MI, univariate sensitivity analysis examined the impact of reducing phone costs. Patients were mostly female (66 %) and African American (70 %) with a mean age of 61 years. TI patients were more likely to schedule DFE [65 vs. 42 %; relative risk (RR) 1.54; CI 1.20-1.96; P < 0.001] versus UC patients. Obtaining a DFE within 90 days of suggested return was also significantly higher among TI patients compared to UC patients (51 vs. 36 %, RR 1.41; CI 1.05-1.89; P = 0.024). MI patients were slightly less likely to schedule DFE versus UC patients (38 vs. 42 %, RR 0.90; CI 0.66-1.22; P = NSS) and obtain a DFE (32 vs. 36 %; RR 0.90; CI 0.63-1.28; P = NSS). The total cost of TI was US$798.28 or US$6.65/patient and the cost/follow-up DFE was US$26.05. Sensitivity analyses revealed that the cost/follow-up can be greatly reduced but remains greater compared to UC (US$2.76 if US$0.25/call, US$11.13 if $1/call; US$22.29 if US$2/call). Personal phone assistance in scheduling DFE follow-up is more effective but also more costly. Follow-up research has been initiated to determine whether automated phone reminders can achieve similar effectiveness at a lower cost.
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Bae, Yeunook; Kim, Dooil; Cho, Hyun-Hee; Singhal, Naresh; Park, Jae-Woo
2012-12-01
In this research, we conducted trichloroethylene (TCE) reduction in a column filled with iron and iron-reducing bacteria (IRB) and developed a mathematical model to investigate the critical reactions between active species in iron/IRB/contaminant systems. The formation of ferrous iron (Fe(II)) in this system with IRB and zero-valent iron (ZVI, Fe(0)) coated with a ferric iron (Fe(III)) crust significantly affected TCE reduction and IRB respiration in various ways. This study presents a new framework for transformation property and reducing ability of both dissolved (Fe(II)(dissolved)) and solid form ferrous iron (Fe(II)(solid)). Results showed that TCE reduction was strongly depressed by Fe(II)(solid) rather than by other inhibitors (e.g., Fe(III) and lactate), suggesting that Fe(II)(solid) might reduce IRB activation due to attachment to IRB cells. Newly exposed Fe(0) from the released Fe(II)(dissolved) was a strong contributor to TCE reduction compared to Fe(II)(solid). In addition, our research confirmed that less Fe(II)(solid) production strongly supported long-term TCE reduction because it may create an easier TCE approach to Fe(0) or increase IRB growth. Our findings will aid the understanding of the contributions of iron media (e.g., Fe(II)(solid), Fe(II)(dissolved), Fe(III), and Fe(0)) to IRB for decontamination in natural groundwater systems. Copyright © 2012 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Gunde, R.; Ha, T.-K.; Günthard, H. H.
1990-08-01
In this paper results of consistent force field modeling (CFF) of the potential function to conversion of the gauche (g) to the trans (t) conformer of 1,2-difluoroethane (DFE) isolated in an argon matrix will be reported. Starting point are locally stable configurations gDFE:Ar 364 (defect GH1) and tDFE:Ar 364 (TH1) obtained in previous work from CFF modeling of a cube shaped Ar 364 fragment containing one DFE molecule in its center. Using the dihedral angle of DFE as an independent parameter the minimum energy path of the conversion process gDFE:Ar 364→tDFE:Ar 364 will be determined by CFF energy minimization. Determination of the minimum energy path is found to require large numbers of energy minimization steps and to lead to a rather complicated motion of the molecule with respect to the crystal fragment. Surprisingly the molecule-matrix interactions lead to a reduction of the g-t barrier by ≈500 cal/mol and to a stabilization of the trans species by ≈500 cal/mol. This finding is a consequence of a delicate interplay of matrix-molecule and matrix-matrix interactions. Calculation of the electric polarization energy (induced dipole-first-order polarization approximation) is based on extended ab initio calculations of dipole and quadrupole moments and a bond polarizability estimate of the first-order polarizability of DFE as a function of the internal rotation angle, on Fourier expansion of multipole components and use of symmetry for reduction of the order of the linear system defining the (self-consistent) induced dipole moments of all Ar atoms. Electric polarization is found to alter the potential function of the conversion process in a profound way: the g-t barrier and the t-g energy difference are increased to ≈3000 cal/mol and to ≈1500 cal/mol respectively (≈2500 and ≈530 cal/mol respectively for free DFE). Further applications of the technique developed in this work to related problems of matrix isolated molecules, e.g., vibrational matrix shifts will be discussed.
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Comparison of NRZ and duo-binary format in adaptive equalization assisted 10G-optics based 25G-EPON
NASA Astrophysics Data System (ADS)
Xia, Junqi; Li, Zhengxuan; Li, Yingchun; Xu, Tingting; Chen, Jian; Song, Yingxiong; Wang, Min
2018-03-01
We investigate and compare the requirements of FFE/DFE based adaptive equalization techniques for NRZ and Duo-binary based 25-Gb/s transmission, which are two of the most promising schemes for 25G-EPON. A 25-Gb/s transmission system based on 10G optical transceivers is demonstrated and the performance of only FFE and combination of FFE and DFE with different number of taps are compared with two modulation formats. The FFE/DFE based Duo-binary receiver shows better performance than NRZ receiver. For Duo-binary receiver, only 13-tap FFE is needed for BtB case and the combination of 17-tap FFE and 5-tap DFE can achieve a sensitivity of -23.45 dBm in 25 km transmission case, which is ∼0.6 dB better than the best performance of NRZ equalization. In addition, the requirements of training sequence length for FFE/DFE based adaptive equalization is verified. Experimental results show that 400 symbols training length is optimal for the two modulations, which shows a small packet preamble in up-stream burst-mode transmission.
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Al-Rasheed, Nouf M.; Attia, Hala A.; Mohamad, Raeesa A.; Al-Rasheed, Nawal M.; Al-Amin, Maha A.; AL-Onazi, Asma
2015-01-01
Previous data indicated the protective effect of date fruit extract on oxidative damage in rat liver. However, the hepatoprotective effects via other mechanisms have not been investigated. This study was performed to evaluate the antifibrotic effect of date flesh extract (DFE) or date pits extract (DPE) via inactivation of hepatic stellate cells (HSCs), reducing the levels of inflammatory, fibrotic and angiogenic markers. Coffee was used as reference hepatoprotective agent. Liver fibrosis was induced by injection of CCl4 (0.4 mL/kg) three times weekly for 8 weeks. DFE, DPE (6 mL/kg), coffee (300 mg/kg), and combination of coffee + DFE and coffee + DPE were given to CCl4-intoxicated rats daily for 8 weeks. DFE, DPE, and their combination with coffee attenuated the elevated levels of inflammatory cytokines including tumor necrosis factor-α, interleukin-6, and interleukin-1β. The increased levels of transforming growth factor-β1 and collagen deposition in injured liver were alleviated by both extracts. CCl4-induced expression of α-smooth muscle actin was suppressed indicating HSCs inactivation. Increased angiogenesis was ameliorated as revealed by reduced levels and expression of vascular endothelial growth factor and CD31. We concluded that DFE or DPE could protect liver via different mechanisms. The combination of coffee with DFE or DPE may enhance its antifibrotic effects. PMID:25945106
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Bu, Hongmei; Wang, Weibo; Song, Xianfang; Zhang, Quanfa
2015-09-01
Dissolved trace elements and physiochemical parameters were analyzed to investigate their physicochemical characteristics and identify their sources at 12 sampling sites of the Jinshui River in the South Qinling Mts., China from October 2006 to November 2008. The two-factor ANOVA indicated significant temporal variations of the dissolved Cu, Fe, Sr, Si, and V (p < 0.001 or p < 0.05). With the exception of Sr (p < 0.001), no significant spatial variations were found. Distributions and concentrations of the dissolved trace elements displayed that dissolved Cu, Fe, Sr, Si, V, and Cr were originated from chemical weathering and leaching from the soil and bedrock. Dissolved Cu, Fe, Sr, As, and Si were also from anthropogenic inputs (farming and domestic effluents). Correlation and regression analysis showed that the chemical and physical processes of dissolved Cu was influenced by water temperature and dissolved oxygen (DO) to some degree. Dissolved Fe and Sr were affected by colloid destabilization or sedimentary inputs. Concentrations of dissolved Si were slightly controlled by biological uptake. Principal component analysis confirmed that Fe, Sr, and V resulted from domestic effluents, agricultural runoff, and confluence, whereas As, Cu, and Si were from agricultural activities, and Cr and Zn through natural processes. The research results provide a reference for ecological restoration and protection of the river environment in the Qinling Mts., China.
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NASA Astrophysics Data System (ADS)
Sihota, Natasha J.; Mayer, K. Ulrich; Toso, Mark A.; Atwater, Joel F.
2013-08-01
The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation—related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur—even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m- 2 s- 1, and CH4 effluxes ranged between non-detect and 9 μmol m- 2 s- 1. At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m- 2 s- 1, and CH4 effluxes ranged between non-detect and 393 μmol m- 2 s- 1. Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions.
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Sihota, Natasha J; Mayer, K Ulrich; Toso, Mark A; Atwater, Joel F
2013-08-01
The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation-related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur-even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 9 μmol m(-2) s(-1). At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 393 μmol m(-2) s(-1). Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions. Copyright © 2013 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Rivaro, Paola; Ianni, Carmela; Massolo, Serena; Abelmoschi, M. Luisa; De Vittor, Cinzia; Frache, Roberto
2011-05-01
The distribution of the dissolved labile and of the particulate Fe and Cu together with dissolved oxygen, nutrients, chlorophyll a and total particulate matter was investigated in the surface waters of Terra Nova Bay polynya in mid-January 2003. The measurements were conducted within the framework of the Italian Climatic Long-term Interactions of the Mass balance in Antarctica (CLIMA) Project activities. The labile dissolved fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The dissolved labile Fe ranges from below the detection limit (0.15 nM) to 3.71 nM, while the dissolved labile Cu from below the detection limit (0.10 nM) to 0.90 nM. The lowest concentrations for both metals were observed at 20 m depth (the shallowest depth for which metals were measured). The concentration of the particulate Fe was about 5 times higher than the dissolved Fe concentration, ranging from 0.56 to 24.83 nM with an average of 6.45 nM. The concentration of the particulate Cu ranged from 0.01 to 0.71 nM with an average of 0.17 nM. The values are in agreement with the previous data collected in the same area. We evaluated the role of the Fe and Cu as biolimiting metals. The N:dissolved labile Fe ratios (18,900-130,666) would or would not allow a complete nitrate removal, on the basis of the N:Fe requirement ratios that we calculated considering the N:P and the C:P ratios estimated for diatoms. This finding partially agrees with the Si:N ratio that we found (2.29). Moreover we considered a possible influence of the dissolved labile Cu on the Fe uptake process.
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NASA Astrophysics Data System (ADS)
Measures, C. I.; Brown, M. T.; Selph, K. E.; Apprill, A.; Zhou, M.; Hatta, M.; Hiscock, W. T.
2013-06-01
Dissolved trace element distributions near Elephant Island in the Drake Passage show extremely high levels of dissolved Fe and Mn in waters above the shelf. The entrainment of this enriched shelf water by the Fe-poor Antarctic Circumpolar Current (ACC) as it passes through the Shackleton Gap delivers an estimated 2.8×106 mol yr-1 dissolved Fe to the offshore waters of the Drake Passage. The magnitude and spatial distribution of dissolved Fe, Mn and Al over the shelf are consistent with a diagenetically produced sedimentary source, but are inconsistent with eolian or upwelling sources. The systematics of the Mn and Fe concentrations suggest that there are two distinct sources of dissolved Fe to the surface waters of this region. The highest Fe concentrations are associated with Bransfield Strait water, which can be identified by its characteristic temperature and salinity (T/S) properties both inside the Bransfield Strait and in the Bransfield Current outflow between Elephant and Clarence Islands. Most of the shelf area is dominated by a second water type with T/S properties that are typical of modified Antarctic Surface Water, which while also enriched has a lower Fe:Mn ratio. The predominantly linear relationships between the Fe and Mn concentrations at the stations in each of these water mass types suggest that the distribution of these elements is largely controlled by physical mixing processes and that biological removal of Fe on the shelf, while certainly occurring, is limited, perhaps as a result of rapid physical flushing processes and relatively slow biological growth rates. The consequent export of large quantities of this shelf-derived Fe into the ACC is likely responsible for the extensive regions of enhanced primary production seen in satellite imagery downstream of the Drake Passage.
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40-Gb/s PAM4 with low-complexity equalizers for next-generation PON systems
NASA Astrophysics Data System (ADS)
Tang, Xizi; Zhou, Ji; Guo, Mengqi; Qi, Jia; Hu, Fan; Qiao, Yaojun; Lu, Yueming
2018-01-01
In this paper, we demonstrate 40-Gb/s four-level pulse amplitude modulation (PAM4) transmission with 10 GHz devices and low-complexity equalizers for next-generation passive optical network (PON) systems. Simple feed-forward equalizer (FFE) and decision feedback equalizer (DFE) enable 20 km fiber transmission while high-complexity Volterra algorithm in combination with FFE and DFE can extend the transmission distance to 40 km. A simplified Volterra algorithm is proposed for reducing computational complexity. Simulation results show that the simplified Volterra algorithm reduces up to ∼75% computational complexity at a relatively low cost of only 0.4 dB power budget. At a forward error correction (FEC) threshold of 10-3 , we achieve 31.2 dB and 30.8 dB power budget over 40 km fiber transmission using traditional FFE-DFE-Volterra and our simplified FFE-DFE-Volterra, respectively.
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Influence of sea level rise on iron diagenesis in an east Florida subterranean estuary
Roy, M.; Martin, J.B.; Cherrier, J.; Cable, J.E.; Smith, C.G.
2010-01-01
Subterranean estuary occupies the transition zone between hypoxic fresh groundwater and oxic seawater, and between terrestrial and marine sediment deposits. Consequently, we hypothesize, in a subterranean estuary, biogeochemical reactions of Fe respond to submarine groundwater discharge (SGD) and sea level rise. Porewater and sediment samples were collected across a 30-m wide freshwater discharge zone of the Indian River Lagoon (Florida, USA) subterranean estuary, and at a site 250. m offshore. Porewater Fe concentrations range from 0.5 ??M at the shoreline and 250. m offshore to about 286 ??M at the freshwater-saltwater boundary. Sediment sulfur and porewater sulfide maxima occur in near-surface OC-rich black sediments of marine origin, and dissolved Fe maxima occur in underlying OC-poor orange sediments of terrestrial origin. Freshwater SGD flow rates decrease offshore from around 1 to 0.1. cm/day, while bioirrigation exchange deepens with distance from about 10. cm at the shoreline to about 40. cm at the freshwater-saltwater boundary. DOC concentrations increase from around 75 ??M at the shoreline to as much as 700 ??M at the freshwater-saltwater boundary as a result of labile marine carbon inputs from marine SGD. This labile DOC reduces Fe-oxides, which in conjunction with slow discharge of SGD at the boundary, allows dissolved Fe to accumulate. Upward advection of fresh SGD carries dissolved Fe from the Fe-oxide reduction zone to the sulfate reduction zone, where dissolved Fe precipitates as Fe-sulfides. Saturation models of Fe-sulfides indicate some fractions of these Fe-sulfides get dissolved near the sediment-water interface, where bioirrigation exchanges oxic surface water. The estimated dissolved Fe flux is approximately 0.84 ??M Fe/day per meter of shoreline to lagoon surface waters. Accelerated sea level rise predictions are thus likely to increase the Fe flux to surface waters and local primary productivity, particularly along coastlines where groundwater discharges through sediments. ?? 2010 Elsevier Ltd.
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Schemel, L.E.; Kimball, B.A.; Bencala, K.E.
2000-01-01
Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO4, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO4 waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO4, and dissolved silica through the two mixing zones and small losses (< 10%) of colloidal Al, Fe and Zn from the water column.
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Brown, C.J.; Misut, P.E.
2010-01-01
The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.The simulated injection of buffered, oxic city water into a hypothetical ASR well increased the hydraulic head at the well, displaced the ambient groundwater, and formed a spheroid of injected water with lower concentrations of Fe, Mn and major ions in water surrounding the ASR well, than in ambient water. Both the dissolved O2 concentrations and the pH of water near the well generally increased in magnitude during the simulated 5-a injection phase. The resultant oxidation of Fe2+ and attendant precipitation of goethite during injection provided a substrate for sorption of dissolved Fe during the 8-a extraction phase. The baseline scenario with a low (0.001M) concentration of pyrite in aquifer sediments, indicated that nearly 190% more water with acceptably low concentrations of dissolved Fe could be extracted than was injected. Scenarios with larger amounts of pyrite in aquifer sediments generally resulted in less goethite precipitation, increased acidity, and increased concentrations of dissolved Fe in extracted water. In these pyritic scenarios, the lower amounts of goethite precipitated and the lower pH during the extraction phase resulted in decreased sorption of Fe2+ and a decreased amount of extractable water with acceptably low concentrations of dissolved Fe (5.4??10-6M). A linear decrease in recovery efficiency with respect to dissolved Fe concentrations is caused by pyrite dissolution and the associated depletion of dissolved O2 (DO) and increase in acidity. Simulations with more than 0.0037M of pyrite, which is the maximum amount dissolved in the baseline scenario, had just over a 50% recovery efficiency. The precipitation of ferric hydroxide minerals (goethite) at the well screen, and a possible associated decrease in specific capacity of the ASR well, was not apparent during the extraction phase of ASR simulations, but the model does not incorporate the microbial effects and biofouling associated with ferric hydroxide precipitation.The host groundwater chemistry in calcite-poor Cretaceous aquifers of the NYC area consists of low alkalinity and moderate to low pH. The dissolution of goethite in scenarios with unbuffered injectate indicates that corrosion of the well could occur if the injectate is not buffered. Simulations with buffered injectate resulted in greater precipitation of goethite, and lower concentrations of dissolved Fe, in the extracted water. Dissolved Fe concentrations in extracted water were highest in simulations of aquifers (1) in which pyrite and siderite in the aquifer were in equilibrium, and (2) in coastal areas affected by saltwater intrusion, where high dissolved-cation concentrations provide a greater exchange of Fe2+ (FeX2). Results indicate that ASR in pyrite-beari
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Double-spiral magnetic structure of the Fe/Cr multilayer revealed by nuclear resonance reflectivity
NASA Astrophysics Data System (ADS)
Andreeva, M. A.; Baulin, R. A.; Chumakov, A. I.; Rüffer, R.; Smirnov, G. V.; Babanov, Y. A.; Devyaterikov, D. I.; Milyaev, M. A.; Ponomarev, D. A.; Romashev, L. N.; Ustinov, V. V.
2018-01-01
We have studied the magnetization depth profiles in a [57Fe (dFe) /Cr (dCr) ]30 multilayer with ultrathin Fe layers and nominal thickness of the chromium spacers dCr≈2.0 nm using nuclear resonance scattering of synchrotron radiation. The presence of a broad pure-magnetic half-order (1/2) Bragg reflection has been detected at zero external field. The joint fit of the reflectivity curves and Mössbauer spectra of reflectivity measured near the critical angle and at the "magnetic" peak reveals that the magnetic structure of the multilayer is formed by two spirals, one in the odd and another one in the even iron layers, with the opposite signs of rotation. The double-spiral structure starts from the surface with the almost-antiferromagnetic alignment of the adjacent Fe layers. The rotation of the two spirals leads to nearly ferromagnetic alignment of the two magnetic subsystems at some depth, where the sudden turn of the magnetic vectors by ˜180∘ (spin flop) appears, and both spirals start to rotate in opposite directions. The observation of this unusual double-spiral magnetic structure suggests that the unique properties of giant magnetoresistance devices can be further tailored using ultrathin magnetic layers.
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A motor vehicle accident fatality involving the inhalation of 1,1-difluoroethane.
Hahn, Timothy; Avella, Joseph; Lehrer, Michael
2006-10-01
A 24-year-old female driver with a history of substance abuse was pronounced dead following a single car motor vehicle accident. A surviving front seat passenger witnessed the decedent inhaling "Dust Off" cleaner just prior to losing control of the vehicle. The propellant compound used in this product is the halogenated hydrocarbon 1,1-difluoroethane (DFE). Sealed autopsy specimens were examined for the presence and subsequent quantitation of DFE utilizing an Agilent 6850 gas chromatograph (GC)-flame-ionization detector. The levels of DFE obtained were as follows: 29.8 mg/L in femoral blood, 40.3 mg/L in pulmonary arterial blood, 85.6 mg/L in aortic blood, 79.9 mg/L in chest cavity blood, 21.2 mg/L in vitreous, 11.7 mg/kg in brain, 27.9 mg/kg in liver, 71.0 mg/L in urine, and 51.8 mg/total gastric contents. The presence of DFE was confirmed in the decedent's urine by injection on an Agilent 6890/5973 GC-mass spectrometer in full scan mode. This case presents a uniquely witnessed observation of the apparent impairing effects and consequences of the acute inhalation of halogenated hydrocarbons such as DFE and the operation of a motor vehicle. The proximity of time of death to inhalant use may also provide insight to postmortem distribution patterns of DFE in relation to normal physiologic blood flow. With further investigations, estimating the time of final use of an inhalant prior to death may be deciphered from such patterns, although a degree of caution should be applied in deaths resulting from severe trauma in which normal tissue structure is compromised because postmortem redistribution may result.
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Study of CNG/diesel dual fuel engine's emissions by means of RBF neural network.
Liu, Zhen-tao; Fei, Shao-mei
2004-08-01
Great efforts have been made to resolve the serious environmental pollution and inevitable declining of energy resources. A review of Chinese fuel reserves and engine technology showed that compressed natural gas (CNG)/diesel dual fuel engine (DFE) was one of the best solutions for the above problems at present. In order to study and improve the emission performance of CNG/diesel DFE, an emission model for DFE based on radial basis function (RBF) neural network was developed which was a black-box input-output training data model not require priori knowledge. The RBF centers and the connected weights could be selected automatically according to the distribution of the training data in input-output space and the given approximating error. Studies showed that the predicted results accorded well with the experimental data over a large range of operating conditions from low load to high load. The developed emissions model based on the RBF neural network could be used to successfully predict and optimize the emissions performance of DFE. And the effect of the DFEmain performance parameters, such as rotation speed, load, pilot quantity and injection timing, were also predicted by means of this model. In resumé, an emission prediction model for CNG/diesel DFE based on RBF neural network was built for analyzing the effect of the main performance parameters on the CO, NOx, emissions of DFE. The predicted results agreed quite well with the traditional emissions model, which indicated that the model had certain application value, although it still has some limitations, because of its high dependence on the quantity of the experimental sample data.
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New method for the direct determination of dissolved Fe(III) concentration in acid mine waters
To, T.B.; Nordstrom, D. Kirk; Cunningham, K.M.; Ball, J.W.; McCleskey, R. Blaine
1999-01-01
A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) >> Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), AI(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 ??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II)???Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2/??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.
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Uranium chloride extraction of transuranium elements from LWR fuel
Miller, W.E.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Pierce, R.D.
1992-08-25
A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800 C to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein. 1 figure.
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Uranium chloride extraction of transuranium elements from LWR fuel
Miller, William E.; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Pierce, R. Dean
1992-01-01
A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800.degree. C. to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein.
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Sokolowski, A; Wolowicz, M; Hummel, H
2001-10-01
Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.
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Shulkin, Vladimir; Zhang, Jing
2014-11-15
This paper compares the distributions of dissolved and particulate forms of Mn, Fe, Ni, Cu, Zn, Cd, and Pb in the estuaries of the largest rivers in East Asia: the Amur River and the Changjiang (Yangtze River). High suspended solid concentrations, elevated pH, and relatively low dissolved trace metal concentrations are characteristics of the Changjiang. Elevated dissolved Fe and Mn concentrations, neutral pH, and relatively low suspended solid concentrations are characteristics of the Amur River. The transfer of dissolved Fe to suspended forms is typical in the Amur River estuary, though Cd and Mn tend to mobilize to solution, and Cu and Ni are diluted in the estuarine system. Metal concentrations in suspended matter in the Amur River estuary are controlled by the ratio of terrigenous riverine material, enriched in Al and Fe, and marine biogenic particles, enriched in Cu, Mn, Cd, and in some cases Ni. The increase in dissolved forms of Mn, Fe, Ni, Cu, Cd, and Pb compared with river end-member is unique to the Changjiang estuary. Particle-solution interactions are not reflected in bulk suspended-solid metal concentrations in the Changjiang estuary due to the dominance of particulate forms of these metals. Cd is an exception in the Changjiang estuary, where the increase in dissolved Cd is of comparable magnitude to the decrease in particulate Cd. Despite runoff in the Amur River being lower than that in the Changjiang, the fluxes of dissolved Mn, Zn and Fe in the Amur River exceed those in the Changjiang. Dissolved Ni, and Cd fluxes are near equal in both estuaries, but dissolved Cu is lower in the Amur River estuary. The hydrological and physico-chemical river characteristics are dominated at the assessment of river influence on the adjoining coastal sea areas despite differences in estuarine processes. Copyright © 2014 Elsevier B.V. All rights reserved.
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Reactive Iron Delivery to the Central Gulf of Alaska via Two Mesoscale Eddies (Invited)
NASA Astrophysics Data System (ADS)
Lippiatt, S. M.; Brown, M. T.; Lohan, M. C.; Bruland, K. W.
2010-12-01
Coastal waters in the northern Gulf of Alaska (GoA) are considered Fe-rich and nitrate-poor, in contrast to the Fe-poor, high-nitrate, low chlorophyll (HNLC) waters of the central GoA. Mixing between these two regimes can lead to enhanced primary productivity. Mesoscale anticyclonic eddies are an important mechanism for cross-shelf exchange of coastal and HNLC waters. This presentation will discuss findings from a cruise in the GoA during late summer 2007, namely dissolved Fe, leachable particulate Fe (defined as the portion of the particulate Fe that is solubilized with a two hour, 25% acetic acid leach with a short heating step and a reducing agent), and nitrate. Leachable particulate Fe concentrations in coastal surface waters between Yakutat, AK and the Kenai Peninsula ranged from over 1 uM in the Alsek River plume to less than 5 nM at the base of Cook Inlet, and were more variable and at least an order of magnitude higher than dissolved Fe concentrations. Relatively low and consistent dissolved Fe (~2 nM) suggests that the system’s ability to solubilize this large concentration of leachable particulate Fe is overwhelmed by the massive input of glacial-derived particulate Fe. Suspended leachable particulate Fe is available for exchange to the dissolved phase and is suggested to maintain a relatively constant 2 nM concentration of dissolved Fe in the coastal GoA. Glacial meltwaters were not a significant source of nitrate compared to central GoA HNLC or upwelled waters. The work completed in the coastal GoA set the stage for assessing the delivery of this glacial-derived coastal Fe to HNLC waters via mesoscale eddies. Two mesoscale eddies were sampled during this study: a Sitka eddy located off Yakutat, Alaska and a Kenai eddy sampled off the shelf break near Kodiak Island. The temperature and salinity structures of the eddies reflected their coastal origin; core waters were warmer and fresher than surrounding basin waters, coincident with elevated dissolved and leachable particulate Fe. In the core of the Yakutat eddy at 50 - 100 m depth there was on average 0.8 nM reactive Fe (dissolved + leachable particulate Fe), approximately five times more reactive Fe compared to adjacent GoA basin waters (0.16 nM). At the same depths in the core of the Kenai eddy there was on average 1.9 nM reactive Fe, ten times more reactive Fe than the basin waters (0.19 nM). In addition, for a given density, core waters had elevated nitrate and silicate compared to outside the eddy. Storms can mix Fe-enriched eddy core waters to the surface. Furthermore, anticyclonic GoA eddies can be a significant source of Fe to HNLC waters when they propagate into the central GoA and eventually relax with the Fe and nutrient rich subsurface waters rebounding or upwelling towards the surface. The transport of coastal waters into central GoA waters via mesoscale eddies is shown to be an important mechanism for Fe delivery into this HNLC region.
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Monitoring propranolol treatment in periocular infantile haemangioma.
Burne, R; Taylor, R
2014-11-01
To develop a tool for assessing amblyopic risk and monitoring the treatment effect of propranolol in periocular haemangioma management. We present a study of nine children with periocular haemangioma who underwent propranolol treatment at York Hospital between 2009 and 2013.A proposed measure of amblyogenic risk based on the induced anisometropia resulting from a periocular haemangioma was calculated in the form of a single quantitative value, measured in dioptres. This calculation used published work and developed it to produce a new function, termed the delta defocus equivalent (DFE-∂).Refraction measurements were retrospectively collected from patients' notes in order to measure the trend of DFE-∂ over the treatment period with propranolol. The average DFE-∂ at commencement of propranolol was 1.54 (±0.62) D. The average at the end of treatment was 0.39 (±0.38) D. This work presents a possible tool for assessing amblyopic risk in cases of periocular infantile haemangioma. The DFE-∂ gives a measure in dioptres, which may represent the true amblyopic risk, and so be useful in supporting treatment decisions in paediatric ophthalmology.
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Uptake and distribution of the abused inhalant 1,1-difluoroethane in the rat.
Avella, Joseph; Kunaparaju, Naveen; Kumar, Sunil; Lehrer, Michael; Zito, S William; Barletta, Michael
2010-09-01
1,1-Difluoroethane (DFE) is a halogenated hydrocarbon used as a propellant in products designed for dusting electronic equipment and air brush painting. When abused, inhaled DFE produces intoxication and loss of muscular coordination. To investigate DFE toxicokinetics, groups (n = 3) of Sprague-Dawley rats were exposed to 30 s of 20 L/min DFE. The experimental model was designed to mimic exposure during abuse, a protocol which has not been conducted. Tissue collection (blood, brain, heart, liver, and kidney) occurred at 0, 10, 20, 30, 45, 60, 120, 240, 480, and 900 s. Average peak DFE levels were blood 352, brain 519, heart 338, liver 187, and kidney 364 mg/L or mg/kg. The total percent uptake of the administered dose was 4.0%. Uptake into individual compartments was 2.72, 0.38, 0.15, 0.41, and 0.32% for blood, brain, heart, liver, and kidney, respectively. All animals showed signs of intoxication within 20 s manifested as lethargy, prostration and loss of righting reflex. Marked intoxication continued for about 4 min when DFE averaged 21 mg/L in blood and 17 mg/kg in brain. Between 4 and 8 min, animals continued to show signs of sedation as evidenced by reduced aggression and excitement during handling. No discernable intoxication was evident after 8 min and blood and brain levels had fallen to 10 and 6 mg/L or kg, respectively. Plots of concentration (log) versus time were consistent with a two compartment model. Initial distribution was rapid with average half life (t((1/2))) during the alpha phase of 9 s for blood, 18 s for brain and 27 s in cardiac tissue. During beta slope elimination average t((1/2)) was 86 s in blood, 110 s in brain and 168 s in heart. Late elimination half lives were longer with blood gamma = 240 s, brain gamma = 340 s, and heart gamma = 231 s. Following acute exposure the Vd = 0.06 L, beta = 0.48 min(-1), AUC = 409.8 mg.min L(-1), and CL from blood was 0.03 L min(-1). The calculated toxicokinetic data may underestimate these parameters if DFE is abused chronically due to continued uptake into lowly perfused tissues with repeated dosing.
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NASA Astrophysics Data System (ADS)
Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick
2015-02-01
The present study investigated the weathering and transport mechanisms of Fe in the Amazon River. A particular emphasis was placed on Fe partitioning, speciation, and isotopic fractionation in the contrasting waters of the Solimões and Negro rivers and their mixing zone at the beginning of the Amazon River. Samples collected in the end-member rivers and thirteen sites distributed throughout the mixing zone were processed through frontal vacuum filtration and tangential-flow ultrafiltration to separate the different suspended solid fractions, i.e., particulate (P > 0.45 μm and P > 0.22 μm), colloidal (0.22 μm > C > 5 kDa) and truly dissolved elements (TD < 5 kDa). The Fe isotopic composition and electron paramagnetic resonance (EPR) species were measured on these different pore-sized fractions. The acidic and organo-Fe-rich waters of the Negro River displayed dissolved and colloidal fractions enriched in heavy isotopes (∼1.2‰, in δ57Fe values relative to IRMM-14), while the particulate fractions yielded light isotopic compositions of -0.344‰ for P > 0.22 μm and -0.104‰ for P > 0.45 μm fractions). The mineral particulate-rich waters of the Solimões River had dissolved and colloidal fractions with light isotopic composition (-0.532‰ and -0.176‰, respectively), whereas the particulate fractions yielded δ57Fe values close to those of the continental crust (i.e., -0.029‰ for P > 0.22 μm and 0.028‰ for P > 0.45 μm). Ten kilometers downstream from the Negro and Solimões junction, the concentrations of colloidal and dissolved Fe species deviate markedly from conservative mixing. A maximum Fe loss of 43 μg/L (i.e., 50% of the dissolved and colloidal Fe) is observed 110 km downstream from the rivers junction. The contrasting Negro and Solimões Rivers isotopic compositions along the pore-sized water fractions is attributable to the biogeochemical processes involving different types of upland soils and parental materials. For instance, the isotopic composition of colloidal and dissolved Fe from the Negro River are consistent with Fe oxidation and complexation mechanisms at the interface between waterlogged podzols and river networks, as supported by strong organo-Fe complexes signals observed by EPR. Conversely, the particulate and colloidal fractions from the Solimões River have δ57Fe consistent with strong mechanical erosion in the Andean Cordillera and upland soils, as evidenced by high concentrations of Fe3+-oxides sensu lato measured by EPR. The massive dissolved and colloidal Fe removal is associated with the evolution of the physical and chemical composition of the waters (i.e., ionic strength) during mixing, which influences organo-Fe3+ and Fe3+-oxyhydroxides stability. Several models are discussed to explain Fe non-conservative behavior, including dissociation of organo-Fe complexes and the subsequent formation of solid Fe3+-oxyhydroxides and semiquinone free radicals, as evidenced by EPR spectra demonstrating that organo-Fe signals decrease as Fe3+-oxyhydroxides and free radicals signals increase. As in estuarine regions, the mechanisms involving Fe transfer and loss in the mixing zone has a negligible effect on the bulk water Fe isotopic composition. This result suggests that a tropical basin similar to the Amazon River Basin delivers to the ocean waters with an Fe isotopic composition similar to that of the Earth's continental crust.
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NASA Astrophysics Data System (ADS)
Twining, B. S.; Jacquot, J. E.; Rauschenberg, S.; Enright, J.; Marchetti, A.; Cohen, N.; Brown, M.; Parker, C.; Bruland, K. W.
2016-02-01
Iron is a critical micronutrient that controls primary production in large swaths of the global ocean. Experiments with laboratory cultures indicate that phytoplankton differ in their ability to compete for and store Fe in response to varying ambient Fe concentrations. However there are very few measurements of the physiological responses of natural phytoplankton populations to gradients in Fe availability. Incubation experiments were conducted off the coast of California and Oregon at two sites characterized by a 10-fold difference in dissolved Fe (0.3 and 3 nM). In each experiment, incubation water was amended with either dissolved Fe (5-10 nM), the model siderophore desferrioxamine B (DFB; 200 nM), or left unamended. Iron contents of three abundant diatom groups (Chaetoceros sp. and large and small pennate diatoms) were monitored by synchrotron X-ray fluorescence, along with dissolved and bulk particulate trace metals and macronutrients over the course of 3 days. Transcriptomic samples were also collected at daily timepoints to assess molecular responses. Added dissolved Fe was drawn down in both experiments, while DFB appeared to solubilize a fraction of ambient particulate Fe in the high-Fe experiment. Iron quotas of unamended diatoms were nearly 10-fold higher under high-Fe conditions. Quotas increased in response to added Fe in both experiments, but the magnitude of changes varied between diatom taxa. DFB additions resulted in reduced Fe quotas in the low-Fe incubation, since cells were presumably forced to use internal Fe stores to support growth. These data demonstrate significant plasticity in the abilities of phytoplankton to take advantage of changing micronutrient inputs. Quota data will be compared to transcript abundance data to ascertain mechanisms of Fe quota maintenance.
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Federal Register 2010, 2011, 2012, 2013, 2014
2012-03-21
... designed to be delivered to staff at the SCA/DFE sites. The key elements from the ICMS approach that are... to design an MET approach appropriate for the SCA/DFE intervention which may differ from the... approaches, techniques, or design aspects proposed that will enhance the project? Organizational (35%) Does...
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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).
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The geochemical cycling of trace elements in a biogenic meromictic lake
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.
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Weingarten, Evan; Chen, Qijia; McAdams, Maxwell; Yi, Jessica; Hepler, Justin; Albarracin, Dolores
2016-01-01
This paper presents a summary of the conclusions drawn from a meta-analysis of the behavioral impact of presenting words connected to an action or a goal representation (Weingarten et al., 2016). The average and distribution of 352 effect sizes from 133 studies (84 reports) revealed a small behavioral priming effect (dFE = 0.332, dRE= 0.352), which was robust across methodological procedures and only minimally biased by the publication of positive (vs. negative) results. More valued behavior or goal concepts (e.g., associated with important outcomes or values) were associated with stronger priming effects than were less valued behaviors. In addition, opportunities for goal satisfaction appeared to decrease priming effects. PMID:27957520
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NASA Astrophysics Data System (ADS)
Sanders, Christian J.; Santos, Isaac R.; Barcellos, Renato; Silva Filho, Emmanoel V.
2012-07-01
Groundwater underlying a mangrove habitat was studied to determine the geochemical nature of Ba, Fe and Mn as related to dissolved organic carbon (DOC), SO4 and salinity (Sepetiba Bay, Brazil). Wells were placed across geobotanic facies and sampled monthly for a year. We observed non-conservative behavior and elevated concentrations of dissolved metals relative to local end-members (i.e., fresh river water and seawater). Average Ba concentrations were near 2000 nM in an area with low salinity (˜5.3). Dissolved Fe (up to 654 μM) was two orders of magnitude greater in fresh groundwater than in the seaward sampling stations. Manganese concentrations were greatest (112 μM) in the high salinity (˜65) zone, being directly influenced by salinity. Groundwater Ba, Fe and Mn showed differing site specific concentrations, likely related to ion exchange processes and redox-controlled cycling along distinct mangrove facies. The results of this work show that metal concentrations are altered relative to conservative mixing between terrestrial and marine endmembers, illustrating the importance of mangrove subterranean estuaries as biogeochemical reactors. Roughly-estimated submarine groundwater discharge-derived dissolved Ba, Fe and Mn fluxes were at least one order of magnitude greater than river-derived fluxes into Sepetiba Bay.
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NASA Astrophysics Data System (ADS)
Rivaro, Paola; Luisa Abelmoschi, Maria; Grotti, Marco; Ianni, Carmela; Magi, Emanuele; Margiotta, Francesca; Massolo, Serena; Saggiomo, Vincenzo
2012-04-01
Surface water (<100 m) samples were collected from the Terra Nova Bay polynya region of the Ross Sea (Antarctica) in January 2006, with the aim of evaluating the individual and combined effects of hydrographic structure, iron and copper concentration and availability on the phytoplankton growth. The measurements were conducted within the framework of the Climatic Long Term Interaction for the Mass-balance in Antarctica (CLIMA) Project of the Programma Nazionale di Ricerca in Antartide activities. Dissolved oxygen, nutrients, phytoplankton pigments and concentration and complexation of dissolved trace metals were determined. Experimental data were elaborated by Principal Component Analysis (PCA). As a result of solar heating and freshwater inputs from melting sea-ice, the water column was strongly stratified with an Upper Mixed Layer 4-16 m deep. The integrated Chl a in the layer 0-100 m ranged from 60 mg m-2 to 235 mg m-2, with a mean value of 138 mg m-2. The pigment analysis showed that diatoms dominated the phytoplankton assemblage. Major nutrients were generally high, with the lowest concentration at the surface and they were never fully depleted. The Si:N drawdown ratio was close to the expected value of 1 for Fe-replete diatoms. We evaluated both the total and the labile dissolved fraction of Fe and Cu. The labile fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The total dissolved Fe ranged from 0.48 to 3.02 nM, while the total dissolved Cu from 3.68 to 6.84 nM. The dissolved labile Fe ranged from below the detection limit (0.15 nM) to 1.22 nM, and the dissolved labile Cu from 0.31 to 1.59 nM, respectively. The labile fractions measured at 20 m were significantly lower than values in 40-100 m samples. As two stations were re-sampled 5 days later, we evaluated the short-term variability of the physical and biogeochemical properties. In particular, in a re-sampled station at 20 m, the total dissolved Fe increased and the total dissolved Cu decreased, while their labile fraction was relatively steady. As a result of the increase in total Fe, the percentage of the labile Fe decreased. An increase of the Si:N, Si:P and Si:FUCO ratios was measured also in the re-sampled station. On this basis, we speculated that a switch from a Fe-replete to a Fe-deplete condition was occurring.
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Majumder, Santanu; Nath, Bibhash; Sarkar, Simita; Chatterjee, Debashis; Roman-Ross, Gabriela; Hidalgo, Manuela
2014-01-15
Dissolved organic carbon (DOC) and Fe mineral phases are known to influence the mobility of arsenic (As) in groundwater. Arsenic can be associated with colloidal particles containing organic matter and Fe. Currently, no data is available on the dissolved phase/colloidal association of As in groundwater of alluvial aquifers in West Bengal, India. This study investigated the fractional distribution of As (and other metals/metalloids) among the particulate, colloidal and dissolved phases in groundwater to decipher controlling behavior of organic and inorganic colloids on As mobility. The result shows that 83-94% of As remained in the 'truly dissolved' phases (i.e., <0.05 μm size). Strong positive correlation between Fe and As (r(2) between 0.65 and 0.94) is mainly observed in the larger (i.e., >0.05 μm size) colloidal particles, which indicates the close association of As with larger Fe-rich inorganic colloids. In smaller (i.e., <0.05 μm size) colloidal particles strong positive correlation is observed between As and DOC (r(2)=0.85), which highlights the close association of As with smaller organic colloids. As(III) is mainly associated with larger inorganic colloids, whereas, As(V) is associated with smaller organic/organometallic colloids. Scanning Electron Microscopy and Energy Dispersive X-ray spectroscopy confirm the association of As with DOC and Fe mineral phases suggesting the formation of dissolved organo-Fe complexes and colloidal organo-Fe oxide phases. Attenuated total reflectance-Fourier transform infrared spectroscopy further confirms the formation of As-Fe-NOM organometallic colloids, however, a detailed study of these types of colloids in natural waters is necessary to underpin their controlling behavior. © 2013 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Rapp, I.; Schlosser, C.; Gledhill, M.; Achterberg, E. P.
2016-02-01
Fe availability in surface waters determines primary production, N2 fixation and microbial community structure and thus plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling areas with oxygen minimum zones, such as the Mauritanian shelf region, are typically associated with elevated Fe concentrations with shelf sediments as key source of Fe to bottom and surface waters. The magnitude of vertical and horizontal Fe fluxes from shelf sediments to onshore and offshore surface waters are not well constrained and there are still large uncertainties concerning the stabilisation of Fe once released from sediments into suboxic and oxic waters. Supportive data of other trace metals can be used as an indicator of sediment release, scavenging processes and biological utilisation. Here we present soluble (<0.02 µm), dissolved (<0.2 µm) and total dissolvable (unfiltered) trace metal data collected at 10 stations on a 90 nautical mile transect across the Mauritanian shelf region in June 2014 (cruise Meteor 107). The samples were pre-concentrated using an automated off-line pre-concentration device and analysed simultaneously for Cd, Pb, Fe, Ni, Cu, Zn, Mn and Co using a high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). First results indicate the importance of benthic sources to the overall Fe budget in this region. Both dissolved Fe and Mn showed enhanced concentrations close to the shelf at depths between 40 and 180 m corresponding with low oxygen concentrations (<50 µmol L-1). Elevated soluble, dissolved, and total dissolvable Fe and Mn concentrations at an offshore station coincided with the location of a cyclonic Eddie that was characterised by an oxygen depleted water body. To further assess the accuracy of vertical and horizontal fluxes of Fe and other trace metals, we compare diffusivity estimates determined by a microstructure profiler and the scale length method (de Jong et al. 2012) with observed isotopic Ra data.
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Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers
Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Snyder, D.M.; McCleskey, R. Blaine; Amils, R.; Poulson, S.R.
2008-01-01
A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Ri??o Tinto, Ri??o Odiel, and Ri??o Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66????M at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3??nmol L- 1 s- 1) and maximum rates of Fe(III) photoreduction (1.7 to 4.3??nmol L- 1 s- 1). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Ri??o Tinto in about 30??days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans. Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research. ?? 2008 Elsevier B.V. All rights reserved.
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In-situ arsenic remediation by aquifer iron coating: Field trial in the Datong basin, China
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xie, Xianjun; Pi, Kunfu; Liu, Yaqing
2016-01-01
In situ As removal from groundwater used for water supply has been performed in Daying village of Shanyin County where mild alkaline groundwater contains high dissolved As concentration. The objective of this study was to evaluate in situ As treatment by aquifer Fe coating technology. The groundwater in the studied aquifer contains As dominated by aqueous As(III) and low dissolved Fe(II) concentration, which are unfavorable conditions for forming Fe-oxides/hydroxides for As removal. In addition, high As(III) concentration limits As adsorption onto Fe-oxides/hydroxides. Accordingly, dissolved Fe(II) (5mM) and NaClO (5mM) were injected into the studied aquifer to form Fe-oxides/hydroxides and oxidizemore » As(III) to As(V), creating favorable conditions for As removal via adsorption and/or co-precipitation. During alternatively cycled injection of Fe(II) and NaClO, the As concentration in groundwater from the pumping well significantly decreased to below drinking water standard. The developed approach can be applied similarly in many parts of the world containing high As concentrations.« less
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Schroth, A.W.; Crusius, John; Chever, F.; Bostick, B.C.; Rouxel, O.J.
2011-01-01
Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.
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A normative inference approach for optimal sample sizes in decisions from experience
Ostwald, Dirk; Starke, Ludger; Hertwig, Ralph
2015-01-01
“Decisions from experience” (DFE) refers to a body of work that emerged in research on behavioral decision making over the last decade. One of the major experimental paradigms employed to study experience-based choice is the “sampling paradigm,” which serves as a model of decision making under limited knowledge about the statistical structure of the world. In this paradigm respondents are presented with two payoff distributions, which, in contrast to standard approaches in behavioral economics, are specified not in terms of explicit outcome-probability information, but by the opportunity to sample outcomes from each distribution without economic consequences. Participants are encouraged to explore the distributions until they feel confident enough to decide from which they would prefer to draw from in a final trial involving real monetary payoffs. One commonly employed measure to characterize the behavior of participants in the sampling paradigm is the sample size, that is, the number of outcome draws which participants choose to obtain from each distribution prior to terminating sampling. A natural question that arises in this context concerns the “optimal” sample size, which could be used as a normative benchmark to evaluate human sampling behavior in DFE. In this theoretical study, we relate the DFE sampling paradigm to the classical statistical decision theoretic literature and, under a probabilistic inference assumption, evaluate optimal sample sizes for DFE. In our treatment we go beyond analytically established results by showing how the classical statistical decision theoretic framework can be used to derive optimal sample sizes under arbitrary, but numerically evaluable, constraints. Finally, we critically evaluate the value of deriving optimal sample sizes under this framework as testable predictions for the experimental study of sampling behavior in DFE. PMID:26441720
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Nitroaromatic pesticides (NAPs) are hydrophobic contaminants that can accumulate in sediments by the deposition of suspended solids from surface waters. Fe(II) and dissolved organic matter (DOM), present in suboxic and anoxic zones of freshwater sediments, can transform NAPs in n...
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Han, Shuping; Naito, Wataru; Masunaga, Shigeki
To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron.
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In situ arsenic removal in an alkaline clastic aquifer
Welch, A.H.; Stollenwerk, K.G.; Paul, A.P.; Maurer, D.K.; Halford, K.J.
2008-01-01
In situ removal of As from ground water used for water supply has been accomplished elsewhere in circum-neutral ground water containing high dissolved Fe(II) concentrations. The objective of this study was to evaluate in situ As ground-water treatment approaches in alkaline ground-water (pH > 8) that contains low dissolved Fe (
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Thorium distributions in high- and low-dust regions and the significance for iron supply
NASA Astrophysics Data System (ADS)
Hayes, Christopher T.; Rosen, Jeffrey; McGee, David; Boyle, Edward A.
2017-02-01
Thorium and uranium isotopes (232Th, 230Th, 238U, and 234U) were investigated to refine their use for estimating mineral dust deposition and Fe delivery to the ocean. U concentrations and isotope ratios were consistent with conservative behavior and can safely be described using published U-salinity relationships and global average seawater isotopic composition. Near Barbados, waters affected by the Amazon outflow contained elevated 232Th. This signals one region where the thorium-dust method is inaccurate because of a confounding continental input. Dissolved 232Th fluxes in this region suggest that Amazonian Fe supply to the adjacent open ocean is much larger than local atmospheric deposition. The colloidal content of dissolved Th south of Bermuda was found to be quite small (2-6%), similar to that found north of Hawaii, despite the order of magnitude higher dust deposition in the Atlantic. This finding supports the assumption that dissolved 232Th and 230Th are scavenged at the same rate despite their different sources and also sheds light on the increase of dissolved 232Th fluxes with integrated depth. Outside the region influenced by Amazon River waters, dissolved 232Th fluxes are compared with Bermudan aerosol Fe deposition to estimate that fractional Th solubility is around 20% in this region. Finally, new dissolved and soluble Fe, Mn, and Cr data from the subtropical North Pacific support the idea that Fe concentrations in the remote ocean are highly buffered, whereas 232Th has a larger dynamic range between high- and low-dust regions.
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ERIC Educational Resources Information Center
Black, Alison; Costello, Rebecca; Craft, Anna; Katene, Will
2015-01-01
Between 2011 and 2013, the Department for Education (DfE) in England made £3.3 million available to support the development of opportunities for young disabled people to access high-quality physical education and school sport. The DfE with the Youth Sport Trust (YST) developed a range of initiatives to help meet this aim, including Project…
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Evaluation of Fe(II) oxidation at an acid mine drainage site using laboratory-scale reactors
NASA Astrophysics Data System (ADS)
Brown, Juliana; Burgos, William
2010-05-01
Acid mine drainage (AMD) is a severe environmental threat to the Appalachian region of the Eastern United States. The Susquehanna and Potomac River basins of Pennsylvania drain to the Chesapeake Bay, which is heavily polluted by acidity and metals from AMD. This study attempted to unravel the complex relationships between AMD geochemistry, microbial communities, hydrodynamic conditions, and the mineral precipitates for low-pH Fe mounds formed downstream of deep mine discharges, such as Lower Red Eyes in Somerset County, PA, USA. This site is contaminated with high concentrations of Fe (550 mg/L), Mn (115 mg/L), and other trace metals. At the site 95% of dissolved Fe(II) and 56% of total dissolved Fe is removed without treatment, across the mound, but there is no change in the concentration of trace metals. Fe(III) oxides were collected across the Red Eyes Fe mound and precipitates were analyzed by X-ray diffraction, electron microscopy and elemental analysis. Schwertmannite was the dominant mineral phase with traces of goethite. The precipitates also contained minor amounts of Al2O3, MgO,and P2O5. Laboratory flow-through reactors were constructed to quantify Fe(II) oxidation and Fe removal over time at terrace and pool depositional facies. Conditions such as residence time, number of reactors in sequence and water column height were varied to determine optimal conditions for Fe removal. Reactors with sediments collected from an upstream terrace oxidized more than 50% of dissolved Fe(II) at a ten hour residence time, while upstream pool sediments only oxidized 40% of dissolved Fe(II). Downstream terrace and pool sediments were only capable of oxidizing 25% and 20% of Fe(II), respectively. Fe(II) oxidation rates measured in the reactors were determined to be between 3.99 x 10-8and 1.94 x 10-7mol L-1s-1. The sediments were not as efficient for total dissolved Fe removal and only 25% was removed under optimal conditions. The removal efficiency for all sediments decreased as residence time decreased and as water column depth increased. Control reactors with Co-60 irradiated sediments showed an increase in Fe concentration as a result of dissolution of the sediments; thus, it was concluded that Fe(II) oxidation in the reactors was a result of biological processes and not abiotic oxidation. It was also concluded that Fe(II) oxidation and removal rates were dependent upon geochemical gradients (pH, Fe(II) concentration) rather than depositional facies. Fluorescent in situ hybridization was also performed on field and reactor samples to determine which microbial communities were responsible for the highest Fe(II) oxidation rates.
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Toward a coherent model for the melting behavior of the deep Earth's mantle
NASA Astrophysics Data System (ADS)
Andrault, D.; Bolfan-Casanova, N.; Bouhifd, M. A.; Boujibar, A.; Garbarino, G.; Manthilake, G.; Mezouar, M.; Monteux, J.; Parisiades, P.; Pesce, G.
2017-04-01
Knowledge of melting properties is critical to predict the nature and the fate of melts produced in the deep mantle. Early in the Earth's history, melting properties controlled the magma ocean crystallization, which potentially induced chemical segregation in distinct reservoirs. Today, partial melting most probably occurs in the lowermost mantle as well as at mid upper-mantle depths, which control important aspects of mantle dynamics, including some types of volcanism. Unfortunately, despite major experimental and theoretical efforts, major controversies remain about several aspects of mantle melting. For example, the liquidus of the mantle was reported (for peridotitic or chondritic-type composition) with a temperature difference of ∼1000 K at high mantle depths. Also, the Fe partitioning coefficient (DFeBg/melt) between bridgmanite (Bg, the major lower mantle mineral) and a melt was reported between ∼0.1 and ∼0.5, for a mantle depth of ∼2000 km. Until now, these uncertainties had prevented the construction of a coherent picture of the melting behavior of the deep mantle. In this article, we perform a critical review of previous works and develop a coherent, semi-quantitative, model. We first address the melting curve of Bg with the help of original experimental measurements, which yields a constraint on the volume change upon melting (ΔVm). Secondly, we apply a basic thermodynamical approach to discuss the melting behavior of mineralogical assemblages made of fractions of Bg, CaSiO3-perovskite and (Mg,Fe)O-ferropericlase. Our analysis yields quantitative constraints on the SiO2-content in the pseudo-eutectic melt and the degree of partial melting (F) as a function of pressure, temperature and mantle composition; For examples, we find that F could be more than 40% at the solidus temperature, except if the presence of volatile elements induces incipient melting. We then discuss the melt buoyancy in a partial molten lower mantle as a function of pressure, F and DFeBg/melt. In the lower mantle, density inversions (i.e. sinking melts) appear to be restricted to low F values and highest mantle pressures. The coherent melting model has direct geophysical implications: (i) in the early Earth, the magma ocean crystallization could not occur for a core temperature higher than ∼5400 K at the core-mantle boundary (CMB). This temperature corresponds to the melting of pure Bg at 135 GPa. For a mantle composition more realistic than pure Bg, the right CMB temperature for magma ocean crystallization could have been as low as ∼4400 K. (ii) There are converging arguments for the formation of a relatively homogeneous mantle after magma ocean crystallization. In particular, we predict the bulk crystallization of a relatively large mantle fraction, when the temperature becomes lower than the pseudo-eutectic temperature. Some chemical segregation could still be possible as a result of some Bg segregation in the lowermost mantle during the first stage of the magma ocean crystallization, and due to a much later descent of very low F, Fe-enriched, melts toward the CMB. (iii) The descent of such melts could still take place today. There formation should to be related to incipient mantle melting due to the presence of volatile elements. Even though, these melts can only be denser than the mantle (at high mantle depths) if the controversial value of DFeBg/melt is indeed as low as suggested by some experimental studies. This type of melts could contribute to produce ultra-low seismic velocity anomalies in the lowermost mantle.
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Evolution of the chemistry of Fe bearing waters during CO2 degassing
Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.
2012-01-01
The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.
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Baalousha, Mohamed; Stoll, Serge; Motelica-Heino, Mikaël; Guigues, Nathalie; Braibant, Gilles; Huneau, Frédéric; Le Coustumer, Philippe
2018-02-10
This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (< 10 nm), colloidal (10-450 nm) and particulate (> 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.
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Coupled cycling of Fe and organic carbon in submarine hydrothermal systems: Modelling approach
NASA Astrophysics Data System (ADS)
Legendre, Louis; German, Christopher R.; Sander, Sylvia G.; Niquil, Nathalie
2014-05-01
It has been recently proposed that hydrothermal plumes may be a significant source of dissolved Fe to the oceans. In order to assess this proposal, we investigated the fate of dissolved Fe released from hydrothermal systems to the overlying ocean using an approach that combined modelling and field values. We based our work on a consensus conceptual model developed by members of SCOR-InterRidge Working Group 135. The model was both complex enough to capture the main processes of dissolved Fe released from hydrothermal systems and chemical transformation in the hydrothermal plume, and simple enough to be parameterized with existing field data. It included the following flows: Fe, water and heat in the high temperature vent fluids, in the fluids diffusing around the vent, and in the entrained seawater in the buoyant plume; Fe precipitation in polymetallic sulphides near the vent; transport of Fe in the non-buoyant plume, and both its precipitation in particles onto the sea bottom away from the vent and dissolution into deep-sea waters. In other words, there were three Fe input flows into the buoyant hydrothermal plume (vent-fluids; entrained diffuse flow; entrained seawater) and three Fe output flows (sedimentation from the buoyant plume as polymetallic sulfides; sedimentation from the non-buoyant plume in particulate form; export to the deep ocean in dissolved or nanoparticulate form). The output flows balanced the input flows. We transformed the conceptual model into equations, and parameterized these with field data. To do so, we assumed that all hydrothermal systems, globally, can be represented by the circumstances that prevail at the EPR 9°50'N hydrothermal field, although we knew this assumption not to be accurate. We nevertheless achieved, by following this approach, two important goals, i.e. we could assemble into a coherent framework, for the first time, several discrete data sets acquired independently over decades of field work, and we could obtain model results that were consistent with recent field observations. We used our model to explore scenarios of Fe emissions and transformations under various constraints. The modelling exercises indicated that the provision of significant amounts of dissolved Fe to the oceans by hydrothermal plumes was consistent with realistic model parameters. This supported the proposition that hydrothermal systems play significant roles in the global biogeochemical Fe cycle.
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Thermally induced phase transformation in multi-phase iron oxide nanoparticles on vacuum annealing
NASA Astrophysics Data System (ADS)
Anupama, A. V.; Keune, W.; Sahoo, B.
2017-10-01
The evolution of magnetic phases in multi-phase iron oxide nanoparticles, synthesized via the transferred arc plasma induced gas phase condensation method, was investigated by X-ray diffraction, vibrating sample magnetometry and 57Fe Mössbauer spectroscopy. The particles are proposed to be consisting of three different iron oxide phases: α-Fe2O3, γ-Fe2O3 and Fe3O4. These nanoparticles were exposed to high temperature (∼935 K) under vacuum (10-3 mbar He pressure), and the thermally induced phase transformations were investigated. The Rietveld refinement of the X-ray diffraction data corroborates the least-squares fitting of the transmission Mössbauer spectra in confirming the presence of Fe3O4, γ-Fe2O3 and α-Fe2O3 phases before the thermal treatment, while only Fe3O4 and α-Fe2O3 phases exist after thermal treatment. On thermal annealing in vacuum, conversion from γ-Fe2O3 to Fe3O4 and α-Fe2O3 was observed. Interestingly, we have observed a phase transformation occurring in the temperature range ∼498 K-538 K, which is strikingly lower than the phase transformation temperature of γ-Fe2O3 to α-Fe2O3 (573-623 K) in air. Combining the results of Rietveld refinement of X-ray diffraction patterns and Mössbauer spectroscopy, we have attributed this phase transformation to the phase conversion of a metastable "defected and strained" d-Fe3O4 phase, present in the as-prepared sample, to the α-Fe2O3 phase. Stabilization of the phases by controlling the phase transformations during the use of different iron-oxide nanoparticles is the key factor to select them for a particular application. Our investigation provides insight into the effect of temperature and chemical nature of the environment, which are the primary factors governing the phase stability, suitability and longevity of the iron oxide nanomaterials prepared by the gas-phase condensation method for various applications.
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Nonlinear filter based decision feedback equalizer for optical communication systems.
Han, Xiaoqi; Cheng, Chi-Hao
2014-04-07
Nonlinear impairments in optical communication system have become a major concern of optical engineers. In this paper, we demonstrate that utilizing a nonlinear filter based Decision Feedback Equalizer (DFE) with error detection capability can deliver a better performance compared with the conventional linear filter based DFE. The proposed algorithms are tested in simulation using a coherent 100 Gb/sec 16-QAM optical communication system in a legacy optical network setting.
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Zhang, Guosong; Hovem, Jens M.; Dong, Hefeng
2012-01-01
Underwater communication channels are often complicated, and in particular multipath propagation may cause intersymbol interference (ISI). This paper addresses how to remove ISI, and evaluates the performance of three different receiver structures and their implementations. Using real data collected in a high-frequency (10–14 kHz) field experiment, the receiver structures are evaluated by off-line data processing. The three structures are multichannel decision feedback equalizer (DFE), passive time reversal receiver (passive-phase conjugation (PPC) with a single channel DFE), and the joint PPC with multichannel DFE. In sparse channels, dominant arrivals represent the channel information, and the matching pursuit (MP) algorithm which exploits the channel sparseness has been investigated for PPC processing. In the assessment, it is found that: (1) it is advantageous to obtain spatial gain using the adaptive multichannel combining scheme; and (2) the MP algorithm improves the performance of communications using PPC processing. PMID:22438755
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Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing
NASA Astrophysics Data System (ADS)
Shi, Z.; Bonneville, S.; Krom, M. D.; Carslaw, K. S.; Jickells, T. D.; Baker, A. R.; Benning, L. G.
2010-11-01
We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (<20 μm: PM20; <10 μm: PM10; and <2.5 μm: PM2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h-1 at pH=1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50-60 times and 3000-4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5-2%, 1-3% and 15-40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three phases, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe is solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.
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Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing
NASA Astrophysics Data System (ADS)
Shi, Z.; Bonneville, S.; Krom, M. D.; Carslaw, K. S.; Jickells, T. D.; Baker, A. R.; Benning, L. G.
2011-02-01
We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (<20 μm: PM20; <10 μm: PM10; and <2.5 μm: PM2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k (h-1) of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h-1 at pH = 1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50-60 times and 3000-4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5-2%, 1-3% and 15-40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three pools, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe may be solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.
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Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina
NASA Astrophysics Data System (ADS)
Parker, Stephen R.; Gammons, Christopher H.; Pedrozo, Fernando L.; Wood, Scott A.
2008-12-01
Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters. The results of this study of a naturally-acidic river are very similar to diel trends recently obtained from mining-impacted streams receiving acid rock drainage. The results are also used to explore the link between geochemistry and microbiology in acidic eco-systems. For example, Fe(III) photoreduction produces chemical potential energy (in the form of metastable Fe 2+) that helps support the bacterial community in this unique extreme environment.
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Cravotta,, Charles A.
1991-01-01
Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous solubility of O2 is not limiting, and oxidation of pyrite by O2 and Fe3+ accounts for most SO42- and Fe2+ observed in acidic ground water. However, in a system closed to O2, such as in the saturated zone, O2 solubility is limiting; hence, ferric oxidation of pyrite is a reasonable explanation for the observed elevated SO42- with increasing depth below the water table.
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Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface
NASA Astrophysics Data System (ADS)
van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype
2014-05-01
Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone, with Fe(II) oxidation taking place in the soil surrounding the ditch during summer and in the surface water during winter. The dynamics in Fe(II) oxidation did not affect the dissolved P concentrations. The dissolved P concentrations of the in-stream reservoirs water were an order of magnitude lower than observed in the groundwater and have no seasonal trend. Our data showed preferential binding of P during initial stage of the Fe(II) oxidation process, indicating the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at the groundwater-surface water interface is an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and therefore a major control on the P retention in natural waters that drain anaerobic aquifers.
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Trace element distributions in the water column near the Deepwater Horizon well blowout.
Joung, DongJoo; Shiller, Alan M
2013-03-05
To understand the impact of the Deepwater Horizon well blowout on dissolved trace element concentrations, samples were collected from areas around the oil rig explosion site during four cruises in early and late May 2010, October 2010, and October 2011. In surface waters, Ba, Fe, Cu, Ni, Mn, and Co were relatively well correlated with salinity during all cruises, suggesting mixing with river water was the main influence on metal distributions in these waters. However, in deep oil/gas plumes (1000-1400 m depth), modestly elevated concentrations of Co and Ba were observed in late May, compared with postblowout conditions. Analysis of the oil itself along with leaching experiments confirm the oil as the source of the Co, whereas increased Ba was likely due to drilling mud used in the top kill attempt. Deep plume dissolved Mn largely reflected natural benthic input, though some samples showed slight elevation probably associated with the top kill. Dissolved Fe concentrations were low and also appeared largely topographically controlled and reflective of benthic input. Estimates suggest that microbial Fe demand may have affected the Fe distribution but probably not to the extent of Fe becoming a growth-limiting factor. Experiments showed that the dispersant can have some limited impact on dissolved-particulate metal partitioning.
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Triggered Seismicity in Utah from the November 3, 2002, Denali Fault Earthquake
NASA Astrophysics Data System (ADS)
Pankow, K. L.; Nava, S. J.; Pechmann, J. C.; Arabasz, W. J.
2002-12-01
Coincident with the arrival of the surface waves from the November 3, 2002, Mw 7.9 Denali Fault, Alaska earthquake (DFE), the University of Utah Seismograph Stations (UUSS) regional seismic network detected a marked increase in seismicity along the Intermountain Seismic Belt (ISB) in central and north-central Utah. The number of earthquakes per day in Utah located automatically by the UUSS's Earthworm system in the week following the DFE was approximately double the long-term average during the preceding nine months. From these preliminary data, the increased seismicity appears to be characterized by small magnitude events (M = 3.2) and concentrated in five distinct spatial clusters within the ISB between 38.75°and 42.0° N. The first of these earthquakes was an M 2.2 event located ~20 km east of Salt Lake City, Utah, which occurred during the arrival of the Love waves from the DFE. The increase in Utah earthquake activity at the time of the arrival of the surface waves from the DFE suggests that these surface waves triggered earthquakes in Utah at distances of more than 3,000 km from the source. We estimated the peak dynamic shear stress caused by these surface waves from measurements of their peak vector velocities at 43 recording sites: 37 strong-motion stations of the Advanced National Seismic System and six broadband stations. (The records from six other broadband instruments in the region of interest were clipped.) The estimated peak stresses ranged from 1.2 bars to 3.5 bars with a mean of 2.3 bars, and generally occurred during the arrival of Love waves of ~15 sec period. These peak dynamic shear stress estimates are comparable to those obtained from recordings of the 1992 Mw 7.3 Landers, California, earthquake in regions where the Landers earthquake triggered increased seismicity. We plan to present more complete analyses of UUSS seismic network data, further testing our hypothesis that the DFE remotely triggered seismicity in Utah. This hypothesis is important to investigate because well-documented evidence for triggering of seismicity by distant earthquakes comes primarily from areas characterized by recent volcanic or geothermal activity. The regions of apparent triggered seismicity from the DFE in Utah fall into neither of these two categories.
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Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction
Landa, E.R.; Phillips, E.J.P.; Lovley, D.R.
1991-01-01
Uranium mill tailings were anaerobically incubated in the presence of H2 with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226Ra from uranium mill tailings. ?? 1991.
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Bernstein, Hans C; Beam, Jacob P; Kozubal, Mark A; Carlson, Ross P; Inskeep, William P
2013-08-01
The role of dissolved oxygen as a principal electron acceptor for microbial metabolism was investigated within Fe(III)-oxide microbial mats that form in acidic geothermal springs of Yellowstone National Park (USA). Specific goals of the study were to measure and model dissolved oxygen profiles within high-temperature (65-75°C) acidic (pH = 2.7-3.8) Fe(III)-oxide microbial mats, and correlate the abundance of aerobic, iron-oxidizing Metallosphaera yellowstonensis organisms and mRNA gene expression levels to Fe(II)-oxidizing habitats shown to consume oxygen. In situ oxygen microprofiles were obtained perpendicular to the direction of convective flow across the aqueous phase/Fe(III)-oxide microbial mat interface using oxygen microsensors. Dissolved oxygen concentrations dropped from ∼ 50-60 μM in the bulk-fluid/mat surface to below detection (< 0.3 μM) at a depth of ∼ 700 μm (∼ 10% of the total mat depth). Net areal oxygen fluxes into the microbial mats were estimated to range from 1.4-1.6 × 10(-4) μmol cm(-2) s(-1) . Dimensionless parameters were used to model dissolved oxygen profiles and establish that mass transfer rates limit the oxygen consumption. A zone of higher dissolved oxygen at the mat surface promotes Fe(III)-oxide biomineralization, which was supported using molecular analysis of Metallosphaera yellowstonensis 16S rRNA gene copy numbers and mRNA expression of haem Cu oxidases (FoxA) associated with Fe(II)-oxidation. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.
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Geochemical drivers of organic matter decomposition in Arctic tundra soils
Herndon, Elizabeth M.; Yang, Ziming; Graham, David E.; ...
2015-12-07
Climate change is warming tundra ecosystems in the Arctic, resulting in the decomposition of previously-frozen soil organic matter (SOM) and release of carbon (C) to the atmosphere; however, the processes that control SOM decomposition and C emissions remain highly uncertain. In this study, we evaluate geochemical factors that influence anaerobic production of carbon dioxide (CO 2) and methane (CH 4) in the active layers of four ice-wedge polygons. Surface and soil pore waters were collected during the annual thaw season over a two-year period in an area containing waterlogged, low-centered polygons and well-drained, high-centered polygons. We report spatial and seasonalmore » patterns of dissolved gases in relation to the geochemical properties of Fe and organic C as determined using spectroscopic and chromatographic techniques. Iron was present as Fe(II) in soil solution near the permafrost boundary but enriched as Fe(III) in the middle of the active layer, similar to dissolved aromatic-C and organic acids. Dissolved CH 4 increased relative to dissolved CO 2 with depth and varied with soil moisture in the middle of the active layer in patterns that were positively correlated with the proportion of dissolved Fe(III) in transitional and low-centered polygon soils but negatively correlated in the drier flat- and high-centered polygons. These results suggest that microbial-mediated Fe oxidation and reduction influence respiration/fermentation of SOM and production of substrates (e.g., low-molecular-weight organic acids) for methanogenesis. As a result, we infer that geochemical differences induced by water saturation dictate microbial products of SOM decomposition, and Fe geochemistry is an important factor regulating methanogenesis in anoxic tundra soils.« less
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North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with d...
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NASA Astrophysics Data System (ADS)
de Jong, S.; Huang, Y.; Huisman, R.; Massee, F.; Thirupathaiah, S.; Gorgoi, M.; Schaefers, F.; Follath, R.; Goedkoop, J. B.; Golden, M. S.
2009-03-01
Photoemission data taken with hard x-ray radiation on cleaved single crystals of the barium parent compound of the MFe2As2 pnictide high-temperature superconductor family are presented. Making use of the increased bulk sensitivity upon hard x-ray excitation, and comparing the results to data taken at conventional vacuum ultraviolet photoemission excitation energies, it is shown that the BaFe2As2 cleavage surface provides an electrostatic environment that is slightly different to the bulk, most likely in the form of a modified Madelung potential. However, as the data argue against a different surface doping level, and the surface-related features in the spectra are by no means as dominating as seen in systems such as YBa2Cu3Ox , we can conclude that the itinerant, near- EF electronic states are almost unaffected by the existence of the cleavage surface. Furthermore, exploiting the strong changes in photoionization cross section between the Fe and As states across the wide photon energy range employed, it is shown that the degree of energetic overlap between the iron 3d and arsenic 4p valence bands is particularly small at the Fermi level, which can only mean a very low degree of hybridization between the Fe3d and As4p states near and at EF . Consequently, this means that the itinerancy of the charge carriers in this group of materials involves mainly the Fe3d-Fe3d overlap integrals with at best a minor role for the Fe3d-As4p hopping parameters and that the states which support superconductivity upon doping are essentially of Fe3d character.
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NASA Astrophysics Data System (ADS)
Waters, Laura E.; Lange, Rebecca A.
2017-06-01
The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.
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Bactericidal Effect of Zero-Valent Iron Nanoparticles on Escherichia coli
Lee, Changha; Kim, Jee Yeon; Lee, Won Il; Nelson, Kara L.; Yoon, Jeyong; Sedlak, David L.
2008-01-01
Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia coli (E. coli). A strong bactericidal effect of nano-Fe0 was found under deaerated conditions, with a linear correlation between log inactivation and nano-Fe0 dose (0.82 log inactivation / mg/L nano-Fe0 · hr). The inactivation of E. coli under air saturation required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Significant physical disruption of the cell membranes was observed in E. coli exposed to nano-Fe0, which may have caused the inactivation, or enhanced the biocidal effects of dissolved iron. The reaction of Fe(II) with intracellular oxygen or hydrogen peroxide also may have induced oxidative stress by producing reactive oxygen species. The bactericidal effect of nano-Fe0 was a unique property of nano-Fe0, which was not observed in other types of iron-based compounds. PMID:18678028
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Fractionation of Fe isotopes by soil microbes and organic acids
Brantley, Susan L.; Liermann, Laura; Bullen, Thomas D.
2001-01-01
Small natural variations in Fe isotopes have been attributed to biological cycling. However, without understanding the mechanism of fractionation, it is impossible to interpret such variations. Here we show that the δ56Fe of Fe dissolved from a silicate soil mineral by siderophore-producing bacteria is as much as 0.8% lighter than bulk Fe in the mineral. A smaller isotopic shift is observed for Fe released abiotically by two chelates, and the magnitude of the shift increases with affinity of the ligand for Fe, consistent with a kinetic isotope effect during hydrolysis of Fe at the mineral surface. Fe dissolved abiotically without chelates shows no isotopic shift. The δ56Fe of the exchange fraction on soil grains is also lighter by ~0.6%-1% than Fe from both hornblende and iron oxyhydroxides. The kinetic isotope effect is therefore preserved in open systems such as soils. when recorded in the rock record, Fe isotopic fractionation could document Fe transport by organic molecules or by microbes where such entities were present in the geologic past.
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Thermal and ion-induced surface reactions of 1,1-difluoroethylene on Si(111)7 x 7 and vitreous SiO2.
He, Zhenhua; Leung, K T
2005-08-11
Thermal and ion-induced reactions of 1,1-difluoroethylene (1,1-C2H2F2 or iso-DFE) on Si(111)7 x 7 and vitreous SiO2 surfaces have been investigated by vibrational electron energy loss spectroscopy and thermal desorption spectrometry. Like ethylene, iso-DFE predominantly chemisorbs via a [2 + 2] cycloaddition mechanism onto the 7 x 7 surface as a di-sigma-bonded difluoroethane-1,2-diyl adstructure, which undergoes H abstraction and defluorination, producing hydrocarbon fragments and SiF(x) (x = 1-3) upon annealing to >700 K. Ion irradiation of Si(111)7 x 7 in iso-DFE at 50 eV impact energy appears to substantially enhance the production of hydrocarbon fragments and SiF(x)(), leading to stronger SiF4 desorption products over an extended temperature range (400-900 K). The observed SiC and SiF(x) produced on the 7 x 7 surface by ion irradiation in iso-DFE are found to be similar to those obtained by ion irradiation in the fluoromethane homologues, CF4 and CH2F2. The production of higher relative concentrations for the larger SiF(x) and C2-containing fragments is evidently favored on the 7 x 7 surface. On a vitreous SiO2 surface, ion irradiation in iso-DFE, unlike that in CF4 and CH2F2, appears to produce less SiF(x) than that on the 7 x 7 surface, which indicates that surface O does not interact strongly with the C2-containing fragments. The presence or absence of a C=C bond and the relative F-to-C ratio of the sputtering gas could therefore produce important effects on the resulting surface products obtained by low-energy ion irradiation.
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Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.
Flynn, Elaine D; Catalano, Jeffrey G
2018-06-05
During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.
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Hoch, A.R.; Reddy, M.M.; Drever, J.I.
1996-01-01
Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.
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NASA Astrophysics Data System (ADS)
Ma, Shufen; Noble, Abigail; Butcher, Derek; Trouwborst, Robert E.; Luther, George W., III
2006-11-01
The oxidation and precipitation of H 2S were investigated in Torquay Canal and Bald Eagle Creek, two tributaries of northern Rehoboth Bay, one of the Delaware Inland Bays. These man-made dead end canals develop seasonal anoxia and have been the site of past fish kills and harmful algal blooms. The canals have multiple holes over 5.5 m deep compared to an average low tide depth of 2 m. In situ determination for dissolved O 2, H 2S and other Fe and S redox species were conducted with a solid-state Au/Hg microelectrode in 2003 and 2004. Laboratory analyses of discrete samples were also performed to measure dissolved and particulate Fe, Mn, and S 8 to follow the seasonal dynamics of O, S, Fe and Mn redox species. Our results indicate that the water in the holes becomes stratified with O 2 decreasing with depth and H 2S increasing with depth. Dissolved Fe was as high as 30 μM whereas dissolved Mn was only 0.2 μM in the water column, indicating that Fe is the dominant metal involved in S redox cycling and precipitation. In surface oxic waters, the dominant form of Fe was particulate Fe(III) (oxy)hydroxides. When seasonal anoxia developed, Fe(III) (oxy)hydroxides were reduced by H 2S to Fe(II) at the oxic-anoxic interface. The Fe(II) reduced from particulate Fe can be re-oxidized to Fe(III) by O 2 above and at the interface to form a catalytic cycle to oxidize H 2S. Elemental S is the predominant oxidation product and was as high as 30 μM level (as S 0) at the interface. When the system was stable, the Fe catalytic cycle prevented H 2S from being released into surface waters during seasonal anoxia. However, when storms came, the water column was overturned and H 2S was released to the surface water. The reaction rates for the Fe catalytic cycle are not fast enough and the concentration of Fe was not high enough to regulate the high concentration of H 2S in surface waters during storm and mixing events.
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Scott, Durelle T.; Runkel, Robert L.; McKnight, Diane M.; Voelker, Bettina M.; Kimball, Briant A.; Carraway, Elizabeth R.
2003-01-01
An in-stream injection of two dissolved organic acids (phthalic and aspartic acids) was performed in an acidic mountain stream to assess the effects of organic acids on Fe photoreduction and H2O2 cycling. Results indicate that the fate of Fe is dependent on a net balance of oxidative and reductive processes, which can vary over a distance of several meters due to changes in incident light and other factors. Solution phase photoreduction rates were high in sunlit reaches and were enhanced by the organic acid addition but were also limited by the amount of ferric iron present in the water column. Fe oxide photoreduction from the streambed and colloids within the water column resulted in an increase in the diurnal load of total filterable Fe within the experimental reach, which also responded to increases in light and organic acids. Our results also suggest that Fe(II) oxidation increased in response to the organic acids, with the result of offsetting the increase in Fe(II) from photoreductive processes. Fe(II) was rapidly oxidized to Fe(III) after sunset and during the day within a well-shaded reach, presumably through microbial oxidation. H2O 2, a product of dissolved organic matter photolysis, increased downstream to maximum concentrations of 0.25 ??M midday. Kinetic calculations show that the buildup of H2O2 is controlled by reaction with Fe(III), but this has only a small effect on Fe(II) because of the small formation rates of H2O2 compared to those of Fe(II). The results demonstrate the importance of incorporating the effects of light and dissolved organic carbon into Fe reactive transport models to further our understanding of the fate of Fe in streams and lakes.
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Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer
Brown, C.J.; Schoonen, M.A.A.; Candela, J.L.
2000-01-01
Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO4/2- in the aerobic zone, and to the reduction of SO4/2- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55 x 10-4 to 48.6 x 10-4 mmol 1-1 yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO4/2- (1.31 x 10-4 to 15 x 10-4 mmol 1-1 yr-1). The overall increase in SO4/2- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO4/2- loss through microbial reduction is exceeded by SO4/2- gain through diffusion from sediments and through the oxidation of FeS2. Geochemichal and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO4/2- -rich zones have localized SO4/2- -reducing zones in which the formation of iron disulfides been depleted by microbial reduction and resulted in decreases dissolved iron concentrations. These localized zones of SO4/2- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling. (C) 2000 Elsevier Science B.V.Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO42- in the aerobic zone, and to the reduction of SO42- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55??10-4 to 48.6??10-4mmol l-1yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO42- (1.31??10-4 to 15??10-4mmol l-1yr-1). The overall increase in SO42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO42- loss through microbial reduction is exceeded by SO42- gain through diffusion from sediments and through the oxidation of FeS2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO42--rich zones have been depleted by microbial reduction and resulted in localized SO42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.
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NASA Astrophysics Data System (ADS)
Liang, Liyuan; McCarthy, John F.; Jolley, Louwanda W.; McNabb, J. Andrew; Mehlhorn, Tonia L.
1993-05-01
The dynamics of dissolved, colloidal, and deposited iron phases were examined during a forced-gradient field experiment. The experiment involved the injection of oxygenated water containing high levels of natural organic matter (NOM) into a sandy aquifer. The initial redox potential of the aquifer favored Fe(II) in the groundwater. The changes in the concentrations of Fe(II) and Fe(III) were observed in sampling wells. Under the increased dissolved oxygen (DO) conditions, Fe(II) oxygenation was rapid, resulting in the formation of Fe(III) (hydr) oxide colloids. The oxidation follows the rate law as given in STUMM and MORGAN (1981): d[ Fe(II)] /dt = - k obs[ O2( aq)] /[ H+] 2[ Fe(II)] , with a rate constant, kobs to be 1.9 × 10 -12 M min -1. For an averaged pH and DO of the groundwater, the half time of Fe(II) oxidation is 49 h. The NOM was postulated to stabilize the newly formed colloids, thereby increasing the turbidity in the groundwater. The additional increase in the colloidal fraction of Fe(III) oxide suggested that transport of the colloidal particles was occurring. At those locations where DO remained constantly low, the turbidity increase was moderate, and up to 80% of Fe(III) was in the dissolved phase (< 3000 mol. wt). The latter observation was attributed to the presence of NOM, forming Fe(III)-organic complexes. In addition, NOM may play a role in the oxygen consumption through a Fe(II)/Fe(III) catalyzed oxidation of organic matter as outlined by STUMM and MORGAN (1981, p. 469). In this mechanism, Fe(II) oxidation is slow, maintaining a near constant Fe(II) concentration, in agreement with field data. The overall increase in Fe(III) under low DO conditions was postulated to be a combination of (1) slow oxidation, (2) ligand-promoted and catalytic dissolution of deposited iron phases, and (3) the transport of newly formed iron oxide colloids along flow paths.
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Kang, Heerim; Lee, Chang Hyung; Kim, Jong Rhan; Kwon, Jung Yeon; Son, Myoung-Jin; Kim, Jong-Eun; Lee, Ki Won
2017-02-01
Cacao beans from Theobroma cacao are an abundant source of polyphenols, particularly flavonoids. Previous studies demonstrated that cacao flavanols decrease pro-inflammatory cytokines resulting in the alleviation of allergic symptoms. We sought to investigate the effects of cacao extract (CE) on Dermatophagoides farinae extract (DFE)-induced atopic dermatitis (AD)-like symptoms. CE attenuated DFE-induced AD-like symptoms as assessed by skin lesion analyses, dermatitis score, and skin thickness. Histopathological analysis revealed that CE suppressed DFE-induced immune cell infiltration into the skin. These observations occurred concomitantly with the downregulation of inflammatory markers including serum immunoglobulin (Ig) E, chemokine; thymus and activation-regulated chemokine and macrophage-derived chemokine as well as the skin-derived cytokines interleukin (IL)-4, IL-5, and interferon-γ. CE also significantly alleviated transepidermal water loss and increased skin hydration. These results suggest that CE, a natural phytochemical-rich food, has potential therapeutic efficacy for the treatment of AD. Copyright © 2016. Published by Elsevier Ltd.
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Nimick, D.A.; Gurrieri, J.T.; Furniss, G.
2009-01-01
Methods for assessing natural background water quality of streams affected by historical mining are vigorously debated. An empirical method is proposed in which stream-specific estimation equations are generated from relationships between either pH or dissolved Cu concentration in stream water and the Fe/Cu concentration ratio in Fe-precipitates presently forming in the stream. The equations and Fe/Cu ratios for pre-mining deposits of alluvial ferricrete then were used to reconstruct estimated pre-mining longitudinal profiles for pH and dissolved Cu in three acidic streams in Montana, USA. Primary assumptions underlying the proposed method are that alluvial ferricretes and modern Fe-precipitates share a common origin, that the Cu content of Fe-precipitates remains constant during and after conversion to ferricrete, and that geochemical factors other than pH and dissolved Cu concentration play a lesser role in determining Fe/Cu ratios in Fe-precipitates. The method was evaluated by applying it in a fourth, naturally acidic stream unaffected by mining, where estimated pre-mining pH and Cu concentrations were similar to present-day values, and by demonstrating that inflows, particularly from unmined areas, had consistent effects on both the pre-mining and measured profiles of pH and Cu concentration. Using this method, it was estimated that mining has affected about 480 m of Daisy Creek, 1.8 km of Fisher Creek, and at least 1 km of Swift Gulch. Mean values of pH decreased by about 0.6 pH units to about 3.2 in Daisy Creek and by 1-1.5 pH units to about 3.5 in Fisher Creek. In Swift Gulch, mining appears to have decreased pH from about 5.5 to as low as 3.6. Dissolved Cu concentrations increased due to mining almost 40% in Daisy Creek to a mean of 11.7 mg/L and as much as 230% in Fisher Creek to 0.690 mg/L. Uncertainty in the fate of Cu during the conversion of Fe-precipitates to ferricrete translates to potential errors in pre-mining estimates of as much as 0.25 units for pH and 22% for dissolved Cu concentration. The method warrants further testing in other mined and unmined watersheds. Comparison of pre-mining water-quality estimates derived from the ferricrete and other methods in single watersheds would be particularly valuable. The method has potential for use in monitoring remedial efforts at mine sites with ferricrete deposits. A reasonable remediation objective might be realized when the downstream pattern of Fe/Cu ratios in modern streambed Fe-precipitates corresponds to the pattern in pre-mining alluvial ferricrete deposits along a stream valley.
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Noble, Abigail E.; Moran, Dawn M.; Allen, Andrew E.; Saito, Mak A.
2013-01-01
Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO3−4 ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions. PMID:24790953
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NASA Astrophysics Data System (ADS)
Noble, Abigail; Saito, Mak; Moran, Dawn; Allen, Andrew
2013-10-01
Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO43- ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions.
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Pleasant, Saraya; O'Donnell, Amanda; Powell, Jon; Jain, Pradeep; Townsend, Timothy
2014-07-01
High concentrations of iron (Fe(II)) and manganese (Mn(II)) reductively dissolved from soil minerals have been detected in groundwater monitoring wells near many municipal solid waste landfills. Air sparging and vadose zone aeration (VZA) were evaluated as remedial approaches at a closed, unlined municipal solid waste landfill in Florida, USA. The goal of aeration was to oxidize Fe and Mn to their respective immobile forms. VZA and shallow air sparging using a partially submerged well screen were employed with limited success (Phase 1); decreases in dissolved iron were observed in three of nine monitoring wells during shallow air sparging and in two of 17 wells at VZA locations. During Phase 2, where deeper air sparging was employed, dissolved iron levels decreased in a significantly greater number of monitoring wells surrounding injection points, however no radial pattern was observed. Additionally, in wells affected positively by air sparging (mean total iron (FeTOT) <4.2mg/L, after commencement of air sparging), rising manganese concentrations were observed, indicating that the redox potential of the groundwater moved from an iron-reducing to a manganese-reducing environment. The mean FeTOT concentration observed in affected monitoring wells throughout the study was 1.40 mg/L compared to a background of 15.38 mg/L, while the mean Mn concentration was 0.60 mg/L compared to a background level of 0.27 mg/L. Reference wells located beyond the influence of air sparging areas showed little variation in FeTOT and Mn, indicating the observed effects were the result of air injection activities at study locations and not a natural phenomenon. Air sparging was found effective in intercepting plumes of dissolved Fe surrounding municipal landfills, but the effect on dissolved Mn was contrary to the desired outcome of decreased Mn groundwater concentrations. Copyright © 2014 Elsevier B.V. All rights reserved.
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The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume
Ziegler, Brady A.; Schreiber, Madeline E.; Cozzarelli, Isabelle M.
2017-01-01
In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011–2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich “iron curtain,” associated with the anoxic-suboxic transition zone, migrated 30 m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter.
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The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume.
Ziegler, Brady A; Schreiber, Madeline E; Cozzarelli, Isabelle M
2017-09-01
In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011-2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich "iron curtain," associated with the anoxic-suboxic transition zone, migrated 30m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter. Copyright © 2017 Elsevier B.V. All rights reserved.
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Zhan, Xiaohui; Yi, Qiangying; Cai, Shuang; Zhou, Xiaoxi; Ma, Shaohua; Lan, Fang; Gu, Zhongwei; Wu, Yao
2017-12-15
In this study, we report a facile and versatile strategy for preparing a type of pH-responsive superparamagnetic hybrid coassemblies featuring a series of controls over the morphology and multi-functionalization simultaneously and efficiently. Via the entanglement interactions, the combine of fixed PEG-b-P4VP modified Fe 3 O 4 NPs (D-Fe 3 O 4 @mPEG-b-P4VP) and different well-designed free PEG-b-P4VP, which are analogous to two amphiphiles, contributes these hybrid superstructures with multiple, well-defined morphologies and targeted fluorescent properties. In contrast to other studies, our work overcame several defects (e.g., interior NPs' randomness, cumbersome assembly parameter adjustment and functionalization) of the conventional assembly of modified inorganic NPs and demonstrated that this coassembly strategy can be used as a versatile tool for the controllable assembly of other NPs or polymers. Finally, taking the coassembly C1 as a desirable drug delivery carrier, good biocompatibility and pH-triggered drug release were successfully verified. The current study indicated that these magnetic coassemblies are promising as multifunctional and multipurpose carriers in biological, medical, catalytic, and coating applications. Copyright © 2017. Published by Elsevier Inc.
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Slenkamp, Karla M; Lynch, Michael S; Van Kuiken, Benjamin E; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira
2014-02-28
Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O and formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm(-1). The mixed-mode anharmonicities range from 2 to 14 cm(-1). In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm(-1). This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.
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Sisó-Terraza, Patricia; Rios, Juan J; Abadía, Javier; Abadía, Anunciación; Álvarez-Fernández, Ana
2016-01-01
Iron (Fe) is abundant in soils but generally poorly soluble. Plants, with the exception of Graminaceae, take up Fe using an Fe(III)-chelate reductase coupled to an Fe(II) transporter. Whether or not nongraminaceous species can convert scarcely soluble Fe(III) forms into soluble Fe forms has deserved little attention so far. We have used Beta vulgaris, one among the many species whose roots secrete flavins upon Fe deficiency, to study whether or not flavins are involved in Fe acquisition. Flavins secreted by Fe-deficient plants were removed from the nutrient solution, and plants were compared with Fe-sufficient plants and Fe-deficient plants without flavin removal. Solubilization of a scarcely soluble Fe(III)-oxide was assessed in the presence or absence of flavins, NADH (nicotinamide adenine dinucleotide, reduced form) or plant roots, and an Fe(II) trapping agent. The removal of flavins from the nutrient solution aggravated the Fe deficiency-induced leaf chlorosis. Flavins were able to dissolve an Fe(III)-oxide in the presence of NADH. The addition of extracellular flavins enabled roots of Fe-deficient plants to reductively dissolve an Fe(III)-oxide. We concluded that root-secretion of flavins improves Fe nutrition in B. vulgaris. Flavins allow B. vulgaris roots to mine Fe from Fe(III)-oxides via reductive mechanisms. © 2015 CSIC New Phytologist © 2015 New Phytologist Trust.
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NASA Astrophysics Data System (ADS)
Conway, Tim M.; John, Seth G.
2015-09-01
Dissolved stable isotope ratios of the transition metals provide useful information, both for understanding the cycling of these bioactive trace elements through the oceans, and tracing their marine sources and sinks. Here, we present seawater dissolved Fe, Zn and Cd concentration and stable isotope ratio (δ56Fe, δ66Zn, and δ114Cd) profiles from two stations in the Pacific Ocean, the SAFe Station (30°N 140°W) in the subtropical North East Pacific from the GEOTRACES IC2 cruise, and the marginal San Pedro Basin (33.8°N 118.4°W) within the South California Bight. These data represent, to our knowledge, the first full-water column profiles for δ66Zn and δ56Fe from the open-ocean North Pacific, and the first observations of dissolved δ66Zn and δ114Cd in a low-oxygen marginal basin. At the SAFe station, δ56Fe is isotopically lighter throughout the water column (-0.6 to +0.1‰, relative to IRRM-014) compared to the North Atlantic, suggesting significant differences in Fe sources or Fe cycling between these two ocean basins. A broad minimum in δ56Fe associated with the North Pacific oxygen minimum zone (OMZ; <75 μmol kg-1 dissolved oxygen; ∼550-2000 m depth) is consistent with reductive sediments along the California margin being an important source of dissolved Fe to the North Pacific. Other processes which may influence δ56Fe at SAFe include biological cycling in the upper ocean, and input of Fe from hydrothermal vents and oxic sediments below the OMZ. Zn and Cd concentration profiles at both stations broadly match the distribution of the macronutrients silicate and phosphate, respectively. At SAFe, δ114Cd increases towards the surface, reflecting the biological preference for assimilation of lighter Cd isotopes, while negative Cd∗ (-0.12) associated with low oxygen waters supports the recently proposed hypothesis of water-column CdS precipitation. In contrast to δ114Cd, δ66Zn at SAFe decreases towards the surface ocean, perhaps due to scavenging of isotopically heavy Zn, while at intermediate depths δ66Zn provides further evidence of a mid-depth dissolved δ66Zn maximum. We suggest this may be a global feature of Zn biogeochemistry related to either regeneration of heavy adsorbed Zn, or to ZnS formation and removal within the water column. Data from San Pedro shows that anoxic sediments can be a source of isotopically light Zn to the water column (δ66Zn of ∼-0.3‰ relative to JMC Lyon), though evidence of this signal is not observed being transported to SAFe. Within North Pacific Intermediate Water at SAFe (NPIW; ∼500 m) elevated Cd∗ and Zn∗ and a focused minimum in δ56Fe suggest possible transport of Fe, Zn, and Cd over thousands of km from subpolar waters, meaning that NPIW may have a strong influence on the subsurface distribution of trace metals throughout the North Pacific.
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Distinct Siderophores Contribute to Iron Cycling in the Mesopelagic at Station ALOHA
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bundy, Randelle M.; Boiteau, Rene M.; McLean, Craig
The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L -1 in the surface to 1.6 nmol L -1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxaminemore » siderophores were most abundant in the upper water column, with concentrations between 0.1-2 pmol L -1, while a suite of amphibactins were found below 200 m with concentrations between 0.8-11 pmol L -1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log ) ranging from 12.0-12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0-14.4, within the range of observed L1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.« less
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Distinct Siderophores Contribute to Iron Cycling in the Mesopelagic at Station ALOHA
Bundy, Randelle M.; Boiteau, Rene M.; McLean, Craig; ...
2018-03-01
The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L -1 in the surface to 1.6 nmol L -1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxaminemore » siderophores were most abundant in the upper water column, with concentrations between 0.1-2 pmol L -1, while a suite of amphibactins were found below 200 m with concentrations between 0.8-11 pmol L -1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log ) ranging from 12.0-12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0-14.4, within the range of observed L1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.« less
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Augustine, Daniel; Yaqub, Mohammad; Szmigielski, Cezary; Lima, Eduardo; Petersen, Steffen E; Becher, Harald; Noble, J Alison; Leeson, Paul
2015-02-01
Three-dimensional fusion echocardiography (3DFE) is a novel postprocessing approach that utilizes imaging data acquired from multiple 3D acquisitions. We assessed image quality, endocardial border definition, and cardiac wall motion in patients using 3DFE compared to standard 3D images (3D) and results obtained with contrast echocardiography (2DC). Twenty-four patients (mean age 66.9 ± 13 years, 17 males, 7 females) undergoing 2DC had three, noncontrast, 3D apical volumes acquired at rest. Images were fused using an automated image fusion approach. Quality of the 3DFE was compared to both 3D and 2DC based on contrast-to-noise ratio (CNR) and endocardial border definition. We then compared clinical wall-motion score index (WMSI) calculated from 3DFE and 3D to those obtained from 2DC images. Fused 3D volumes had significantly improved CNR (8.92 ± 1.35 vs. 6.59 ± 1.19, P < 0.0005) and segmental image quality (2.42 ± 0.99 vs. 1.93 ± 1.18, P < 0.005) compared to unfused 3D acquisitions. Levels achieved were closer to scores for 2D contrast images (CNR: 9.04 ± 2.21, P = 0.6; segmental image quality: 2.91 ± 0.37, P < 0.005). WMSI calculated from fused 3D volumes did not differ significantly from those obtained from 2D contrast echocardiography (1.06 ± 0.09 vs. 1.07 ± 0.15, P = 0.69), whereas unfused images produced significantly more variable results (1.19 ± 0.30). This was confirmed by a better intraclass correlation coefficient (ICC 0.72; 95% CI 0.32-0.88) relative to comparisons with unfused images (ICC 0.56; 95% CI 0.02-0.81). 3DFE significantly improves left ventricular image quality compared to unfused 3D in a patient population and allows noncontrast assessment of wall motion that approaches that achieved with 2D contrast echocardiography. © 2014, Wiley Periodicals, Inc.
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Mondal, Saptarsi; Halder, Ritaban; Biswas, Biswajit; Jana, Biman; Singh, Prashant Chandra
2016-05-14
The self-aggregation property of the perfluoro group containing molecules makes it important in the research fields of biology and polymer and organic synthesis. In the quest of understanding the role of the perfluoro group on the photophysical properties of perfluoro-containing molecules in biologically important fluoroethanol solvents, we have applied photophysical as well as molecular dynamics simulation techniques to explore the properties of perfluoro groups containing molecule coumarin-153 (C153) in ethanol (ETH), monofluoroethanol (MFE), difluoroethanol (DFE), and trifluoroethanol (TFE) and compared them with the molecules without perfluoro moiety, namely coumarin-6H (C6H) and coumarin-480 (C480). In contrast to C6H and C480, the excited state lifetime of C153 in fluorinated ETHs is not monotonic. The excited state lifetime of C153 decreases in MFE and DFE as compared to ETH, whereas in TFE, it increases as compared to MFE and DFE. Molecular dynamics simulation reveals that the carbon terminal away from the OH group of fluorinated ETHs has a preferential orientation near the perfluoro (CF3) group of C153. In MFE and DFE, the CF3 group of C153 prefers to have a CF2-F⋯H -(CHF) type of electrostatic interaction over CF2-F⋯F -(CH2) kind of dispersion interaction which increases the rate of nonradiative decay, probably due to the electrostatic nature of the CF2-F⋯H -(CHF) hydrogen bond. On the other hand, in TFE, C-F⋯ F-C type of dispersion interaction, also known as fluorous interaction, takes place between the CF3 groups of C153 and TFE which decreases the rate of nonradiative rate as compared to MFE and DFE, leading to the increased lifetime of C153 in TFE. Photophysical and MD simulation studies clearly depict that the structural organization of solvents and their interaction with the fluorocarbon group are crucial factors for the photophysical behavior of the fluorocarbon containing molecules.
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NASA Astrophysics Data System (ADS)
Mondal, Saptarsi; Halder, Ritaban; Biswas, Biswajit; Jana, Biman; Singh, Prashant Chandra
2016-05-01
The self-aggregation property of the perfluoro group containing molecules makes it important in the research fields of biology and polymer and organic synthesis. In the quest of understanding the role of the perfluoro group on the photophysical properties of perfluoro-containing molecules in biologically important fluoroethanol solvents, we have applied photophysical as well as molecular dynamics simulation techniques to explore the properties of perfluoro groups containing molecule coumarin-153 (C153) in ethanol (ETH), monofluoroethanol (MFE), difluoroethanol (DFE), and trifluoroethanol (TFE) and compared them with the molecules without perfluoro moiety, namely coumarin-6H (C6H) and coumarin-480 (C480). In contrast to C6H and C480, the excited state lifetime of C153 in fluorinated ETHs is not monotonic. The excited state lifetime of C153 decreases in MFE and DFE as compared to ETH, whereas in TFE, it increases as compared to MFE and DFE. Molecular dynamics simulation reveals that the carbon terminal away from the OH group of fluorinated ETHs has a preferential orientation near the perfluoro (CF3) group of C153. In MFE and DFE, the CF3 group of C153 prefers to have a CF2—F⋯H —(CHF) type of electrostatic interaction over CF2—F⋯F —(CH2) kind of dispersion interaction which increases the rate of nonradiative decay, probably due to the electrostatic nature of the CF2—F⋯H —(CHF) hydrogen bond. On the other hand, in TFE, C—F⋯ F—C type of dispersion interaction, also known as fluorous interaction, takes place between the CF3 groups of C153 and TFE which decreases the rate of nonradiative rate as compared to MFE and DFE, leading to the increased lifetime of C153 in TFE. Photophysical and MD simulation studies clearly depict that the structural organization of solvents and their interaction with the fluorocarbon group are crucial factors for the photophysical behavior of the fluorocarbon containing molecules.
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Study of a co-designed decision feedback equalizer, deinterleaver, and decoder
NASA Technical Reports Server (NTRS)
Peile, Robert E.; Welch, Loyd
1990-01-01
A technique that promises better quality data from band limited channels at lower received power in digital transmission systems is presented. Data transmission, in such systems often suffers from intersymbol interference (ISI) and noise. Two separate techniques, channel coding and equalization, have caused considerable advances in the state of communication systems and both concern themselves with removing the undesired effects of a communication channel. Equalizers mitigate the ISI whereas coding schemes are used to incorporate error-correction. In the past, most of the research in these two areas has been carried out separately. However, the individual techniques have strengths and weaknesses that are complementary in many applications: an integrated approach realizes gains in excess to that of a simple juxtaposition. Coding schemes have been successfully used in cascade with linear equalizers which in the absence of ISI provide excellent performance. However, when both ISI and the noise level are relatively high, nonlinear receivers like the decision feedback equalizer (DFE) perform better. The DFE has its drawbacks: it suffers from error propagation. The technique presented here takes advantage of interleaving to integrate the two approaches so that the error propagation in DFE can be reduced with the help of error correction provided by the decoder. The results of simulations carried out for both, binary, and non-binary, channels confirm that significant gain can be obtained by codesigning equalizer and decoder. Although, systems with time-invariant channels and simple DFE having linear filters were looked into, the technique is fairly general and can easily be modified for more sophisticated equalizers to obtain even larger gains.
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Wakame, Koji; Komatsu, Ken-Ichi; Inagawa, Hiroyuki; Nishizawa, Takashi
2015-08-01
Pantoea agglomerans LPS (immunopotentiator from Pantoea agglomerans 1: IP-PA1) has been reported to have anti-inflammatory effects in in vitro and in vivo models. The aim of the present study was to investigate the effects of orally-administered IP-PA1 on atopic dermatitis (AD) symptoms induced by Dermatophagoides farinae body extract (DFE) in NC/Nga mice. Using the NC/Nga AD murine model, mice were orally administered 0.1% (High) or 0.01% (Low) water-containing IP-PA1. Skin lesion assessment and blood collection from the caudal vein was performed on days 0, 7, 21 and 31. On day 31, all mice were sacrificed and blood, skin, spleen, as well as intestine samples, were obtained. Assessment score of the skin lesion and serum immunoglobulin E (IgE) level of both IP-PA1 groups were significantly lower than that of the DFE group on days 14 and 21. The serum periostin and thymus and activation-regulated chemokine (TARC) level of IP-PA1-Low group was significantly lower than that of the DFE group on day 31. On histological examination of the skin, hyperplasia of epidermal and dermal layers and infiltration of inflammatory cells were suppressed by IP-PA1 administration. Deposition of periostin was observed in the DFE group skin tissue. Moreover, the CD4(+)/CD8(+) ratio of splenic T-cells increased by IP-PA1 administration. IP-PA1 administration may have an inhibitory effect on AD skin lesions. Copyright© 2015 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.
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Characterizability of metabolic pathway systems from time series data.
Voit, Eberhard O
2013-12-01
Over the past decade, the biomathematical community has devoted substantial effort to the complicated challenge of estimating parameter values for biological systems models. An even more difficult issue is the characterization of functional forms for the processes that govern these systems. Most parameter estimation approaches tacitly assume that these forms are known or can be assumed with some validity. However, this assumption is not always true. The recently proposed method of Dynamic Flux Estimation (DFE) addresses this problem in a genuinely novel fashion for metabolic pathway systems. Specifically, DFE allows the characterization of fluxes within such systems through an analysis of metabolic time series data. Its main drawback is the fact that DFE can only directly be applied if the pathway system contains as many metabolites as unknown fluxes. This situation is unfortunately rare. To overcome this roadblock, earlier work in this field had proposed strategies for augmenting the set of unknown fluxes with independent kinetic information, which however is not always available. Employing Moore-Penrose pseudo-inverse methods of linear algebra, the present article discusses an approach for characterizing fluxes from metabolic time series data that is applicable even if the pathway system is underdetermined and contains more fluxes than metabolites. Intriguingly, this approach is independent of a specific modeling framework and unaffected by noise in the experimental time series data. The results reveal whether any fluxes may be characterized and, if so, which subset is characterizable. They also help with the identification of fluxes that, if they could be determined independently, would allow the application of DFE. Copyright © 2013 Elsevier Inc. All rights reserved.
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Characterizability of Metabolic Pathway Systems from Time Series Data
Voit, Eberhard O.
2013-01-01
Over the past decade, the biomathematical community has devoted substantial effort to the complicated challenge of estimating parameter values for biological systems models. An even more difficult issue is the characterization of functional forms for the processes that govern these systems. Most parameter estimation approaches tacitly assume that these forms are known or can be assumed with some validity. However, this assumption is not always true. The recently proposed method of Dynamic Flux Estimation (DFE) addresses this problem in a genuinely novel fashion for metabolic pathway systems. Specifically, DFE allows the characterization of fluxes within such systems through an analysis of metabolic time series data. Its main drawback is the fact that DFE can only directly be applied if the pathway system contains as many metabolites as unknown fluxes. This situation is unfortunately rare. To overcome this roadblock, earlier work in this field had proposed strategies for augmenting the set of unknown fluxes with independent kinetic information, which however is not always available. Employing Moore-Penrose pseudo-inverse methods of linear algebra, the present article discusses an approach for characterizing fluxes from metabolic time series data that is applicable even if the pathway system is underdetermined and contains more fluxes than metabolites. Intriguingly, this approach is independent of a specific modeling framework and unaffected by noise in the experimental time series data. The results reveal whether any fluxes may be characterized and, if so, which subset is characterizable. They also help with the identification of fluxes that, if they could be determined independently, would allow the application of DFE. PMID:23391489
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Zhuang, J Ming; Hobenshield, Evan; Walsh, Tony
2009-02-01
A two-stage (I and II) lab-scale treatment system has been studied for arsenic removal from water using Fe(II) and lignosulphonates with aeration. In stage I, using an Fe/As mole ratio of 1.5-2.5 at a pH of around 6.5-7.5, the dissolved arsenic can be reduced with Fe(II) oxidation-precipitation from an initial 72 mg L(-1) to < 2 mg L(-1). The generated sludge is entirely recycled to the second tank of stage II. In the first tank of stage II, the water is further treated with the same amount of Fe(II) as that used in stage I, in the presence of lignosulphonates and aeration. The air-oxidization of Fe(II) to Fe(III) is continued for about 30 minutes at a pH of around 7.0-8.0. The water output from the first tank is transferred to the second tank in which mixing under aeration occurs with the sludge recycled from stage I. Accordingly, the dissolved arsenic in the effluent is reduced to < 0.1 mg L(-1). The results show that this two-stage process can save more than 50% of total chemical costs, and reduce the amount of sludge by more than 50%, in comparison with the conventional Fe(III)/lime-treatment process. According to US EPA regulations, the final Fe-As sludge is classified as non-hazardous materials by the Toxicity Characteristic Leaching Procedure. But, the study shows that the instability of Fe-As sludge could be influenced by some factors, such as higher pH levels, a longer water-leaching time and larger water-leaching volume, leading to the liberation of more dissolvable As species. After being treated with Ligmet stabilizer, the Fe-As sludge showed an improved stability under varying pH conditions and large amounts of water leaching. The treated Fe-As sludge is suitable for landfill disposal.
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NASA Astrophysics Data System (ADS)
Jilbert, Tom; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Asmala, Eero; Hietanen, Susanna
2016-04-01
Iron (Fe) and manganese (Mn) play important roles in sedimentary carbon cycling in both freshwater and marine systems. Dissimilatory reduction of Fe and Mn oxides is known to be a major pathway of suboxic organic matter remineralization in surface sediments, while recent studies have shown that Fe and Mn oxides may be involved in the anaerobic oxidation of methane deeper in the sediment column (e.g., Egger et al., 2015). Estuaries are transitional environments, characterized by gradients of salinity and redox conditions which impact on the mobility of Fe and Mn. In turn, the distribution of Fe and Mn in estuarine sediments, and the role of the two metals in carbon cycling, is expected to be spatially heterogeneous. However, few studies have attempted to describe the sedimentary distribution of Fe and Mn in the context of processes occurring in the estuarine water column. In particular, salinity-driven flocculation and redox shuttling are two key processes whose relative impacts on sedimentary Fe and Mn have not been clearly demonstrated. In this study we investigated the coupled water column and sedimentary cycling of Fe and Mn along a 60km non-tidal estuarine transect in the Gulf of Finland, Baltic Sea. We show that riverine Fe entering the estuary as colloidal oxides associated with dissolved organic matter (DOM) is quickly flocculated and sedimented within 5 km of the river mouth, despite the shallow lateral salinity gradient. Sediments within this range are enriched in Fe (up to twice the regional average), principally in the form of crystalline Fe oxides as determined by sequential extractions. The high crystallinity implies relative maturity of the oxide mineralogy, likely due to sustained oxic conditions and long residence time in the river catchment. Despite the reducing conditions below the sediment-water interface, Fe is largely retained in the sediments close to the river mouth. In contrast, sedimentary Mn concentrations are highest in a deep silled basin more than 10km downstream. Throughout the estuary, Mn oxides are reductively dissolved shallower in the sediment column than Fe oxides, resulting in strong effluxes of dissolved Mn from the sediments. Subsequent oxidation of bottom water dissolved Mn to particulate oxides and lateral transport ("redox shuttling") account for the sedimentary Mn enrichments in the deep silled basin. Porewater data suggest that the heterogeneity of Fe and Mn availability in the estuarine sediments may influence the relative importance of the two metals for anaerobic oxidation of methane. Egger, M. et al., Environmental Science and Technology 49(1), 277-283, 2015.
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NASA Astrophysics Data System (ADS)
Mork, Steven W.; Miller, C. Cameron; Philips, Laura A.
1992-09-01
The high resolution infrared spectrum of 1,2-difluoroethane (DFE) in a molecular beam has been obtained over the 2978-2996 cm-1 spectral region. This region corresponds to the symmetric combination of asymmetric C-H stretches in DFE. Observed rotational fine structure indicates that this C-H stretch is undergoing vibrational mode coupling to a single dark mode. The dark mode is split by approximately 19 cm-1 due to tunneling between the two identical gauche conformers. The mechanism of the coupling is largely anharmonic with a minor component of B/C plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. Analysis of the fine structure identifies the dark state as being composed of C-C torsion, CCF bend, and CH2 rock. Coupling between the C-H stretches and the C-C torsion is of particular interest because DFE has been observed to undergo vibrationally induced isomerization from the gauche to trans conformer upon excitation of the C-H stretch.
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Nie, F L; Zheng, Y F
2012-07-01
Conventional microcrystalline pure iron (MC-Fe) becomes a new candidate as biodegradable metals, which has the insufficient physical feature and inferior biodegradation behavior. Novel bulk nanocrystalline pure iron (NC-Fe) was fabricated via equal channel angular pressing technique in the present work to overcome these problems. The contact angle test with water and glycerol droplets shows a smaller angle (though >90°) of NC-Fe than that of MC-Fe, which implies a lower surface energy of NC-Fe. The surface roughness of NC-Fe increased greatly than that of MC-Fe. A further comparative study of corrosion and electrochemistry performance between NC-Fe and its original MC-Fe was investigated in physiological saline with different dissolved oxygen concentration, aiming to in vitro simulate the corrosion process of coronary stent occurred in physiological environment. The electrochemical impedance spectra analysis and anodic polarization measurements indicated that the NC-Fe exhibited higher corrosion resistance than that of the MC-Fe; meanwhile obvious enhanced corrosion resistance with the decrement of dissolved oxygen concentration was observed. Related equivalent circuit model and surface reconstruction process were further discussed, and the degradation mechanism of the MC-Fe and NC-Fe were finally established. Copyright © 2012 Wiley Periodicals, Inc.
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Trace Metals in Urban Stormwater Runoff and their Management
NASA Astrophysics Data System (ADS)
Li, T.; Hall, K.; Li, L. Y.; Schreier, H.
2009-04-01
In past decades, due to the rapid urbanization, land development has replaced forests, fields and meadows with impervious surfaces such as roofs, parking lots and roads, significantly affecting watershed quality and having an impact on aquatic systems. In this study, non-point source pollution from a diesel bus loop was assessed for the extent of trace metal contamination of Cu, Mn, Fe, and Zn in the storm water runoff. The study was carried out at the University of British Columbia (UBC) in the Greater Vancouver Regional District (GVRD) of British Columbia, Canada. Fifteen storm events were monitored at 3 sites from the diesel bus loop to determine spatial and temporal variations of dissolved and total metal concentrations in the storm water runoff. The dissolved metal concentrations were compared with the provincial government discharge criteria and the bus loop storm water quality was also compared with previous studies conducted across the GVRD urban area. To prevent storm water with hazardous levels of contaminants from being discharged into the urban drainage system, a storm water catch basin filter was installed and evaluated for its efficiency of contaminants removal. The perlite filter media adsorption capacities for the trace metals, oil and grease were studied for better maintenance of the catch basin filter. Dissolved copper exceeded the discharge criteria limit in 2 out of 15 cases, whereas dissolved zinc exceeded the criteria in 4 out of 15 cases, and dissolved manganese was below the criteria in all of the events sampled. Dissolved Cu and Zn accounted for 36 and 45% of the total concentration, whereas Mn and Fe only accounted for 20 and 4% of their total concentration, respectively. Since they are more mobile and have higher bioaccumulation potentials, Zn and Cu are considered to be more hazardous to the aquatic environment than Fe and Mn. With high imperviousness (100%) and intensive traffic at the UBC diesel bus loop, trace metal concentrations were 3, 0.7, 9, and 3.2 times higher than the GVRD urban area limits for Cu, Mn, Fe, and Zn, respectively. The filter showed high and stable capture efficiencies in total metals (Cu 62%, Mn 75%, Fe 83%, Zn 62%), dissolved metals (Cu 39%, Mn 37%, Fe 47%, Zn 32%), turbidity (72%), and suspended solids (74%) removal during the first month of operation. After that, there was gradual degradation. The catch basin filter performance improved significantly for the suspended solids and total metal removal after cleaning. However, the perlite filter medium showed poor performance for dissolved metal removal in the second study period. Based on the findings, a catch basin filter is effective in storm water management to control suspended solids loading from storm water runoff.
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Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.
2017-01-01
Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH)4− was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.
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NASA Astrophysics Data System (ADS)
van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.
2014-06-01
The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.
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NASA Astrophysics Data System (ADS)
van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.
2014-11-01
The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.
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Iron in the aquifer system of Suffolk County, New York, 1990–98
Brown, Craig J.; Walter, Donald A.; Colabufo, Steven
1999-01-01
High concentrations of dissolved iron in ground water contribute to the biofouling of public-supply wells, and the treatment and remediation of biofouling are costly. Water companies on Long Island, N.Y., spend several million dollars annually to recondition, redevelop, and replace supply wells and distribution lines; treat dissolved iron with sequestering agents or by filtration; and respond to iron-related complaints by customers. This report summarizes the results of studies done by the U.S. Geological Survey, in cooperation with the Suffolk County Water Authority, to characterize the geochemistry and microbiology of iron in the aquifer system of Suffolk County. This information should be helpful for the siting and operation of supply wells.Concentrations of dissolved iron in Long Island's ground water, and the frequency of iron biofouling of wells, are highest in ground-water-discharge zones, particularly near the south shore. Ground water along a deep north-south flowpath of the Magothy aquifer in southwestern Suffolk County becomes anaerobic (oxygen deficient) and Fe(III) reducing at a distance of 8 to 10 kilometers south of the ground-water divide, and this change coincides with the downgradient increase in dissolved iron concentrations. The distribution of organic carbon, and the distribution and local variations in reactivity of Fe(III), in Magothy aquifer sediments have resulted in localized differences in redox microenvironments. For example, Fe(III)-reducing zones are associated with anaerobic conditions, where relatively large amounts of Fe(III) oxyhydroxide grain coatings are present, whereas sulfate-reducing zones are associated with lignite-rich lenses of silt and clay and appear to have developed in response to the depletion of available Fe(III) oxyhydroxides. The sulfate-reducing zones are characterized by relatively low concentrations of dissolved iron (resulting from iron-disulfide precipitation) and may be large enough to warrant water-supply development.Specific-capacity and water-quality data from wells screened in the Magothy aquifer indicate that water from biofouled wells contains higher median concentrations of total and dissolved iron and manganese, total phosphate, and dissolved sulfate, and lower median concentrations of dissolved oxygen and alkalinity, and lower pH, than does water from unaffected wells. Corresponding data from wells screened in the upper glacial aquifer indicate that water from biofouled wells contains higher median concentrations of total and dissolved manganese and dissolved sulfate, and lower pH, than does water from unaffected wells.Filamentous bacteria were detected in 31 (or 72 percent) of the 43 biofilm samples obtained from biofouled wells during reconditioning. The predominant filamentous organism was Gallionella ferruginea, a major biofouling agent in the upper glacial and Magothy aquifers throughout Suffolk County. Mineral-saturation indices indicate that most of the well-encrusting material is deposited when the wells are shut down. Furthermore, the use of treated water (which has a high pH and sometimes high concentrations of dissolved iron) for pump prelubrication when wells are shut down could greatly increase the rate of iron oxidation.
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Authigenesis of trace metals in energetic tropical shelf environments
Breckel, E.J.; Emerson, S.; Balistrieri, L.S.
2005-01-01
We evaluated authigenic changes of Fe, Mn, V, U, Mo, Cd and Re in suboxic, periodically remobilized, tropical shelf sediments from the Amazon continental shelf and the Gulf of Papua. The Cd/Al, Mo/Al, and U/Al ratios in Amazon shelf sediments were 82%, 37%, and 16% less than those in Amazon River suspended sediments, respectively. Very large depletions of U previously reported in this environment were not observed. The Cd/Al ratios in Gulf of Papua sediments were 76% lower than measurements made on several Papua New Guinea rivers, whereas U/Al ratios in the shelf sediments were enriched by approximately 20%. Other metal/Al ratios in the Papua New Guinea river suspended sediments and continental shelf sediments were not distinguishably different. Comparison of metal/Al ratios to grain size distributions in Gulf of Papua samples indicates that our observations cannot be attributed to differences in grain size between the river suspended sediments and continental shelf sediments. These two shelves constitute a source of dissolved Cd to the world ocean equal to 29-100% of the dissolved Cd input from rivers, but only 3% of the dissolved Mo input and 4% of the dissolved U input. Release of Cd, Mo, and U in tropical shelf sediments is likely a result of intense Fe and Mn oxide reduction in pore waters and resuspension of the sediments. Since we do not observe depletions of particulate Fe and Mn in the shelf sediments most of these dissolved metals must reoxidize in the overlying waters and reprecipitate. As Cd exhibits the largest losses on these tropical shelves, we examined the ability of newly formed Fe and Mn oxides to adsorb dissolved Cd using a geochemical diffuse double-layer surface complexation model and found the oxide surfaces are relatively ineffective at readsorbing Cd in seawater due to surface-site competition by Mg and Ca. If the remobilization and reoxidation of Fe and Mn occurs frequently enough before sediment is buried significant amounts of Cd may be removed from the oxide surfaces. Because a much greater percentage of Mn than Fe becomes remobilized in these shelf sediments, metals closely associated with Mn oxides (like Cd) are more likely to show losses during deposition. ?? 2005 Elsevier Ltd. All rights reserved.
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Cardiomyopathy from 1,1-Difluoroethane Inhalation.
Kumar, Suwen; Joginpally, Tejaswini; Kim, David; Yadava, Mrinal; Norgais, Konchok; Laird-Fick, Heather S
2016-10-01
Consumer aerosol products can be inhaled for their psychoactive effects, but with attendant adverse health effects including "sudden sniffing death." Cardiomyopathy has rarely been described in association with 1,1-difluoroethane (DFE), a common aerosol propellant. We report a 33-year-old male who developed acute myocardial injury and global hypokinesis along with rhabdomyolysis, acute kidney injury, and fulminant hepatitis after 2 days' nearly continuous huffing. Workup for other causes, including underlying coronary artery disease, was negative. His cardiac function improved over time. The exact mechanism of DFE's effects is uncertain but may include catecholamine-induced cardiomyopathy, coronary vasospasm, or direct cellular toxicity.
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Yan, Zhao-Da; Zhou, Chong-Guang; Su, Shi-Chuan; Liu, Zhen-Tao; Wang, Xi-Zhen
2003-01-01
In order to predict and improve the performance of natural gas/diesel dual fuel engine (DFE), a combustion rate model based on forward neural network was built to study the combustion process of the DFE. The effect of the operating parameters on combustion rate was also studied by means of this model. The study showed that the predicted results were good agreement with the experimental data. It was proved that the developed combustion rate model could be used to successfully predict and optimize the combustion process of dual fuel engine.
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Factors influencing the dissolved iron input by river water to the open ocean
NASA Astrophysics Data System (ADS)
Krachler, R.; Jirsa, F.; Ayromlou, S.
The influence of natural metal chelators on the bio-available iron input to the ocean by river water was studied. Ferrous and ferric ions present as suspended colloidal particles maintaining the semblance of a dissolved load are coagulated and settled as their freshwater carrier is mixed with seawater at the continental boundary. However, we might argue that different iron-binding colloids become sequentially destabilized in meeting progressively increasing salinities. By use of a 59Fe tracer method, the partitioning of the iron load from the suspended and dissolved mobile fraction to storage in the sediments was measured with high accuracy in mixtures of natural river water with artificial sea water. The results show a characteristic sequence of sedimentation. Various colloids of different stability are removed from a water of increasing salinity, such as it is the case in the transition from a river water to the open sea. However, the iron transport capacities of the investigated river waters differed greatly. A mountainous river in the Austrian Alps would add only about 5% of its dissolved Fe load, that is about 2.0 µg L-1 Fe, to coastal waters. A small tributary draining a sphagnum peat-bog, which acts as a source of refractory low-molecular-weight fulvic acids to the river water, would add approximately 20% of its original Fe load, that is up to 480 µg L-1 Fe to the ocean's bio-available iron pool. This points to a natural mechanism of ocean iron fertilization by terrigenous fulvic-iron complexes originating from weathering processes occurring in the soils upstream.
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Factors influencing the dissolved iron input by river water to the open ocean
NASA Astrophysics Data System (ADS)
Krachler, R.; Jirsa, F.; Ayromlou, S.
2005-05-01
The influence of natural metal chelators on the bio-available iron input to the ocean by river water was studied. Ferrous and ferric ions present as suspended colloidal particles maintaining the semblance of a dissolved load are coagulated and settled as their freshwater carrier is mixed with seawater at the continental boundary. However, we might argue that different iron-binding colloids become sequentially destabilized in meeting progressively increasing salinities. By use of a 59Fe tracer method, the partitioning of the iron load from the suspended and dissolved mobile fraction to storage in the sediments was measured with high accuracy in mixtures of natural river water with artificial sea water. The results show a characteristic sequence of sedimentation. Various colloids of different stability are removed from a water of increasing salinity, such as it is the case in the transition from a river water to the open sea. However, the iron transport capacities of the investigated river waters differed greatly. A mountainous river in the Austrian Alps would add only about 5% of its dissolved Fe load, that is about 2.0 µg L-1 Fe, to coastal waters. A small tributary draining a sphagnum peat-bog, which acts as a source of refractory low-molecular-weight fulvic acids to the river water, would add approximately 20% of its original Fe load, that is up to 480 µg L-1 Fe to the ocean's bio-available iron pool. This points to a natural mechanism of ocean iron fertilization by terrigenous fulvic-iron complexes originating from weathering processes occurring in the soils upstream.
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Atmospheric Processing of Volcanic Glass: Effects on Iron Solubility and Redox Speciation.
Maters, Elena C; Delmelle, Pierre; Bonneville, Steeve
2016-05-17
Volcanic ash from explosive eruptions can provide iron (Fe) to oceanic regions where this micronutrient limits primary production. Controls on the soluble Fe fraction in ash remain poorly understood but Fe solubility is likely influenced during atmospheric transport by condensation-evaporation cycles which induce large pH fluctuations. Using glass powder as surrogate for ash, we experimentally simulate its atmospheric processing via cycles of pH 2 and 5 exposure. Glass fractional Fe solubility (maximum 0.4%) is governed by the pH 2 exposure duration rather than by the pH fluctuations, however; pH 5 exposure induces precipitation of Fe-bearing nanoparticles which (re)dissolve at pH 2. Glass leaching/dissolution release Fe(II) and Fe(III) which are differentially affected by changes in pH; the average dissolved Fe(II)/Fetot ratio is ∼0.09 at pH 2 versus ∼0.18 at pH 5. Iron release at pH 2 from glass with a relatively high bulk Fe(II)/Fetot ratio (0.5), limited aqueous Fe(II) oxidation at pH 5, and possibly glass-mediated aqueous Fe(III) reduction may render atmospherically processed ash a significant source of Fe(II) for phytoplankton. By providing new insight into the form(s) of Fe associated with ash as wet aerosol versus cloud droplet, we improve knowledge of atmospheric controls on volcanogenic Fe delivery to the ocean.
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Iron isotope constraints on arsenic release from Mekong Delta sediments, Cambodia
NASA Astrophysics Data System (ADS)
Matsumoto, T.; Yamaguchi, K. E.; Hirata, T.; Yamagata, Y.; Yamaguchi, A.; Abe, G.
2017-12-01
Arsenic-contaminated groundwater is a world-wide environmental problem and threatens more than 100 million people living in delta areas of South, SE and East Asia. It is typically associated with reducing aquifers with organic-rich alluvial sediments, little thermal gradients, low sulfate concentrations, and slow flushing rates. Such conditions are typical for low-lying countries in Asian deltas; however, compared to Bangladesh, Cambodia has received far less attention. Upon reductive dissolution of Fe-(oxyhydr)oxides that adsorbed As, Fe and As are released into solution as dissolved Fe2+ and arsenate, respectively. Following the oxidation of dissolved Fe2+, newly-formed Fe-(oxyhydr)oxides adsorb As again. Thus, in anoxic waters, concentrations of As correlate with those of dissolved Fe2+. Fluctuating redox conditions in the aquifer are control As release, although inhibition of adsorption of arsenate and arsenite onto the Fe-(oxyhydr)oxides occurs when the concentrations of phosphate, bicarbonate, silicate, and/or organic matter become sufficiently high. Biogeochemical redox reactions of Fe result in significant isotope fractionation (e.g., Johnson et al., 2008). We hypothesized that magnitude of isotope fractionation of Fe in the aquifer sediments, reflecting repeated (incomplete) redox reactions of Fe, may be proportional to the amount of total As release. We aim to calibrate the As release from aquifer sediment by Fe isotope analysis. As a preliminary study, series of sediment samples were collected from the Mekong Delta, Cambodia, in September 2016. Based on measurements by XRF, ICP-AES and ICP-MS, concentrations of As varied significantly covering the range from 4.5 to 15.5 µg/g with a median value of 11 µg/g (higher than the average crustal value of 5 µg/g), and those of Fe is from 2.6 to 9.7 wt.% with a median value of 7.1 wt.%. Concentrations of As and Fe show positive correlation (R2 = 0.72), indicating an effective redox cycling of Fe and As as stated above. Sediment incubation experiment to explore various pathways of As release would show time-series correlated changes in the Fe isotope compositions and As concentrations. The data obtained here are essential in investigating the mechanism of As release.
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Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer
NASA Astrophysics Data System (ADS)
Brown, C. J.; Schoonen, M. A. A.; Candela, J. L.
2000-11-01
Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O 2 and SO 42- in the aerobic zone, and to the reduction of SO 42- in the anaerobic zone; estimated rates of CO 2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO 2 production calculated from dissolved inorganic carbon mass transfer (2.55×10 -4 to 48.6×10 -4 mmol l -1 yr-1) generally were comparable to the calculated rates of CO 2 production by the combined reduction of O 2, Fe(III) and SO 42- (1.31×10 -4 to 15×10 -4 mmol l -1 yr-1). The overall increase in SO 42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in δ34S values along the flow path indicate that SO 42- loss through microbial reduction is exceeded by SO 42- gain through diffusion from sediments and through the oxidation of FeS 2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO 42--rich zones have been depleted by microbial reduction and resulted in localized SO 42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO 42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.
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Iron persistence in a distal hydrothermal plume supported by dissolved-particulate exchange
NASA Astrophysics Data System (ADS)
Fitzsimmons, Jessica N.; John, Seth G.; Marsay, Christopher M.; Hoffman, Colleen L.; Nicholas, Sarah L.; Toner, Brandy M.; German, Christopher R.; Sherrell, Robert M.
2017-02-01
Hydrothermally sourced dissolved metals have been recorded in all ocean basins. In the oceans' largest known hydrothermal plume, extending westwards across the Pacific from the Southern East Pacific Rise, dissolved iron and manganese were shown by the GEOTRACES program to be transported halfway across the Pacific. Here, we report that particulate iron and manganese in the same plume also exceed background concentrations, even 4,000 km from the vent source. Both dissolved and particulate iron deepen by more than 350 m relative to 3He--a non-reactive tracer of hydrothermal input--crossing isopycnals. Manganese shows no similar descent. Individual plume particle analyses indicate that particulate iron occurs within low-density organic matrices, consistent with its slow sinking rate of 5-10 m yr-1. Chemical speciation and isotopic composition analyses reveal that particulate iron consists of Fe(III) oxyhydroxides, whereas dissolved iron consists of nanoparticulate Fe(III) oxyhydroxides and an organically complexed iron phase. The descent of plume-dissolved iron is best explained by reversible exchange onto slowly sinking particles, probably mediated by organic compounds binding iron. We suggest that in ocean regimes with high particulate iron loadings, dissolved iron fluxes may depend on the balance between stabilization in the dissolved phase and the reversibility of exchange onto sinking particles.
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Liu, Y-Y; Haynes, R J
2013-01-01
The aim of this study was to examine the effects of replacement of phosphoric acid with nitric or acetic acid, and replacement of NaOH with KOH, as cleaning agents in dairy factories, on the effects that irrigation of dairy factory effluent (DFE) has on the soil-plant system. A 16-week greenhouse study was carried out in which the effects of addition of synthetic dairy factory effluent containing (a) milk residues alone or milk residues plus (b) H(3)PO(4)/NaOH, (c) H(3)PO(4)/HNO(3)/NaOH or (d) CH(3)COOH/KOH, on soil's chemical, physical and microbial properties and perennial ryegrass growth and nutrient uptake were investigated. The cumulative effect of DFE addition was to increase exchangeable Na, K, Ca, Mg, exchangeable sodium percentage, microbial biomass C and N and basal respiration in the soil. Dry matter yields of ryegrass were increased by additions of DFE other than that containing CH(3)COOH. Plant uptake of P, Ca and Mg was in the same order as their inputs in DFE but for Na; inputs were an order of magnitude greater than plant uptake. Replacement of NaOH by KOH resulted in increased accumulation of exchangeable K. The effects of added NaOH and KOH on promoting breakdown of soil aggregates during wet sieving (and formation of a < 0.25 mm size class) were similar. Replacement of H(2)PO(4) by HNO(3) is a viable but CH(3)COOH appears to have detrimental effects on plant growth. Replacement of NaOH by KOH lowers the likelihood of phytotoxic effects of Na, but K and Na have similar effects on disaggregation.
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Adaptive reconfigurable V-BLAST type equalizer for cognitive MIMO-OFDM radios
NASA Astrophysics Data System (ADS)
Ozden, Mehmet Tahir
2015-12-01
An adaptive channel shortening equalizer design for multiple input multiple output-orthogonal frequency division multiplexing (MIMO-OFDM) radio receivers is considered in this presentation. The proposed receiver has desirable features for cognitive and software defined radio implementations. It consists of two sections: MIMO decision feedback equalizer (MIMO-DFE) and adaptive multiple Viterbi detection. In MIMO-DFE section, a complete modified Gram-Schmidt orthogonalization of multichannel input data is accomplished using sequential processing multichannel Givens lattice stages, so that a Vertical Bell Laboratories Layered Space Time (V-BLAST) type MIMO-DFE is realized at the front-end section of the channel shortening equalizer. Matrix operations, a major bottleneck for receiver operations, are accordingly avoided, and only scalar operations are used. A highly modular and regular radio receiver architecture that has a suitable structure for digital signal processing (DSP) chip and field programable gate array (FPGA) implementations, which are important for software defined radio realizations, is achieved. The MIMO-DFE section of the proposed receiver can also be reconfigured for spectrum sensing and positioning functions, which are important tasks for cognitive radio applications. In connection with adaptive multiple Viterbi detection section, a systolic array implementation for each channel is performed so that a receiver architecture with high computational concurrency is attained. The total computational complexity is given in terms of equalizer and desired response filter lengths, alphabet size, and number of antennas. The performance of the proposed receiver is presented for two-channel case by means of mean squared error (MSE) and probability of error evaluations, which are conducted for time-invariant and time-variant channel conditions, orthogonal and nonorthogonal transmissions, and two different modulation schemes.
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Kim, Ji-Yun; Jeong, Mi Sook; Park, Mi Kyung; Lee, Mi-Kyung; Seo, Seong Jun
2014-01-01
Atopic dermatitis (AD) is a complicated skin condition influenced by genetic background and environmental factors. In this study, we applied Dermatophagoides farinae body extract (DfE) to the barrier-disrupted skin of NC/Nga mice twice a week for 8 weeks to identify the clinical and immunological factors in AD progression. Repeated application of the DfE to the skin of NC/Nga mice showed the similar consequences for the natural course of progression in human AD, histologically and immunologically. We confirmed that the AD-like skin lesions in NC/Nga mice did not last for the whole period of our experiment in spite of repeated topical applications of DfE twice a week. Topical DfE stimulation increased the skin mRNA expressions of Th1-, Th2- and Th17-related cytokines in the acute phase. The expression patterns of IL-4 and IL-13 in splenic T cells and skin lesions were consistent with the time course alterations of clinical features of AD-like skin symptoms. We also showed that there was a remission phase either just before or right after the chronic phase in this experimental model. Interestingly, splenic T-cell-derived IL-5 expression began to increase in the chronic phase, while skin-derived IL-5 mRNA expression increased in the acute phase. In conclusion, our results suggest that we should pay attention to the characteristics of each stage of AD progression and choose a suitable corresponding stage of animal model not only to elucidate the pathogenesis of AD but also to develop and evaluate therapeutic drugs for AD. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
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NASA Astrophysics Data System (ADS)
Atekwana, E. A.; Enright, A.; Ntarlagiannis, D.; Slater, L. D.; Bernier, R.; Beaver, C. L.; Rossbach, S.
2016-12-01
We investigated the chemical and stable carbon isotope composition of groundwater in a highly saline aquifer contaminated with hydrocarbon. Our aim to evaluate hydrocarbon degradation and to constrain the geochemical conditions that generated high anomalous magnetic susceptibility (MS) signatures observed at the water table interface. The occurrence of high MS in the water table fluctuating zone has been attributed to microbial iron reduction, suggesting the use of MS as a proxy for iron cycling. The highly saline aquifer had total dissolved solids concentrations of 3.7 to 29.3 g/L and sulfate concentrations of 787 to 37,100 mg/L. We compared our results for groundwater locations with high hydrocarbon contamination (total petroleum hydrocarbon (TPH) >10 mg/L), at lightly contaminated (TPH <10 mg/L) and locations with no contaminations. Our results for the terminal electron acceptors (TEAs) dissolved oxygen (DO), nitrate (NO3-), dissolved iron (Fe2+) , dissolved manganese (Mn2+), sulfate (SO42-) and methane (CH4) suggest a chemically heterogeneous aquifer, probably controlled by heterogeneous distribution of TEAs and contamination (type of hydrocarbon, phase and age of contamination). The concentrations of dissolved inorganic carbon (DIC) ranged from 67 to 648 mg C/L and the stable carbon isotope (δ13CDIC) ranged from -30.0‰ to 1.0 ‰ and DIC-δ13CDIC modeling indicates that the carbon in the DIC is derived primarily from hydrocarbon degradation. The concentrations of Fe2+ in the aquifer ranged from 0.1 to 55.8 mg/L, but was mostly low, averaging 2.7+10.9 mg/L. Given the low Fe2+ [AE1] in the aqueous phase and the high MS at contaminated locations, we suggest that the high MS observed does not arise from iron reduction but rather from sulfate reduction. Sulfate reduction produces H2S which reacts with Fe2+ to produce ferrous sulfide (Fe2+S) or the mixed valence greigite (Fe2+Fe3+2S4). We conclude that in highly saline aquifers with high concentrations of sulfate and contaminated with hydrocarbon, dominance of sulfate reduction as the TEA is responsible for iron cycling and therefore the high MS associated with biodegradation. [AE1]What about sulfate concentrations? And the range in salinity? You need to add these values to the bastrcat
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Mohanty, Subhasish; Barua, Bipul; Listwan, Joseph
In financial year 2017, we are focusing on developing a mechanistic fatigue model of surge line pipes for pressurized water reactors (PWRs). To that end, we plan to perform the following tasks: (1) conduct stress- and strain-controlled fatigue testing of surge-line base metal such as 316 stainless steel (SS) under constant, variable, and random fatigue loading, (2) develop cyclic plasticity material models of 316 SS, (3) develop one-dimensional (1D) analytical or closed-form model to validate the material models and to understand the mechanics associated with 316 SS cyclic hardening and/or softening, (4) develop three-dimensional (3D) finite element (FE) models withmore » implementation of evolutionary cyclic plasticity, and (5) develop computational fluid dynamics (CFD) model for thermal stratification, thermal-mechanical stress, and fatigue of example reactor components, such as a PWR surge line under plant heat-up, cool-down, and normal operation with/without grid-load-following. This semi-annual progress report presents the work completed on the above tasks for a 316 SS laboratory-scale specimen subjected to strain-controlled cyclic loading with constant, variable, and random amplitude. This is the first time that the accurate 3D-FE modeling of the specimen for its entire fatigue life, including the hardening and softening behavior, has been achieved. We anticipate that this work will pave the way for the development of a fully mechanistic-computer model that can be used for fatigue evaluation of safety-critical metallic components, which are traditionally evaluated by heavy reliance on time-consuming and costly test-based approaches. This basic research will not only help the nuclear reactor industry for fatigue evaluation of reactor components in a cost effective and less time-consuming way, but will also help other safety-related industries, such as aerospace, which is heavily dependent on test-based approaches, where a single full-scale fatigue test can cost millions of dollars and require years of effort to conduct. Toward our goal of demonstration of fully mechanistic fatigue evaluation of reactor components, we also started work on developing a component-level computer model of reactor components, such as 316 SS surge line pipe. This requires developing a thermal-mechanical stress analysis model of the reactor surge line, which, in turn, requires time-dependent temperature and stratification information along the boundary of the pipe. Toward that goal, CFD models of surge lines are being developed. In this report, we also present some preliminary results showing the temperature conditions along the surge line wall under reactor heat-up, cool-down, and steady-state power operation.« less
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Reinsch, Brian C; Forsberg, Brady; Penn, R Lee; Kim, Christopher S; Lowry, Gregory V
2010-05-01
Nanoscale zerovalent iron (NZVI) that was aged in simulated groundwater was evaluated for alterations in composition and speciation over 6 months to understand the possible transformations NZVI could undergo in natural waters. NZVI was exposed to 10 mN of various common groundwater anions (Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), and HCO(3)(-)) or to dissolved oxygen (saturated, approximately 9 mg/L). Fresh and exposed NZVI samples, along with Fe-oxide model compounds, were then analyzed using synchrotron radiation X-ray absorption spectroscopy (XAS) to yield both relative oxidation state, using the X-ray absorption near edge structure (XANES), and quantitative speciation information regarding the types and proportions of mineral species present, from analysis of the extended X-ray absorption fine structure (EXAFS). Over 1 month of aging the dissolved anions inhibited the oxidation of the NZVI to varying degrees. Aging for 6 months, however, resulted in average oxidation states that were similar to each other regardless of the anion used, except for nitrate. Nitrate passivated the NZVI surface such that even after 6 months of aging the particles retained nearly the same mineral and Fe(0) content as fresh NZVI. Linear least-squares combination fitting (LCF) of the EXAFS spectra for 1 month-aged samples indicated that the oxidized particles remain predominantly a binary phase system containing Fe(0) and Fe(3)O(4), while the 6 month aged samples contained additional mineral phases such as vivianite (Fe(3)(PO(4))(2).8H(2)O) and iron sulfate species, possibly schwertmannite (Fe(3+)(16)O(16)(OH,SO(4))(12-13).10-12H(2)O). The presence of these additional mineral species was confirmed using synchrotron-based X-ray diffraction (XRD). NZVI exposed to water saturated with dissolved oxygen showed a rapid (<24 h) loss of Fe(0) and evolved both magnetite and maghemite (gamma-Fe(2)O(3)) within the oxide layer. These findings have implications toward the eventual fate, transport, and toxicity of NZVI used for groundwater remediation.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.
2014-02-28
Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectramore » of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.« less
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Cu-Ni-Fe anodes having improved microstructure
Bergsma, S. Craig; Brown, Craig W.
2004-04-20
A method of producing aluminum in a low temperature electrolytic cell containing alumina dissolved in an electrolyte. The method comprises the steps of providing a molten electrolyte having alumina dissolved therein in an electrolytic cell containing the electrolyte. A non-consumable anode and cathode is disposed in the electrolyte, the anode comprised of Cu--Ni--Fe alloys having single metallurgical phase. Electric current is passed from the anode, through the electrolyte to the cathode thereby depositing aluminum on the cathode, and molten aluminum is collected from the cathode.
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Photochemical Reactivity of Dissolved Organic Matter in Boreal Lakes
NASA Astrophysics Data System (ADS)
Gu, Y.; Vuorio, K.; Tiirola, M.; Perämäki, S.; Vahatalo, A.
2016-12-01
Boreal lakes are rich in dissolved organic matter (DOM) that terrestrially derived from forest soil and wetland, yet little is known about potential for photochemical transformation of aquatic DOM in boreal lakes. Transformation of chromophoric dissolved organic matter (CDOM) can decrease water color and enhance microbial mineralization, affecting primary production and respiration, which both affect the CO2 balance of the lakes. We used laboratory solar radiation exposure experiments with lake water samples collected from 54 lakes located in Finland and Sweden, representing different catchment composition and watershed location to assess photochemical reactivity of DOM. The pH of water samples ranged from 5.4 to 8.3, and the concentrations of dissolved iron (Fe) were between < 0.06 and 22 μmol L-1. The filtered water samples received simulated solar radiation corresponding to a daily dose of sunlight, and photomineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) was measured for determination of spectral apparent quantum yields (AQY). During irradiation, photobleaching decreased the absorption coefficients of CDOM at 330 nm between 4.9 and 79 m-1 by 0.5 to 11 m-1. Irradiation generated DIC from 2.8 to 79 μmol C L-1. The AQY at 330 nm ranged between 31 and 273 ×10-6 mol C mol photons-1 h-1, which was correlated positively with concentration of dissolved Fe, and negatively with pH. Further statistical analyze indicated that the interaction between pH and Fe may explain much of the photochemical reactivity of DOM in the examined lakes, and land cover concerns main catchment areas also can have impact on the photoreaction process. This study may suggest how environmental conditions regulate DOM photomineralization in boreal lakes.
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Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Natsuike, Masafumi; Ito, Hiroaki; Watanabe, Toru; Yoshimura, Chihiro
2017-08-01
Ferrous iron (Fe[II]) oxidation by dissolved oxygen was investigated in the Shizugawa Bay watershed with particular attention given to the effect of dissolved organic matter (DOM) properties on Fe(II) oxidation. To cover a wide spectrum of DOM composition, water samples were collected from various water sources including freshwater (e.g., river water and wastewater effluent) and coastal seawater. Measurement of nanomolar Fe(II) oxidation by using luminol chemiluminescence under dark, air-saturated conditions at 25 °C indicated that spatio-temporal variation of the second-order rate constant (6.7-74.5 M -1 s -1 ) was partially explained by the variation of the sample pH (7.5-8.6). However, at comparable pH values, the oxidation rates for freshwater were generally greater than those for coastal seawater. The substantial decline in oxidation rate constant after the removal of humic-type (allochthonous) DOM suggested that this hydrophobic DOM is a key factor that accelerates the Fe(II) oxidation in the freshwater samples. Observed lower oxidation rates for coastal seawater compared with freshwater and organic ligand-free seawater were likely associated with microbially derived autochthonous DOM, and the variation of Fe(II) oxidation at a fixed pH was best described by fluorescence index that represents the proportion of autochthonous and allochthonous DOM in natural waters. Consistently, Fe(II) oxidation was found to be slower in the presence of cellular exudates from phytoplankton. The present study highlighted the significant effect of DOM composition on the Fe(II) oxidation in inland and coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Roy, Moutusi; Martin, Jonathan B.; Smith, Christopher G.; Cable, Jaye E.
2011-01-01
Iron oxides are important terminal electron acceptors for organic carbon (OC) remineralization in subterranean estuaries, particularly where oxygen and nitrate concentrations are low. In Indian River Lagoon, Florida, USA, terrestrial Fe-oxides dissolve at the seaward edge of the seepage face and flow upward into overlying marine sediments where they precipitate as Fe-sulfides. The dissolved Fe concentrations vary by over three orders of magnitude, but Fe-oxide dissolution rates are similar across the 25-m wide seepage face, averaging around 0.21 mg/cm2/yr. The constant dissolution rate, but differing concentrations, indicate Fe dissolution is controlled by a combination of increasing lability of dissolved organic carbon (DOC) and slower porewater flow velocities with distance offshore. In contrast, the average rate constants of Fe-sulfide precipitation decrease from 21.9 × 10-8 s-1 to 0.64 × 10-8 s-1 from the shoreline to the seaward edge of the seepage face as more oxygenated surface water circulates through the sediment. The amount of OC remineralized by Fe-oxides varies little across the seepage face, averaging 5.34 × 10-2 mg/cm2/yr. These rates suggest about 3.4 kg of marine DOC was remineralized in a 1-m wide, shore-perpendicular strip of the seepage face as the terrestrial sediments were transgressed over the past 280 years. During this time, about 10 times more marine solid organic carbon (SOC) accumulated in marine sediments than were removed from the underlying terrestrial sediments. Indian River Lagoon thus appears to be a net sink for marine OC.
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Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite
Palandri, J.L.; Rosenbauer, R.J.; Kharaka, Y.K.
2005-01-01
Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.
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Kernel-based discriminant feature extraction using a representative dataset
NASA Astrophysics Data System (ADS)
Li, Honglin; Sancho Gomez, Jose-Luis; Ahalt, Stanley C.
2002-07-01
Discriminant Feature Extraction (DFE) is widely recognized as an important pre-processing step in classification applications. Most DFE algorithms are linear and thus can only explore the linear discriminant information among the different classes. Recently, there has been several promising attempts to develop nonlinear DFE algorithms, among which is Kernel-based Feature Extraction (KFE). The efficacy of KFE has been experimentally verified by both synthetic data and real problems. However, KFE has some known limitations. First, KFE does not work well for strongly overlapped data. Second, KFE employs all of the training set samples during the feature extraction phase, which can result in significant computation when applied to very large datasets. Finally, KFE can result in overfitting. In this paper, we propose a substantial improvement to KFE that overcomes the above limitations by using a representative dataset, which consists of critical points that are generated from data-editing techniques and centroid points that are determined by using the Frequency Sensitive Competitive Learning (FSCL) algorithm. Experiments show that this new KFE algorithm performs well on significantly overlapped datasets, and it also reduces computational complexity. Further, by controlling the number of centroids, the overfitting problem can be effectively alleviated.
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Liu, Shasha; Zhu, Yuanrong; Liu, Leizhen; He, Zhongqi; Giesy, John P; Bai, Yingchen; Sun, Fuhong; Wu, Fengchang
2018-03-01
Complexation and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in aquatic systems. Thus, coagulation and fractionation of DOM derived from aquatic plants by Ca(II), Al(III), and Fe(III) ions were investigated. Metal ion-induced removal of DOM was determined by analyzing dissolved organic carbon in supernatants after addition of these metal cations individually. After additions of metal ions, both dissolved and coagulated organic fractions were characterized by use of fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and Fourier transform infrared (FT-IR) spectroscopy. Addition of Ca(II), Fe(III) or Al(III) resulted in net removal of aquatic plant-derived DOM. Efficiencies of removal of DOM by Fe(III) or Al(III) were greater than that by Ca(II). However, capacities to remove plant-derived DOM by the three metals were less than which had been previously reported for humic materials. Molecular and structural features of plant-derived DOM fractions in associations with metal cations were characterized by changes in fluorescent components and infrared absorption peaks. Both aromatic and carboxylic-like organic matters could be removed by Ca(II), Al(III) or Fe(III) ions. Whereas organic matters containing amides were preferentially removed by Ca(II), and phenolic materials were selectively removed by Fe(III) or Al(III). These observations indicated that plant-derived DOM might have a long-lasting effect on water quality and organisms due to its poor coagulation with metal cations in aquatic ecosystems. Plant-derived DOM is of different character than natural organic matter and it is not advisable to attempt removal through addition of metal salts during treatment of sewage. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Campbell, K.M.; Root, R.; O'Day, P. A.; Hering, J.G.
2008-01-01
Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.
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Influence of humic acid imposed changes of ferrihydrite aggregation on microbial Fe(III) reduction
NASA Astrophysics Data System (ADS)
Amstaetter, Katja; Borch, Thomas; Kappler, Andreas
2012-05-01
Microbial reduction of Fe(III) minerals at neutral pH is faced by the problem of electron transfer from the cells to the solid-phase electron acceptor and is thought to require either direct cell-mineral contact, the presence of Fe(III)-chelators or the presence of electron shuttles, e.g. dissolved or solid-phase humic substances (HS). In this study we investigated to which extent the ratio of Pahokee Peat Humic Acids (HA) to ferrihydrite in the presence and absence of phosphate influences rates of Fe(III) reduction by Shewanella oneidensis MR-1 and the identity of the minerals formed. We found that phosphate generally decreased reduction rates by sorption to the ferrihydrite and surface site blocking. In the presence of low ferrihydrite concentrations (5 mM), the addition of HA helped to overcome this inhibiting effect by functioning as electron shuttle between cells and the ferrihydrite. In contrast, at high ferrihydrite concentrations (30 mM), the addition of HA did not lead to an increase but rather to a decrease in reduction rates. Confocal laser scanning microscopy images and ferrihydrite sedimentation behaviour suggest that the extent of ferrihydrite surface coating by HA influences the aggregation of the ferrihydrite particles and thereby their accessibility for Fe(III)-reducing bacteria. We further conclude that in presence of dissolved HA, iron reduction is stimulated through electron shuttling while in the presence of only sorbed HA, no stimulation by electron shuttling takes place. In presence of phosphate the stimulation effect did not occur until a minimum concentration of 10 mg/l of dissolved HA was reached followed by increasing Fe(III) reduction rates up to dissolved HA concentrations of approximately 240 mg/l above which the electron shuttling effect ceased. Not only Fe(III) reduction rates but also the mineral products changed in the presence of HA. Sequential extraction, XRD and 57Fe-Mössbauer spectroscopy showed that crystallinity and grain size of the magnetite produced by Fe(III) reduction in the presence of HA is lower than the magnetite produced in the absence of HA. In summary, this study shows that both the concentration of HA and Fe(III) minerals strongly influence microbial Fe(III) reduction rates and the mineralogy of the reduction products. Thus, deviations in iron (hydr)oxide reactivity with changes in aggregation state, such as HA induced ferrihydrite aggregation, need to be considered within natural environments.
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Magnesium transport extraction of transuranium elements from LWR fuel
Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean
1992-01-01
A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.
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Borrok, D.M.; Wanty, R.B.; Ian, Ridley W.; Lamothe, P.J.; Kimball, B.A.; Verplanck, P.L.; Runkel, R.L.
2009-01-01
Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, ??56Fe and ??66Zn isotopic signatures of filtered stream water samples varied by ???3.5??? and 0.4???, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in ??56Fe were linked to redox and precipitation reactions occurring in the stream, while changes in ??66Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<-2.0???) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4???). Acidic drainage from mine wastes contributed heavier dissolved Fe (???+0.5???) and lighter Zn (???+0.2???) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (??56Fe ??? 0???) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds. ?? 2009 Elsevier Ltd.
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Tian, Zeyuan; Feng, Yong; Guan, Yiyi; Shao, Binbin; Zhang, Yalei; Wu, Deli
2017-12-05
Freshly prepared carbonate structural Fe(II) (CSF) was used to immobilize As(III) and As(V) in wastewater under oxic and anoxic conditions. Dissolved oxygen was found to exert opposite effects on these two arsenic species. The sorption density of As(III) was higher under oxic conditions, whereas that of As(V) was higher under anoxic conditions. X-ray diffraction and infrared spectroscopic analyses indicated that crystalline parasymplesite (Fe(II) 3 (AsO 4 ) 2 ·8H 2 O) was formed when As(V) was removed under anoxic conditions, while an amorphous Fe-As-containing precipitate was formed when As(III) was removed under oxic conditions. The distribution of arsenic and iron between the solution and sediments suggested that the oxidation of structural Fe(II) promoted coprecipitation process and inhibited surface complexation. X-ray photoelectron spectroscopic analyses revealed that more As(III) was oxidized under oxic condition, which contributed to a higher sorption capacity for As(III). The formation of parasymplesite through surface complexation/precipitation was proposed to be more effective for the removal of As(V) by CSF, while As(III) was more efficiently removed through coprecipitation. Together, the results suggest that CSF may be an effective material for sequestering both As(III) and As(V). In addition, attention should be paid to the dissolved oxygen content when remediating different arsenic species.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Senko, John M.; Wanjugi, Pauline; Lucas, Melanie
2008-06-12
We characterized the microbiologically mediated oxidative precipitation of Fe(II) from coalminederived acidic mine drainage (AMD) along flow-paths at two sites in northern Pennsylvania. At the Gum Boot site, dissolved Fe(II) was efficiently removed from AMD whereas minimal Fe(II) removal occurred at the Fridays-2 site. Neither site received human intervention to treat the AMD. Culturable Fe(II) oxidizing bacteria were most abundant at sampling locations along the AMD flow path corresponding to greatest Fe(II) removal and where overlying water contained abundant dissolved O2. Rates of Fe(II) oxidation determined in laboratory-based sediment incubations were also greatest at these sampling locations. Ribosomal RNA intergenicmore » spacer analysis and sequencing of partial 16S rRNA genes recovered from sediment bacterial communities revealed similarities among populations at points receiving regular inputs of Fe(II)-rich AMD and provided evidence for the presence of bacterial lineages capable of Fe(II) oxidation. A notable difference between bacterial communities at the two sites was the abundance of Chloroflexi-affiliated 16S rRNA gene sequences in clone libraries derived from the Gum Boot sediments. Our results suggest that inexpensive and reliable AMD treatment strategies can be implemented by mimicking the conditions present at the Gum Boot field site.« less
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ROLE OF IRON AND MANGANESE OXIDES IN BIOSOLIDS AND BIOSOLIDS-AMENDED SOILS ON METAL BINDING
Biosolids contain high levels of Fe, Mn, and Al. Surfaces of freshly precipitated metal oxides, especially Fe and Mn, are known to be highly active sites for most dissolved metal ion species. We nw have metal sorption/desorption data that illustrate the importance of Fe and Mn fr...
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1D diffusion models may be used to estimate rates of production and consumption of dissolved metabolites in marine sediments, but are applied less often to the solid phase. Here we used a numerical inverse method to estimate solid phase Fe(III) and Fe(II) consumption and product...
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NASA Astrophysics Data System (ADS)
Krupińska, Izabela
2017-09-01
One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.
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NASA Astrophysics Data System (ADS)
Helgoe, J. M.; Townsend, E.; John, S.
2014-12-01
A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.
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Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments
NASA Astrophysics Data System (ADS)
Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng
2017-12-01
Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (<2 μm), the size fraction most prone to long-distance transport as dust. Samples were analyzed by sequential chemical extraction, X-ray diffraction, and diffuse reflectance spectrometry. Our results show that Fe dissolved from easily reducible iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.
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On the early fate of hydrothermal iron at deep-sea vents: A reassessment after in situ filtration
NASA Astrophysics Data System (ADS)
Waeles, M.; Cotte, L.; Pernet-Coudrier, B.; Chavagnac, V.; Cathalot, C.; Leleu, T.; Laës-Huon, A.; Perhirin, A.; Riso, R. D.; Sarradin, P.-M.
2017-05-01
Deep-sea hydrothermal venting is now recognized as a major source of iron (Fe), an essential trace element that controls marine productivity. However, the reactions occurring during dispersal from buoyant plumes to neutrally buoyant hydrothermal plumes are still poorly constrained. Here we report for the first time on the dissolved-particulate partition of Fe after in situ filtration at the early stage of mixing at different hydrothermal discharges, i.e., Lucky Strike (37°N), TAG (26°N), and Snakepit (23°N) on the Mid-Atlantic Ridge. We found that hydrothermal iron is almost completely preserved (>90%) in the dissolved fraction, arguing for low iron-bearing sulfide precipitation of iron in basalt-hosted systems with low Fe:H2S ratios. This result can only be explained by a kinetically limited formation of pyrite. The small part of Fe being precipitated as sulfides in the mixing gradient (<10%) is restricted to the inclusion of Fe in minerals of high Cu and Zn content. We also show that secondary venting is a source of Fe-depleted hydrothermal solutions. These results provide new constrains on Fe fluxes from hydrothermal venting.
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Estimates of atmospheric O2 in the Paleoproterozoic from paleosols
NASA Astrophysics Data System (ADS)
Kanzaki, Yoshiki; Murakami, Takashi
2016-02-01
A weathering model was developed to constrain the partial pressure of atmospheric O2 (PO2) in the Paleoproterozoic from the Fe records in paleosols. The model describes the Fe behavior in a weathering profile by dissolution/precipitation of Fe-bearing minerals, oxidation of dissolved Fe(II) to Fe(III) by oxygen and transport of dissolved Fe by water flow, in steady state. The model calculates the ratio of the precipitated Fe(III)-(oxyhydr)oxides from the dissolved Fe(II) to the dissolved Fe(II) during weathering (ϕ), as a function of PO2 . An advanced kinetic expression for Fe(II) oxidation by O2 was introduced into the model from the literature to calculate accurate ϕ-PO2 relationships. The model's validity is supported by the consistency of the calculated ϕ-PO2 relationships with those in the literature. The model can calculate PO2 for a given paleosol, once a ϕ value and values of the other parameters relevant to weathering, namely, pH of porewater, partial pressure of carbon dioxide (PCO2), water flow, temperature and O2 diffusion into soil, are obtained for the paleosol. The above weathering-relevant parameters were scrutinized for individual Paleoproterozoic paleosols. The values of ϕ, temperature, pH and PCO2 were obtained from the literature on the Paleoproterozoic paleosols. The parameter value of water flow was constrained for each paleosol from the mass balance of Si between water and rock phases and the relationships between water saturation ratio and hydraulic conductivity. The parameter value of O2 diffusion into soil was calculated for each paleosol based on the equation for soil O2 concentration with the O2 transport parameters in the literature. Then, we conducted comprehensive PO2 calculations for individual Paleoproterozoic paleosols which reflect all uncertainties in the weathering-relevant parameters. Consequently, robust estimates of PO2 in the Paleoproterozoic were obtained: 10-7.1-10-5.4 atm at ∼2.46 Ga, 10-5.0-10-2.5 atm at ∼2.15 Ga, 10-5.2-10-1.7 atm at ∼2.08 Ga and more than 10-4.6-10-2.0 atm at ∼1.85 Ga. Comparison of the present PO2 estimates to those in the literature suggests that a drastic rise of oxygen would not have occurred at ∼2.4 Ga, supporting a slightly rapid rise of oxygen at ∼2.4 Ga and a gradual rise of oxygen in the Paleoproterozoic in long term.
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Effects of dissolved oxygen on dye removal by zero-valent iron.
Wang, Kai-Sung; Lin, Chiou-Liang; Wei, Ming-Chi; Liang, Hsiu-Hao; Li, Heng-Ching; Chang, Chih-Hua; Fang, Yung-Tai; Chang, Shih-Hsien
2010-10-15
Effects of dissolved oxygen concentrations on dye removal by zero-valent iron (Fe(0)) were investigated. The Vibrio fischeri light inhibition test was employed to evaluate toxicity of decolorized solution. Three dyes, Acid Orange 7 (AO7, monoazo), Reactive Red 120 (RR120, diazo), and Acid Blue 9 (AB9, triphenylmethane), were selected as model dyes. The dye concentration and Fe(0) dose used were 100 mg L(-1) and 30 g L(-1), respectively. Under anoxic condition, the order for dye decolorization was AO7>RR120>AB9. An increase in the dissolved oxygen concentrations enhanced decolorization and chemical oxygen demand (COD) removal of the three dyes. An increase in gas flow rates also improved dye and COD removals by Fe(0). At dissolved oxygen of 6 mg L(-1), more than 99% of each dye was decolorized within 12 min and high COD removals were obtained (97% for AO7, 87% for RR120, and 93% for AB9). The toxicity of decolorized dye solutions was low (I(5)<40%). An increase in DO concentrations obviously reduced the toxicity. When DO above 2 mg L(-1) was applied, low iron ion concentration (13.6 mg L(-1)) was obtained in the decolorized AO7 solution. 2010 Elsevier B.V. All rights reserved.
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Rates of arsenopyrite oxidation by oxygen and Fe(III) at pH 1.8-12.6 and 15-45 degrees C.
Yu, Yunmei; Zhu, Yongxuan; Gao, Zhenmin; Gammons, Christopher H; Li, Denxian
2007-09-15
The oxidation rate of arsenopyrite by dissolved oxygen was measured using a mixed flow reactor at dissolved O2 concentrations of 0.007-0.77 mM, pH 1.8-12.6, and temperatures of 15-45 degrees C. As(III) was the dominant redox species (>75%) in the experimental system, and the As(III)/As(V) ratio of effluent waters did not change with pH. The results were used to derive the following rate law expression (valid between pH 1.8 and 6.4): r = 10((-2211 +/- 57)T) (mO2)(0.45 +/- 0.05), where r is the rate of release of dissolved As in mol m(-2) s(-1) and T is in Kelvin. Activation energies (Ea) for oxidation of arsenopyrite by 02 at pH 1.8 and 5.9 are 43 and 57 kJ/mol, respectively, and they compare to an Ea value of 16 kJ/mol for oxidation by Fe(III) at pH 1.8. Apparent As release rates passed through a minimum in the pH range 7-8, which may have been due to oxidation of Fe2+ to hydrous ferric oxide (HFO) with attenuation of dissolved As onto the freshly precipitated HFO.
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NASA Astrophysics Data System (ADS)
Shim, M.; Swarzenski, P. W.; Shiller, A. M.
2010-12-01
The Mississippi River (MR) plays an important role as a major fluvial source of dissolved and particulate materials for the Gulf of Mexico (GOM). This region is periodically disturbed by tropical weather systems including major hurricanes. Such storms have the potential to stir up the normally stratified water column of the Louisiana Shelf and thus can serve as a mechanism for the abrupt termination of seasonal bottom water hypoxia. Additionally, strong tropical systems can cause the resuspension of shelf bottom sediments which could result in the injection of trace elements into the water column. In the summer of 2005, two major hurricanes, Katrina and Rita, passed over the Louisiana Shelf within a month of each other. Three weeks after Rita, we participated in a survey of the waters of the Mississippi River delta outflow, examining the distributions of trace elements (including Ba, Co, Cr, Cs, Cu, Fe, Mn, Ni, Re, U, V, and Zn) in a comparison with previous results in this area. We indeed observed that there was limited stratification on the shelf and that bottom waters were no longer hypoxic. This resulted, for instance, in bottom water dissolved Mn being lower than is typically observed during hypoxia, but with concentrations still compatible with Mn-O2 trends previously reported. Interestingly, for no element were we able to identify an obvious effect of sediment resuspension on its distribution. In general, elemental distributions were compatible with previous observations in the Mississippi outflow system. Co and Re, which have not been reported for this system previously, showed behavior consistent with other systems: input for Co likely from desorption and conservative mixing for Re. For Cs, an element for which there is little information regarding its estuarine behavior, conservative mixing was also observed. Our filtration method, which allowed us to distinguish the dissolved (<0.02 µm) from colloidal (0.02 - 0.45 µm) phase, revealed significant colloidal fractions for Fe and Zn, only. For Fe, the colloidal phase was the dominant fraction and was rapidly removed at low salinity. Dissolved Fe, in contrast, persisted out to mid-salinities, being removed in a similar fashion to nitrate. This ability to distinguish the smaller Fe (likely dominantly organically complexed) from larger colloidal suspensates may be useful in better interpreting the bioavailablity of the Fe in estuarine systems.
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Seasonality of major redox constituents in a shallow subterranean estuary
NASA Astrophysics Data System (ADS)
O'Connor, Alison E.; Krask, Julie L.; Canuel, Elizabeth A.; Beck, Aaron J.
2018-03-01
The subterranean estuary (STE), the subsurface mixing zone of outflowing fresh groundwater and infiltrating seawater, is an area of extensive geochemical reactions that determine the composition of groundwater that flows into coastal environments. This study examined the porewater composition of a shallow STE (<5 m depth) in Gloucester Point, VA (USA) over two years to determine seasonal variations in dissolved organic carbon (DOC) and the reduced metabolites Fe, Mn, and sulfide. An additional aim of this study was to investigate the relative importance of salinity gradients (which have great geochemical influence in surface estuaries) versus redox gradients on STE geochemistry. Two freshwater endmembers were identified, between which redox potential and composition varied with depth-a shallow freshwater endmember was oxidizing and high in DOC, whereas a deep freshwater endmember was reducing, lower in DOC, and high in sulfide. Results showed that dissolved Fe, Mn, and sulfide varied along a redox gradient distinct from the salinity gradient, and that three-endmember mixing was required to quantify non-conservative chemical addition/removal in the STE. In addition to salinity, humic carbon was used as a quasi-conservative tracer to quantify mixing according to a three-endmember model. The vertical distributions of DOC and reduced metabolites remained approximately constant over time, but concentrations varied with season. Dissolved organic carbon concentrations were greatest in the summer, and shallow meteoric groundwater supplied the majority of DOC to the STE. In summer, there was additional evidence for shallow non-conservative addition of DOC. Dissolved Fe and Mn were highest in a subsurface plume through the middle of the STE (100-140 cm below sediment surface at the high tide line) which was characterized by higher concentrations and greater non-conservative addition in the winter. In contrast, sulfide was higher in summer at depths within the Fe and Mn plume (100-140 cm). We attribute the contrasting seasonal patterns of dissolved Fe, Mn, and sulfide to differences in microbial response to temperature changes and organic matter availability, and to competition at the ferrous-sulfidic transition zone between dissimilatory metal reduction and sulfate reduction, leading to sulfate/sulfur reducing bacteria (SRB) being more active in summer and metal reducers being more active in winter. Throughout the STE, seasonal temperature and DOC variations determined the spatial distribution and geochemical cycling of Fe, Mn, and sulfur.
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Slenkamp, Karla M.; Lynch, Michael S.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira
2016-01-01
Using polarization-selective two-dimensional infrared (2D IR) and infrared pump-probe spectroscopies, we study vibrational relaxation of the four cyanide stretching (νCN) vibrations found in [(NH3)5RuIIINCFeII(CN)5]− (FeRu) dissolved in D2O or formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5]4− (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled νCN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the νCN modes are ∼2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the νCN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on ∼1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans νCN modes exhibit a ∼3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic νCN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent. PMID:27158634
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Slenkamp, Karla M; Lynch, Michael S; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira
2016-03-01
Using polarization-selective two-dimensional infrared (2D IR) and infrared pump-probe spectroscopies, we study vibrational relaxation of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O or formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled νCN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the νCN modes are ∼2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the νCN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on ∼1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans νCN modes exhibit a ∼3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic νCN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent.
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Matthies, R; Aplin, A C; Horrocks, B R; Mudashiru, L K
2012-04-01
Cyclic-, Differential Pulse- and Steady-state Microdisc Voltammetry (CV, DPV, SMV) techniques have been used to quantify the occurrence and fate of dissolved Fe(ii)/Fe(iii), nano-particulate and micro-particulate iron over a 12 month period in a series of net-acidic and net-alkaline coal mine drainages and passive treatment systems. Total iron in the mine waters is typically 10-100 mg L(-1), with values up to 2100 mg L(-1). Between 30 and 80% of the total iron occurs as solid phase, of which 20 to 80% is nano-particulate. Nano-particulate iron comprises 20 to 70% of the nominally "dissolved" (i.e. <0.45 μm) iron. Since coagulation and sedimentation are the only processes required to remove solid phase iron, these data have important implications for the generation or consumption of acidity during water treatment. In most waters, the majority of truly dissolved iron occurs as Fe(ii) (average 64 ± 22%). Activities of Fe(ii) do not correlate with pH and geochemical modelling shows that no Fe(ii) mineral is supersaturated. Removal of Fe(ii) must proceed via oxidation and hydrolysis. Except in waters with pH < 4.4, activities of Fe(iii) are strongly and negatively correlated with pH. Geochemical modelling suggests that the activity of Fe(iii) is controlled by the solubility of hydrous ferric oxides and oxyhydroxysulfates, supported by scanning and transmission electron microscopic analysis of solids. Nevertheless, the waters are generally supersaturated with respect to ferrihydrite and schwertmannite, and are not at redox equilibrium, indicating the key role of oxidation and hydrolysis kinetics on water treatment. Typically 70-100% of iron is retained in the treatment systems. Oxidation, hydrolysis, precipitation, coagulation and sedimentation occur in all treatment systems and - independent of water chemistry and the type of treatment system - hydroxides and oxyhydroxysulfates are the main iron sinks. The electrochemical data thus reveal the rationale for incomplete iron retention in individual systems and can thus inform future design criteria. The successful application of this low cost and rapid electrochemical method demonstrates its significant potential for real-time, on-site monitoring of iron-enriched waters and may in future substitute traditional analytical methods.
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Chae, Gi-Tak; Yun, Seong-Taek; Choi, Byoung-Young; Yu, Soon-Young; Jo, Ho-Young; Mayer, Bernhard; Kim, Yun-Jong; Lee, Jin-Yong
2008-10-23
Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m3 year(-1)) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH4+, NO3(-), turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L(-1), max. 5.58 mg L(-1)), in addition to dissolved Fe, NH4+, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes. Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.
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NASA Technical Reports Server (NTRS)
Wang, R.; Demerdash, N. A.
1992-01-01
The combined magnetic vector potential - magnetic scalar potential method of computation of 3D magnetic fields by finite elements, introduced in a companion paper, in combination with state modeling in the abc-frame of reference, are used for global 3D magnetic field analysis and machine performance computation under rated load and overload condition in an example 14.3 kVA modified Lundell alternator. The results vividly demonstrate the 3D nature of the magnetic field in such machines, and show how this model can be used as an excellent tool for computation of flux density distributions, armature current and voltage waveform profiles and harmonic contents, as well as computation of torque profiles and ripples. Use of the model in gaining insight into locations of regions in the magnetic circuit with heavy degrees of saturation is demonstrated. Experimental results which correlate well with the simulations of the load case are given.
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NASA Astrophysics Data System (ADS)
Wang, R.; Demerdash, N. A.
1992-06-01
The combined magnetic vector potential - magnetic scalar potential method of computation of 3D magnetic fields by finite elements, introduced in a companion paper, is used for global 3D field analysis and machine performance computations under open-circuit and short-circuit conditions for an example 14.3 kVA modified Lundell alternator, whose magnetic field is of intrinsic 3D nature. The computed voltages and currents under these machine test conditions were verified and found to be in very good agreement with corresponding test data. Results of use of this modelling and computation method in the study of a design alteration example, in which the stator stack length of the example alternator is stretched in order to increase voltage and volt-ampere rating, are given here. These results demonstrate the inadequacy of conventional 2D-based design concepts and the imperative of use of this type of 3D magnetic field modelling in the design and investigation of such machines.
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NASA Technical Reports Server (NTRS)
Wang, R.; Demerdash, N. A.
1992-01-01
The combined magnetic vector potential - magnetic scalar potential method of computation of 3D magnetic fields by finite elements, introduced in a companion paper, is used for global 3D field analysis and machine performance computations under open-circuit and short-circuit conditions for an example 14.3 kVA modified Lundell alternator, whose magnetic field is of intrinsic 3D nature. The computed voltages and currents under these machine test conditions were verified and found to be in very good agreement with corresponding test data. Results of use of this modelling and computation method in the study of a design alteration example, in which the stator stack length of the example alternator is stretched in order to increase voltage and volt-ampere rating, are given here. These results demonstrate the inadequacy of conventional 2D-based design concepts and the imperative of use of this type of 3D magnetic field modelling in the design and investigation of such machines.
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Net alkalinity and net acidity 2: Practical considerations
Kirby, C.S.; Cravotta, C.A.
2005-01-01
The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples. A meaningful "net" acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinitymeasured - Hot Aciditymeasured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = -Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured - Aciditycalculated) is recommended with some cautions. ?? 2005 Elsevier Ltd. All rights reserved.
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The Organic Complexation of Iron in the Marine Environment: A Review
Gledhill, Martha; Buck, Kristen N.
2012-01-01
Iron (Fe) is an essential micronutrient for marine organisms, and it is now well established that low Fe availability controls phytoplankton productivity, community structure, and ecosystem functioning in vast regions of the global ocean. The biogeochemical cycle of Fe involves complex interactions between lithogenic inputs (atmospheric, continental, or hydrothermal), dissolution, precipitation, scavenging, biological uptake, remineralization, and sedimentation processes. Each of these aspects of Fe biogeochemical cycling is likely influenced by organic Fe-binding ligands, which complex more than 99% of dissolved Fe. In this review we consider recent advances in our knowledge of Fe complexation in the marine environment and their implications for the biogeochemistry of Fe in the ocean. We also highlight the importance of constraining the dissolved Fe concentration value used in interpreting voltammetric titration data for the determination of Fe speciation. Within the published Fe speciation data, there appear to be important temporal and spatial variations in Fe-binding ligand concentrations and their conditional stability constants in the marine environment. Excess ligand concentrations, particularly in the truly soluble size fraction, seem to be consistently higher in the upper water column, and especially in Fe-limited, but productive, waters. Evidence is accumulating for an association of Fe with both small, well-defined ligands, such as siderophores, as well as with larger, macromolecular complexes like humic substances, exopolymeric substances, and transparent exopolymers. The diverse size spectrum and chemical nature of Fe ligand complexes corresponds to a change in kinetic inertness which will have a consequent impact on biological availability. However, much work is still to be done in coupling voltammetry, mass spectrometry techniques, and process studies to better characterize the nature and cycling of Fe-binding ligands in the marine environment. PMID:22403574
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McCleskey, R. Blaine; Nordstrom, D. Kirk; Maest, A.S.
2004-01-01
Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.
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Cravotta, C.A.
2007-01-01
This report evaluates the results of a continuous 4.5-day laboratory aeration experiment and the first year of passive, aerobic treatment of abandoned mine drainage (AMD) from a typical flooded underground anthracite mine in eastern Pennsylvania, USA. During 1991-2006, the AMD source, locally known as the Otto Discharge, had flows from 20 to 270 L/s (median 92 L/s) and water quality that was consistently suboxic (median 0.9 mg/L O2) and circumneutral (pH ??? 6.0; net alkalinity >10) with moderate concentrations of dissolved iron and manganese and low concentrations of dissolved aluminum (medians of 11, 2.2, and <0.2 mg/L, respectively). In 2001, the laboratory aeration experiment demonstrated rapid oxidation of ferrous iron (Fe 2+) without supplemental alkalinity; the initial Fe2+ concentration of 16.4 mg/L decreased to less than 0.5 mg/L within 24 h; pH values increased rapidly from 5.8 to 7.2, ultimately attaining a steady-state value of 7.5. The increased pH coincided with a rapid decrease in the partial pressure of carbon dioxide (PCO2) from an initial value of 10 -1.1atm to a steady-state value of 10-3.1atm. From these results, a staged aerobic treatment system was conceptualized consisting of a 2 m deep pond with innovative aeration and recirculation to promote rapid oxidation of Fe2+, two 0.3 m deep wetlands to facilitate iron solids removal, and a supplemental oxic limestone drain for dissolved manganese and trace-metal removal. The system was constructed, but without the aeration mechanism, and began operation in June 2005. During the first 12 months of operation, estimated detention times in the treatment system ranged from 9 to 38 h. However, in contrast with 80-100% removal of Fe2+ over similar elapsed times during the laboratory aeration experiment, the treatment system typically removed less than 35% of the influent Fe2+. Although concentrations of dissolved CO2 decreased progressively within the treatment system, the PCO2 values for treated effluent remained elevated (10-2.4 to 10-1.7atm). The elevated PCO 2 maintained the pH within the system at values less than 7 and hence slowed the rate of Fe2+ oxidation compared to the aeration experiment. Kinetic models of Fe2+ oxidation that consider effects of pH and dissolved O2 were incorporated in the geochemical computer program PHREEQC to evaluate the effects of detention time, pH, and other variables on Fe2+ oxidation and removal rates. These models and the laboratory aeration experiment indicate that performance of this and other aerobic wetlands for treatment of net-alkaline AMD could be improved by aggressive, continuous aeration in the initial stage to decrease PCO 2, increase pH, and accelerate Fe2+ oxidation. ?? 2007 Springer-Verlag.
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Schechter, Clyde B; Basch, Charles E; Caban, Arlene; Walker, Elizabeth A
2008-01-01
In a clinical trial, we have previously shown that a telephone intervention can significantly increase participation in dilated fundus examination (DFE) screening among low-income adults with diabetes. Here the costs and cost-effectiveness ratio of this intervention are calculated. Intervention effectiveness was estimated as the difference in DFE utilization between the telephone intervention and print groups from the clinical trial multiplied by the size of the telephone intervention group. A micro-costing approach was used. Personnel time was aggregated from logs kept during the clinical trial of the intervention. Wage rates were taken from a commercial compensation database. Telephone charges were estimated based on prevailing fees. The cost-effectiveness ratio was calculated as the ratio of total costs of the intervention to the number of DFEs gained by the intervention. A sensitivity analysis estimated the cost-effectiveness of a more limited telephone intervention. A probabilistic sensitivity analysis using bootstrap samples from the clinical trial results quantified the uncertainties in resource utilization and intervention effectiveness. Net intervention costs were US$18,676.06, with an associated gain of 43.7 DFEs and 16.4 new diagnoses of diabetic retinopathy. The cost-effectiveness ratio is US$427.37 per DFE gained. A restricted intervention limiting the number of calls to 5, as opposed to 7, would achieve the same results, but would cost approximately 17% less. In the probabilistic sensitivity analysis, the 5th and 95th percentiles of the cost-effectiveness ratio were US$304.05 and US$692.52 per DFE gained, respectively. Our telephone intervention is more expensive than simple mail or telephone reminders used in other settings to promote preventive care; it is, however, also considerably more effective, and is effective in a low-income minority population at greater risk for diabetes complications. The costs are dominated by labor costs, and may be substantially defrayed, without loss of effectiveness, by restricting the number of telephone calls to 5 per patient. PMID:19668428
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Interactions between magnetite and humic substances: redox reactions and dissolution processes.
Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas
2017-10-19
Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.
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Grosbois, C; Schäfer, J; Bril, H; Blanc, G; Bossy, A
2009-03-01
The Upper Isle River (SW France) drains the second most productive gold-mining district of France. A high resolution survey during one hydrological year of As, Cl(-), Cr, Fe, Mn, Mo, SO(4)(2-), Th and U dissolved concentrations in surface water aimed to better understand pathways of trace element export to the river system downstream from the mining district. Dissolved concentrations of As (up to 35000 ng/L) and Mo (up to 292 ng/L) were about 3-fold higher than the regional dissolved background and showed a negative logarithmic relation with discharge. Dissolved concentrations of Cr (up to 483 ng/L), Th (up to 48 ng/L) and U (up to 184 ng/L) increased with discharge. Geochemical relationships between molar ratios in surface water, geochemical background as well as rain- and groundwater data were combined. The contrasting behavior of distinct element groups was explained by a scenario involving three seasonal components: (i) The high flow component is poorly concentrated in As and Mo but highly concentrated in Cr, Th, U. This has been attributed to diffuse sources such as water-soil interactions, atmospheric inputs, bedrock and bed sediment weathering. Although this component probably also includes a contribution by weathering of sulfide veins, this signal is masked by dilution. (ii) One low flow component presents high SO(4)(2-), Fe, As and Mo and moderate Cr, Th and U concentrations. This component has been attributed to point sources such as mine gallery effluents, mining waste weathering and groundwater inputs from natural and/or mining-induced sulfide oxidation in the ore deposit. (iii) A second low flow component showing high As plus Mo concentrations associated with very low SO(4)(2-), Fe, Cr, Th and U concentrations, probably reflects trace element scavenging by ferric oxyhydroxide formation in the adjacent aquifer. This is supported by the decrease of Fe, Cr, Th and U in surface waters. Flux estimates suggest contrasting element-specific impacts on annual dissolved fluxes. Runoff may account for the major part of annual dissolved As, Mo, Th and U fluxes in the Upper Isle River. Inputs related to sulfide oxidation respectively contributed approximately 30% and approximately 24% to annual As and Mo fluxes. The formation of ferric oxyhydroxides strongly retained Cr, Th and U during the low flow, limiting their dissolved concentrations in surface waters. If this process may eventually decrease As mobility, its impact on dissolved As concentrations in surface water may be limited or/and counterbalanced by As release during sulfide oxidation.
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Behavior of tritium permeation induced by water corrosion of alpha iron around room temperature
DOE Office of Scientific and Technical Information (OSTI.GOV)
Otsuka, T.; Hashizume, K.
2015-03-15
Tritium (T) permeation leakage to surroundings is a great safety concern in fission and fusion reactor systems. T permeation potentially occurs from T contaminated water through cooling tubes or storage tank made of metals which dissolve some T evolved by water corrosion. In order to understand behaviors of hydrogen uptake and permeation in pure α-iron (αFe) during water corrosion around room temperature, hydrogen permeation experiments for an αFe membrane have been conducted by means of tritium tracer techniques. The present study suggests that hydrogen produced by water corrosion of αFe is trapped in product oxide layers to delay hydrogen uptakemore » in αFe for a moment. However, the oxide layers do not work as a sufficient barrier for hydrogen uptake. Some of hydrogen dissolved in αFe normally diffuses and permeates through the bulk in the early stage of permeation. In a later stage, hydrogen permeation could be apparently stopped by the disappearance of concentration difference of tritium. Hydrogen partial pressure at the water/αFe interface could be ranged from 0.7 to 9.5 kPa around room temperature.« less
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Shim, Moo-Joon; Swarzenski, Peter W.; Shiller, Alan M.
2012-01-01
The Mississippi River delta outflow region is periodically disturbed by tropical weather systems including major hurricanes, which can terminate seasonal bottom water hypoxia and cause the resuspension of shelf bottom sediments which could result in the injection of trace elements into the water column. In the summer of 2005, Hurricanes Katrina and Rita passed over the Louisiana Shelf within a month of each other. Three weeks after Rita, we collected water samples in the Mississippi River delta outflow, examining the distributions of trace elements to study the effect of Hurricanes Katrina and Rita. We observed limited stratification on the shelf and bottom waters that were no longer hypoxic. This resulted, for instance, in bottom water dissolved Mn being lower than is typically observed during hypoxia, but with concentrations still compatible with Mn–O2 trends previously reported. Interestingly, for no element were we able to identify an obvious effect of sediment resuspension on its distribution. In general, elemental distributions were compatible with previous observations in the Mississippi outflow system. Co and Re, which have not been reported for this system previously, showed behavior consistent with other systems: input for Co likely from desorption and conservative mixing for Re. For Cs, an element for which there is little information regarding its estuarine behavior, conservative mixing was also observed. Our filtration method, which allowed us to distinguish the dissolved (<0.02 μm) from colloidal (0.02–0.45 μm) phase, revealed significant colloidal fractions for Fe and Zn, only. For Fe, the colloidal phase was the dominant fraction and was rapidly removed at low salinity. Dissolved Fe, in contrast, persisted out to mid-salinities, being removed in a similar fashion to nitrate. This ability to distinguish the smaller Fe (likely dominantly organically complexed) from larger colloidal suspensates may be useful in better interpreting the bioavailablity of the Fe in estuarine systems.
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NASA Astrophysics Data System (ADS)
Shim, Moo-Joon; Swarzenski, Peter W.; Shiller, Alan M.
2012-07-01
The Mississippi River delta outflow region is periodically disturbed by tropical weather systems including major hurricanes, which can terminate seasonal bottom water hypoxia and cause the resuspension of shelf bottom sediments which could result in the injection of trace elements into the water column. In the summer of 2005, Hurricanes Katrina and Rita passed over the Louisiana Shelf within a month of each other. Three weeks after Rita, we collected water samples in the Mississippi River delta outflow, examining the distributions of trace elements to study the effect of Hurricanes Katrina and Rita. We observed limited stratification on the shelf and bottom waters that were no longer hypoxic. This resulted, for instance, in bottom water dissolved Mn being lower than is typically observed during hypoxia, but with concentrations still compatible with Mn-O2 trends previously reported. Interestingly, for no element were we able to identify an obvious effect of sediment resuspension on its distribution. In general, elemental distributions were compatible with previous observations in the Mississippi outflow system. Co and Re, which have not been reported for this system previously, showed behavior consistent with other systems: input for Co likely from desorption and conservative mixing for Re. For Cs, an element for which there is little information regarding its estuarine behavior, conservative mixing was also observed. Our filtration method, which allowed us to distinguish the dissolved (<0.02 μm) from colloidal (0.02-0.45 μm) phase, revealed significant colloidal fractions for Fe and Zn, only. For Fe, the colloidal phase was the dominant fraction and was rapidly removed at low salinity. Dissolved Fe, in contrast, persisted out to mid-salinities, being removed in a similar fashion to nitrate. This ability to distinguish the smaller Fe (likely dominantly organically complexed) from larger colloidal suspensates may be useful in better interpreting the bioavailablity of the Fe in estuarine systems.
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Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones
Glass, Jennifer B.; Kretz, Cecilia B.; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L.; Buck, Kristen N.; Landing, William M.; Morton, Peter L.; Moffett, James W.; Giovannoni, Stephen J.; Vergin, Kevin L.; Stewart, Frank J.
2015-01-01
Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO3−, NO2−, Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu. PMID:26441925
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Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones.
Glass, Jennifer B; Kretz, Cecilia B; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L; Buck, Kristen N; Landing, William M; Morton, Peter L; Moffett, James W; Giovannoni, Stephen J; Vergin, Kevin L; Stewart, Frank J
2015-01-01
Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO[Formula: see text], NO[Formula: see text], Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu.
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NASA Astrophysics Data System (ADS)
Nakaya, Shinji; Chi, Hai; Muroda, Kengo; Masuda, Harue
2018-06-01
In this study, we focus on the behavior of geogenic, toxic trace elements, particularly As, Cs, Cd, and Pb, during their transportation in two rivers for irrigation commonly used in monsoon Asia; one river originates from an active volcano, Mt. Asama, and the other originates from a currently inactive volcano, Yatsugatake Mountains in Nagano, Japan. These rivers were investigated to understand the role of river water as a pollutant of rice and other aquatic plants (via irrigation) and aquatic animals. The results indicated that the behavior of toxic trace elements in river water are likely controlled by their interactions with particulate Fe, Al, and Ti compounds. The majority of Pb and Cd is transported as particulate matter with Fe, Al, and Ti, while the majority of As is transported in the dissolved form, predominantly as arsenate, with low abundance of particulate matter. Cs is transported either as the dissolved form or as particulate matter in both rivers. The investigated elements are transported in the rivers as particulate and dissolved forms, and the ratio of these forms is controlled by the pH and presence of particulate Fe, Al, and Ti phases in the river water. With respect to Cs in both rivers, the parameter governing the concentration and transportation of Cs, in the bimodal form (i.e., particulate and dissolved forms), through the river possibly shifts from sorption to pH by particulate Fe-Al-Ti, according to the abrupt increase in the concentration of Cs in the river. The chemical attraction of particulate Fe-Al-Ti for Cs is weaker than that for Pb and Cd, indicating that the lower electronegativity of Cs weakens the chemical attraction on a colloid for the competitive sorption with the other trace elements. The different relationships between As and Fe in the river and in the irrigation water and soil water, as well as those in paddy rice, suggested that As in paddy rice is not directly derived from As in the irrigation water from the river under flooding.
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NASA Technical Reports Server (NTRS)
Reubush, D. E.; Carlson, J. R.
1982-01-01
A wind-tunnel investigation was conducted to determine the effects of F101 DFE (derivative fighter engine) nozzle axial positioning on the afterbody-nozzle longitudinal aerodynamic characteristics of the F-14 airplane. The model was tested in the Langley 16-Foot Transonic Tunnel at Mach numbers from 0.7 to 1.25 and angles of attack from about -2 to 6 degrees. Compressed air was used to simulate nozzle exhaust flow at jet total-pressure ratios from 1 (jet off) to about 8. The results of the investigation show that for subsonic Mach numbers the intermediate cruise nozzle position of the three positions tested resulted in the lowest drag.
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NASA Astrophysics Data System (ADS)
Lopez, Grecia I.; Marcantonio, Franco; Lyle, Mitch; Lynch-Stieglitz, Jean
2015-12-01
We assess the distribution of 230Th and 232Th along a latitudinal gradient in the Central Equatorial Pacific Ocean (∼155°W-159°W) at two sites: 8°N and the equator. The dissolved 230Th concentration profile at 8°N increases nearly linearly from the surface to 2000 m, exhibiting behavior consistent with thermodynamic reversible scavenging. However, from 2000 m to 3000 m, the dissolved 230Th concentrations exhibit little change, before increasing slightly from 3000 m to the bottom. At this site dissolved 230Th concentrations range from 1.1 fg/kg at 100 m to 55.2 fg/kg at 4600 m. At the equator, dissolved 230Th concentrations are slightly lower, and range from undetectable at 25 m to 19.1 fg/kg at 3038 m. The pattern in the dissolved 230Th concentration profile at the equator is indistinguishable from that at 8°N. The mid-depth-water deviation from equilibrium reversible scavenging between 2 and 3 km in the 230Th profiles (lower concentrations than expected) at both sites occurs in the interval of the water column that is consistent with an interval that has high concentrations of 3He and dissolved Fe at other nearby sites. This 3He- and Fe-rich signal has been traced to hydrothermal plumes from the East Pacific Rise, thousands of kilometers away. We hypothesize that the lower concentrations of 230Th in mid-depth waters of the Central Equatorial Pacific are a result of a 5000-km transit of waters that have had their 230Th scavenged by Fe-Mn particulates close to the EPR. Oceanic residence times of thorium combined with dissolved 232Th concentrations suggest dust fluxes of about ∼ 0.5- 0.6 gm-2yr-1 to the sea surface. These fluxes are in agreement with other empirical studies in the Pacific, but are higher than those suggested by global atmospheric circulation models.
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THE EFFECT OF PH AND DISSOLVED INORGANIC CARBON ON THE PROPERTIES OF IRON COLLOIDAL SUSPENSIONS
Discolored water resulting from suspended iron particles is a relatively common drinking water consumer complaint. These particles result from the oxygenation of Fe(II), and this study shows that pH and dissolved inorganic carbon (DIC) have important effects on their properties....
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NASA Astrophysics Data System (ADS)
Horneman, A.; van Geen, A.; Kent, D. V.; Mathe, P. E.; Zheng, Y.; Dhar, R. K.; O'Connell, S.; Hoque, M. A.; Aziz, Z.; Shamsudduha, M.; Seddique, A. A.; Ahmed, K. M.
2004-09-01
This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility. In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ˜0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R 2 of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10 -9 m 3/kg SI) and was linearly related (R 2 of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ˜200 × 10 -9 m 3/kg SI). This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10 -6, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.
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Wirt, Laurie; Leib, K.J.; Bove, D.J.; Mast, M.A.; Evans, J.B.; Meeker, G.P.
1999-01-01
Prospect Gulch is a major source of iron, aluminum, zinc, and other metals to Cement Creek. Information is needed to prioritize remediation and develop strategies for cleanup of historical abandoned mine sites in Prospect Gulch. Chemical-constituent loads were determined in Prospect Gulch, a high-elevation alpine stream in southwestern Colorado that is affected by natural acid drainage from weathering of hydro-thermally altered igneous rock and acidic metal-laden discharge from historical abandoned mines. The objective of the study was to identify metal sources to Prospect Gulch. A tracer solution was injected into Prospect Gulch during water-quality sampling so that loading of geochemical constituents could be calculated throughout the study reach. A thunderstorm occurred during the tracer study, hence, metal loads were measured for storm-runoff as well as for base flow. Data from different parts of the study reach represents different flow conditions. The beginning of the reach represents background conditions during base flow immediately upstream from the Lark and Henrietta mines (samples PG5 to PG45). Other samples were collected during storm runoff conditions (PG100 to PG291); during the first flush of metal runoff following the onset of rainfall (PG303 to PG504), and samples PG542 to PG700 were collected during low-flow conditions. During base-flow conditions, the percentage increase in loads for major constituents and trace metals was more than an order of magnitude greater than the corresponding 36 % increase in stream discharge. Within the study reach, the highest percentage increases for dissolved loads were 740 % for iron (Fe), 465 % for aluminum (Al), 500 % for lead (Pb), 380 % for copper (Cu), 100 % for sulfate (SO4), and 50 % for zinc (Zn). Downstream loads near the mouth of Prospect Gulch often greatly exceeded the loads generated within the study reach but varied by metal species. For example, the study reach accounts for about 6 % of the dissolved-Fe load, 13 % of the dissolved-Al load, and 18 % of the dissolved-Zn load; but probably contributes virtually all of the dissolved Cu and Pb. The greatest downstream gains in dissolved trace-metal loads occurred near waste-rock dumps for the historical mines. The major sources of trace metals to the study reach were related to mining. The major source of trace metals in the reach near the mouth is unknown, however is probably related to weathering of highly altered igneous rocks, although an unknown component of trace metals could be derived from mining sources The late-summer storm dramatically increased the loads of most dissolved and total constituents. The effects of the storm were divided into two distinct periods; (1) a first flush of higher metal concentrations that occurred soon after rainfall began and (2) the peak discharge of the storm runoff. The first flush contained the highest loads of dissolved Fe, total and dissolved Zn, Cu, and Cd. The larger concentrations of Fe and sulfate in the first flush were likely derived from iron hydroxide minerals such as jarosite and schwertmanite, which are common on mine dumps in the Prospect Gulch drainage basin. Peak storm runoff contained the highest measured loads of total Fe, and of total and dissolved calcium, magnesium, silica and Al, which were probably derived from weathering of igneous rocks and clay minerals in the drainage basin.
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Cravotta, Charles A.
2015-01-01
Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2 mass transfer rate constant (kL,CO2a). The value of kL,CO2a estimated for the stream (0.010 min−1) was within the range for the batch aeration experiments (0–0.033 min−1). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).
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Porewater inputs drive Fe redox cycling in the water column of a temperate mangrove wetland
NASA Astrophysics Data System (ADS)
Holloway, Ceylena J.; Santos, Isaac R.; Rose, Andrew L.
2018-07-01
Iron is a vital micronutrient within coastal marine ecosystems, playing an integral role in the scale and dynamics of primary production and carbon cycling in the world's oceans. We investigated the relative importance of in situ Fe(II) production from photochemical, microbial and thermal Fe reduction in the surface water column as well as advective porewater inputs in a temperate saline wetland in Australia containing mangrove and saltmarsh vegetation. The diel average concentration of Fe(II) (0.63 ± 0.21 μM, accounting for >70% of the total dissolved Fe present in surface water) was much higher than commonly reported in oxygenated marine waters despite high dissolved oxygen concentrations (81-112% saturation), pH (7.7-7.8) and salinity (33-36) that favor Fe oxidation. In situ production of Fe(II) in the surface water column was primarily driven by microbial processes rather than photochemical and thermal reduction, with a maximum production rate of 4.9 × 10-3 nM s-1. Advective porewater Fe(II) inputs to the wetland averaged over a diel cycle (3.0 × 10-1 nM s-1) were an order of magnitude greater than the combined Fe(II) production rate from autochthonous water column processes (1.0 × 10-2 nM s-1). A bottom up model based on the estimated individual fluxes was used to explain the high Fe(II) concentrations measured during a 24 h time series experiment. Combined, different lines of evidence suggest that advective porewater exchange provides significant quantities of Fe(II) to the estuarine wetland.
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Brantner, Justin S.; Haake, Zachary J.; Burwick, John E.; Menge, Christopher M.; Hotchkiss, Shane T.; Senko, John M.
2014-01-01
We evaluated the depth-dependent geochemistry and microbiology of sediments that have developed via the microbially-mediated oxidation of Fe(II) dissolved in acid mine drainage (AMD), giving rise to a 8–10 cm deep “iron mound” that is composed primarily of Fe(III) (hydr)oxide phases. Chemical analyses of iron mound sediments indicated a zone of maximal Fe(III) reducing bacterial activity at a depth of approximately 2.5 cm despite the availability of dissolved O2 at this depth. Subsequently, Fe(II) was depleted at depths within the iron mound sediments that did not contain abundant O2. Evaluations of microbial communities at 1 cm depth intervals within the iron mound sediments using “next generation” nucleic acid sequencing approaches revealed an abundance of phylotypes attributable to acidophilic Fe(II) oxidizing Betaproteobacteria and the chloroplasts of photosynthetic microeukaryotic organisms in the upper 4 cm of the iron mound sediments. While we observed a depth-dependent transition in microbial community structure within the iron mound sediments, phylotypes attributable to Gammaproteobacterial lineages capable of both Fe(II) oxidation and Fe(III) reduction were abundant in sequence libraries (comprising ≥20% of sequences) from all depths. Similarly, abundances of total cells and culturable Fe(II) oxidizing bacteria were uniform throughout the iron mound sediments. Our results indicate that O2 and Fe(III) reduction co-occur in AMD-induced iron mound sediments, but that Fe(II)-oxidizing activity may be sustained in regions of the sediments that are depleted in O2. PMID:24860562
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NASA Astrophysics Data System (ADS)
Nukazawa, Kei; Kihara, Kousuke; Suzuki, Yoshihiro
2017-12-01
Rivers fulfill an essential ecological role by forming networks for material transport from upland forests to coastal areas. The way in which dams affect the organic and inorganic cycles in such systems is not well understood. Herein, we investigated the longitudinal profiles of the various components of the water chemistry across three cascade dams in Japan: the Yamasubaru Dam, Saigou Dam, and Ohuchibaru Dam, which are situated along the sediment-productive Mimi River in different flow conditions. We analyzed the following water quality components: suspended solids (SS), turbidity, total iron (TFe), dissolved iron (DFe), total organic carbon (TOC), total nitrogen (TN), total phosphorus (TP), humic substance (HS), and major ionic components (Na+, Mg2+, Ca2+, Cl-, NO3-, and SO42-) in the downstream channels of the three dams during the low-intermediate-flow and high-flow events from 2012 to 2014. We estimated hourly loads of each component using hourly turbidity data and discharge data (i.e., L-Q model) separately, and the results are integrated to estimate the annual fluxes. The annual fluxes between the methods were compared to verify predictability of the conventional L-Q models. Annual flux of TOC, TN, DFe, and HS estimated by the turbidity displayed similar values, whereas the flux of SS, TFe, and TP tended to increase downstream of the dams. Among the dams, estimated flux proportions for TP and TFe were higher during high-flow events (74%-94%). Considering geographic conditions (e.g., absence of major tributary between the dams), the result implies that accumulated TP and TFe in the reservoirs may be flushed and transported downstream with SS over the short height dams during flood events. Assuming this process, the reservoir dams probably make only a fractional contribution to the organic and inorganic transport in the catchment studied. The percent flux errors for SS, TFe, and TP fluxes ranged from -7.2% to -97% (except for the TP flux in 2013), which highlights the risk of underestimating these components when using an L-Q model.
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Mwangi, Isaac W; Ngila, J Catherine; Ndungu, Patrick; Msagati, Titus A M; Kamau, Joseph N
2013-09-01
Photocatalytic degradation of dissolved organic carbon (DOC) by utilizing Fe(III)-doped TiO2 at the visible radiation range is hereby reported. The photocatalyst was immobilized on sintered glass frits with the coating done by wet method, calcinated at 500 °C and then applied in a photodegradation reactor. The addition of a transition metal dopant, Fe(III), initiated the red shift which was confirmed by UV-Vis spectroscopy, and the photocatalyst was activated by visible radiation. X-ray diffraction patterns showed that Fe(III) doping had an effect on the crystallinity of the photocatalysts. Mixtures of DOC and associated coloured solutions were degraded in first-order kinetics, showing that the degradation process was not dependent on intermediates or other species in solution. A reactor with a catalyst coating area of 12.57 cm(2) was able to degrade 0.623 mg of the dissolved material per minute. Exposure of the reactor to hostile acidic conditions and repeated use did not compromise its efficiency. It was observed that the reactor regenerates itself in the presence of visible light, and therefore, it can be re-used for more than 100 runs before the performance dropped to <95 %. The results obtained indicate that the photocatalyst reactor has a great potential of application for use in tandem with biosorbent cartridges to complement water purification methods for domestic consumption.
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NASA Astrophysics Data System (ADS)
Miller, Hannah M.; Matter, Jürg M.; Kelemen, Peter; Ellison, Eric T.; Conrad, Mark E.; Fierer, Noah; Ruchala, Tyler; Tominaga, Masako; Templeton, Alexis S.
2016-04-01
The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O2/CO2-rich atmosphere. In this work, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca2+, H2 and CH4, as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition. The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H2. Dissolved CH4 in the fluids exhibits the most isotopically heavy carbon in CH4 reported in the literature thus far. The CH4 may have formed through abiotic reduction of dissolved CO2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). The composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.
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Processes affecting transport of uranium in a suboxic aquifer
Davis, J.A.; Curtis, G.P.; Wilkins, M.J.; Kohler, M.; Fox, P.; Naftz, D.L.; Lloyd, J.R.
2006-01-01
At the Naturita site in Colorado, USA, groundwaters were sampled and analyzed for chemical composition and by culture and culture-independent microbiological techniques. In addition, sediments were extracted with a dilute sodium carbonate solution to determine quantities of labile uranium within the sediments. Samples from the upgradient portion of the contaminated aquifer, where very little dissolved Fe(II) is found in the groundwater, have uranium content that is controlled by U(VI) adsorption and few metal-reducing bacteria are observed. In the extreme downgradient portion of the aquifer, where dissolved Fe(II) is observed, uranium content of the sediments includes significant quantities of reduced U(IV) and diverse populations of Fe(III)-reducing bacteria were present in the subsurface with the potential of reducing U(VI) to U(IV). ?? 2006 Elsevier Ltd. All rights reserved.
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Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.
González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M
2014-07-15
The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.
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NASA Astrophysics Data System (ADS)
Srinivas, A. J.; Dinsdale, E. A.; Lipson, D.
2014-12-01
Dissimilatory iron reduction (DIR), where ferric iron (Fe3+) is reduced to ferrous iron (Fe2+) anaerobically, is an important respiratory pathway used by soil bacteria. DIR contributes to carbon dioxide (CO2) efflux from the wet sedge tundra biome in the Arctic Coastal Plain (ACP) in Alaska, and could competitively inhibit the production of methane, a stronger greenhouse gas than CO2, from arctic soils. The occurrence of DIR as a dominant anaerobic process depends on the availability of substantial levels of Fe3+ in soils. Siderophores are metabolites made by microbes to dissolve Fe3+ from soil minerals in iron deficient systems, making Fe3+ soluble for micronutrient uptake. However, as the ACP is not iron deficient, siderophores in arctic soils may play a vital role in anaerobic respiration by dissolving Fe3+ for DIR. We studied the effects of direct siderophore addition to arctic soils through a field study conducted in Barrow, Alaska, and a laboratory incubation study conducted at San Diego State University. In the field experiment, 50μM deferroxamine mesylate (a siderophore), 50μM trisodium nitrilotriacetate (an organic chelator) or an equal volume of water was added to isolated experimental plots, replicated in clusters across the landscape. Fe2+ concentrations were measured in soil pore water samples collected periodically to measure DIR over time in each. In the laboratory experiment, frozen soil samples obtained from drained thaw lake basins in the ACP, were cut into cores and treated with the above-mentioned compounds to the same final concentrations. Along with measuring Fe2+ concentrations, CO2 output was also measured to monitor DIR over time in each core. Experimental addition of siderophores to soils in both the field and laboratory resulted in increased concentrations of soluble Fe3+ and a sustained increase in Fe2+concentrations over time, along with increased respiration rates in siderophore-amended cores. These results show increased DIR in siderophore treated cores compared to the other treatments. From the results of these experiments, we conclude that arctic soil microbes can use siderophores to maintain a pool of dissolved Fe3+ for DIR. This study provides insight into the mechanisms of DIR in this ecosystem, and has relevance for understanding anaerobic soil respiration in the Arctic.
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Automotive Refinishing Industry: Isocyanates Profile
The isocyanates profile document is part of the DfE Auto Refinishing Shop Project and is intended to provide information on refinishing, control technologies, and regulatory status regarding isocyanate compounds
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Oxic limestone drains for treatment of dilute, acidic mine drainage
Cravotta, Charles A.
1998-01-01
Limestone treatment systems can be effective for remediation of acidic mine drainage (AMD) that contains moderate concentrations of dissolved O2 , Fe3+ , or A13+ (1‐5 mg‐L‐1 ). Samples of water and limestone were collected periodically for 1 year at inflow, outflow, and intermediate points within underground, oxic limestone drains (OLDs) in Pennsylvania to evaluate the transport of dissolved metals and the effect of pH and Fe‐ and Al‐hydrolysis products on the rate of limestone dissolution. The influent was acidic and relatively dilute (pH <4; acidity < 90 mg‐L‐1 ) but contained 1‐4 mg‐L‐1 Of O2 , Fe3+ , A13+ , and Mn2+ . The total retention time in the OLDs ranged from 1.0 to 3.1 hours. Effluent remained oxic (02 >1 mg‐L‐1 ) but was near neutral (pH = 6.2‐7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)3 and AI(OH)3, were visible as loosely bound, orange‐yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)3 and AI(OH)3 particles were transported downflow. During the first 6 months of the experiment, Mn 2+ was transported conservatively through the OLDs; however, during the second 6 months, concentrations of Mn in effluent decreased by about 50% relative to influent. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of Mn as indicated by its enrichment relative to Fe in hydrous‐oxide particles and coatings on limestone. Despite thick (~1 mm) hydrous‐oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within the OLD where the limestone was not coated. The rate of limestone dissolution decreased with increased residence time, pH, and concentrations of Ca2+ and HCO3‐ and decreased PCO2. The following overall reaction shows alkalinity as an ultimate product of the iron hydrolysis reaction in an OLD:Fe2+ + 0.25 O2 +CaCO3 + 2.5 H2O --> Fe(OH)3 + 2 Ca2+ + 2 HCO3-where 2 moles of CaCO3 dissolve for each mole of Fe(OH)3 produced. Hence, in an OLD, rapidly dissolving limestone surfaces are not stable substrates for Fe(OH)3 attachment and armoring. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two‐stage treatment system consisting of an anoxic limestone drain an oxidation‐settling pond or wetland. To facilitate removal of hydrous‐oxide sludge, a perforated‐pipe subdrain can be installed within an OLD.
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NASA Astrophysics Data System (ADS)
Datta, S.; Berube, M.; Knappett, P.; Kulkarni, H. V.; Vega, M.; Jewell, K.; Myers, K.
2017-12-01
Elevated levels of dissolved arsenic (As), iron (Fe) and manganese (Mn) are seen in the shallow groundwaters of southeast Bangladesh on the Ganges Brahmaputra Meghna River delta. This study takes a multi disciplinary approach to understand the extent of the natural reactive barrier (NRB) along the Meghna River and evaluate the role of the NRB in As sequestration and release in groundwater aquifers. Shallow sediment cores, and groundwater and river water samples were collected from the east and west banks of the Meghna. Groundwater and river water samples were tested for FeT, MnT, and AsT concentrations. Fluorescence spectroscopic characterization of groundwater dissolved organic matter (DOM) provided insight into the hydro geochemical reactions active in the groundwater and the hyporheic zones. Eight sediment cores of 1.5 m depth were collected 10 m away from the edge of the river. Vertical solid phase concentration profiles of Fe, Mn and As were measured via 1.2 M HCl digestion which revealed solid phase As accumulation along the riverbanks up to concentrations of 1500 mg/kg As. Microbial interactions with DOM prompts the reduction of Fe3+ to Fe2+, causing As to mobilize into groundwater and humic-like DOM present in the groundwater may catalyze this process. The extent to which microbially mediated release of As occurs is limited by labile dissolved organic carbon (DOC) availability. Aqueous geochemical results showed the highest dissolved As concentrations in shallow wells (<30 m depth), where organic matter was fresh, humic-like, and aromatic. Based on fluorescence characterization, shallow groundwater was found to contain microbial and terrestrial derived DOC, and decomposed, humified and aromatic DOM. Deeper aquifers had a significantly larger microbial OM signature than the shallower aquifers and was less aromatic, decomposed and humified. The results from this study illustrate the potential for humic substances to contribute to As cycling and quantify the extent of As accumulation in the sediments and groundwater along a 1 km stretch of the Meghna. These findings contribute to the overall understanding of geochemical processes involved in As release into groundwaters from sediments within a fluvial deltaic environment and close proximity to a possible permeable natural reactive barrier.
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Formation of thin sulfide rinds on the CM parent body. [Abstract only
NASA Technical Reports Server (NTRS)
Browning, L. B.; Mcsween, H. Y., Jr.; Zolensky, M.
1994-01-01
Many of the textures that are observed in CM chondrites have been alternately assigned nebular, parent-body, or combined nebular-parent body origins. Since it is very difficult to substantiate the production of complex textures in the nebula, an alternate approach to this problem is to rigorously determine which of the observable textures could have been produced by reasonable aqueous alteration processes on the CM parent body. Potential parent body reactions involving S deserve special attention because S-bearing phase define many important CM textures, such as rims. We have examined the possibility that the thin (about 5 microns) rinds of sulfides observed around some partially dissolved olivines within the chondrules and matrixes of CM chondrites were formed by the preferential precipitation of sulfides at or near dissolving olivine boundaries during parent-body alteration. Our model defines two infinite and parallel planes of olivine that are separated by pure water. Average separation distances between olivine grains in CM chondrites at the time of accretion (about 100-200 microns) were estimated by assuming a closed system fluid/rock ratio of 45% and varying the bimodal grain-size distribution. We restrict our calculations to the case of an isochemical system with sufficient bisulfide in solution to account for precipitation of pyrrhotite at STP. Our model examines the possibility that dissolving olivines with compositions between Fo(sub 0.9) and Fo(sub 0.4) can produce a strong gradient of Fe(2+) at pHs from 7 to 12 such that the precipitation of pyrrhotite will be initiated at the olivine-fluid boundary. Since CM phase equilibria is consistent with highly reducing conditions, Fe released by olivines would largely remain in solution as Fe(2+) until the solubility product of a Fe(2+) bearing phase was exceeded. Our calculations indicate that all examined combinations of olivine composition and pH yield a strong Fe(2+) gradient at the time the pyrrhotite solubility is exceeded near the olivine-fluid boundary. This favors the initiation of sulfide precipitation around dissolving olivines. However, sulfide rinds are not observed around all partially dissolved olivine grains in CM chondrites, which suggests that the availability of aqueous sulfide species limits the production of the thin sulfide rinds.
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Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Terao, Koumei; Yoshimura, Chihiro
2017-01-01
Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7-8). Rates of Fe(III) reduction were spectrophotometrically determined by a ferrozine method under the simulated sunlight and dark conditions, whereas rates of Fe(II) oxidation were examined in air-saturated solution using luminol chemiluminescence technique. The reduction and oxidation rate constants were determined to substantially vary depending on the type of HS. For example, the first-order rate constants varied by up to 10-fold for photochemical reduction and 7-fold for thermal reduction. The degree of variation in Fe(II) oxidation was larger for the H2O2-mediated reaction compared to the O2-mediated reaction (e.g., 15- and 3-fold changes for the former and latter reactions, respectively, at pH 8). The steady-state Fe(II) fraction under the simulated sunlight indicated that the Fe(II) fraction varies by up to 12-fold. The correlation analysis indicated that variation of Fe(II) oxidation is significantly associated with aliphatic content of HS, suggesting that Fe(II) complexation by aliphatic components accelerates Fe(II) oxidation. The reduction rate constant and steady-state Fe(II) fractions in the presence of sunlight had relatively strong positive relations with free radical content of HS, possibly due to the reductive property of radical semiquinone in HS. Overall, the findings in this study indicated that the Fe reduction and oxidation kinetics and resultant Fe(II) formation are substantially influenced by chemical properties of HS.
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Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products
NASA Astrophysics Data System (ADS)
Dhungana, Suraj; Anthony, Charles R.; Hersman, Larry E.
2007-12-01
Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10 -6 mol m -2 h -1. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H 2S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.
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Butler, Barbara A; Ranville, James F; Ross, Philippe E
2008-06-01
North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.
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Ussher, Simon J; Milne, Angela; Landing, William M; Attiq-ur-Rehman, Kakar; Séguret, Marie J M; Holland, Toby; Achterberg, Eric P; Nabi, Abdul; Worsfold, Paul J
2009-10-12
A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II)+Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100microM concentrations of sulphite a reduction time of 4h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.
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Chakraborty, Parthasarathi; Chakraborty, Sucharita; Jayachandran, Saranya; Madan, Ritu; Sarkar, Arindam; Linsy, P; Nath, B Nagender
2016-10-01
This study describes the effect of varying bottom-water oxygen concentration on geochemical fractionation (operational speciation) of Cu and Pb in the underneath sediments across the oxygen minimum zone (Arabian Sea) in the west coast of India. Both, Cu and Pb were redistributed among the different binding phases of the sediments with changing dissolved oxygen level (from oxic to hypoxic and close to suboxic) in the bottom water. The average lability of Cu-sediment complexes gradually decreased (i.e., stability increased) with the decreasing dissolved oxygen concentrations of the bottom water. Decreasing bottom-water oxygen concentration increased Cu association with sedimentary organic matter. However, Pb association with Fe/Mn-oxyhydroxide phases in the sediments gradually decreased with the decreasing dissolved oxygen concentration of the overlying bottom water (due to dissolution of Fe/Mn oxyhydroxide phase). The lability of Pb-sediment complexes increased with the decreasing bottom-water oxygen concentration. This study suggests that bottom-water oxygen concentration is one of the key factors governing stability and lability of Cu and Pb complexes in the underneath sediment. Sedimentary organic matter and Fe/Mn oxyhydroxide binding phases were the major hosting phases for Cu and Pb respectively in the study area. Increasing lability of Pb-complexes in bottom sediments may lead to positive benthic fluxes of Pb at low oxygen environment. Copyright © 2016 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Fortner, Sarah K.; Lyons, W. Berry
2018-04-01
Here we present a synthesis of the trace element chemistry in melt on the surface Canada Glacier, Taylor Valley, McMurdo Dry Valleys (MDV), Antarctica ( 78°S). The MDV is largely ice-free. Low accumulation rates, strong winds, and proximity to the valley floor make these glaciers dusty in comparison to their inland counterparts. This study examines both supraglacial melt streams and cryoconite holes. Supraglacial streams on the lower Canada Glacier have median dissolved (<0.4 µm) concentrations of Fe, Mn, As, Cu, and V of 71.5, 75.5, 3.7, 4.6, and 4.3 nM. All dissolved Cd concentrations and the vast majority of Pb values are below our analytical detection (i.e. 0.4 and 0.06 nM). Chemical behavior did not follow similar trends for eastern and western draining waters. Heterogeneity likely reflects distinctions eolian deposition, rock:water ratios, and hydrologic connectivity. Future increases in wind-delivered sediment will likely drive dynamic responses in melt chemistry. For elements above detection limits, dissolved concentrations in glacier surface melt are within an order of magnitude of concentrations observed in proglacial streams (i.e. flowing on the valley floor). This suggests that glacier surfaces are an important source of downstream chemistry. The Fe enrichment of cryoconite water relative to N, P, or Si exceeds enrichment observed in marine phytoplankton. This suggests that the glacier surface is an important source of Fe to downstream ecosystems.
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Mladenov, Natalie; Zheng, Yan; Simone, Bailey; Bilinski, Theresa M; McKnight, Diane M; Nemergut, Diana; Radloff, Kathleen A; Rahman, M Moshiur; Ahmed, Kazi Matin
2015-09-15
In some high arsenic (As) groundwater systems, correlations are observed between dissolved organic matter (DOM) and As concentrations, but in other systems, such relationships are absent. The role of labile DOM as the main driver of microbial reductive dissolution is not sufficient to explain the variation in DOM-As relationships. Other processes that may also influence As mobility include complexation of As by dissolved humic substances, and competitive sorption and electron shuttling reactions mediated by humics. To evaluate such humic DOM influences, we characterized the optical properties of filtered surface water (n = 10) and groundwater (n = 24) samples spanning an age gradient in Araihazar, Bangladesh. Further, we analyzed large volume fulvic acid (FA) isolates (n = 6) for optical properties, C and N content, and (13)C NMR spectroscopic distribution. Old groundwater (>30 years old) contained primarily sediment-derived DOM and had significantly higher (p < 0.001) dissolved As concentration than groundwater that was younger than 5 years old. Younger groundwater had DOM spectroscopic signatures similar to surface water DOM and characteristic of a sewage pollution influence. Associations between dissolved As, iron (Fe), and FA concentration and fluorescence properties of isolated FA in this field study suggest that aromatic, terrestrially derived FAs promote As-Fe-FA complexation reactions that may enhance As mobility.
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Mechanisms for Fe(III) oxide reduction in sedimentary environments
Nevin, Kelly P.; Lovely, Derek R.
2002-01-01
Although it was previously considered that Fe(III)-reducing microorganisms must come into direct contact with Fe(III) oxides in order to reduce them, recent studies have suggested that electron-shuttling compounds and/or Fe(III) chelators, either naturally present or produced by the Fe(III)-reducing microorganisms themselves, may alleviate the need for the Fe(III) reducers to establish direct contact with Fe(III) oxides. Studies with Shewanella alga strain BrY and Fe(III) oxides sequestered within microporous beads demonstrated for the first time that this organism releases a compound(s) that permits electron transfer to Fe(III) oxides which the organism cannot directly contact. Furthermore, as much as 450 w M dissolved Fe(III) was detected in cultures of S. alga growing in Fe(III) oxide medium, suggesting that this organism releases compounds that can solublize Fe(III) from Fe(III) oxide. These results contrast with previous studies, which demonstrated that Geobacter metallireducens does not produce electron-shuttles or Fe(III) chelators. Some freshwater aquatic sediments and groundwaters contained compounds, which could act as electron shuttles by accepting electrons from G. metallireducens and then transferring the electrons to Fe(III). However, other samples lacked significant electron-shuttling capacity. Spectroscopic studies indicated that the electron-shuttling capacity of the waters was not only associated with the presence of humic substances, but water extracts of walnut, oak, and maple leaves contained electron-shuttling compounds did not appear to be humic substances. Porewater from a freshwater aquatic sediment and groundwater from a petroleum-contaminated aquifer contained dissolved Fe(III) (4-16 w M), suggesting that soluble Fe(III) may be available as an electron acceptor in some sedimentary environments. These results demonstrate that in order to accurately model the mechanisms for Fe(III) reduction in sedimentary environments it will be necessary to have information on the concentrations of electron-shuttling compounds and possibly Fe(III) ligands. Furthermore, as it is now apparent that different genera of Fe(III)-reducing microorganisms may reduce Fe(III) via different mechanisms, knowledge of which Fe(III)-reducing microorganisms predominate in the environment of interest is essential in order to model this process appropriately.
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NASA Astrophysics Data System (ADS)
Galeczka, Iwona; Wolff-Boenisch, Domenik; Oelkers, Eric H.; Gislason, Sigurdur R.
2014-05-01
A novel high pressure column flow reactor (HPCFR) was used to investigate the evolution of fluid chemistry along a 2.3 meter flow path during 37-104 days of pure water- and CO2-charged water- (0.3 M CO2(aq)) basaltic glass interaction experiments at 22 and 50 ° C. The scale of the HPCFR, the ability to sample a reactive fluid at discrete spatial intervals under pressure and the possibility to measure the dissolved inorganic carbon and pH in situ all render the HPCFR unique in comparison with other reactors constructed for studies of CO2-charged water-rock interaction. During the pure water-basaltic glass interaction experiment, the pH of the injected water evolved rapidly from 6.7 to 9-9.5 and most of the dissolved iron was consumed by secondary mineral formation, similar to natural basaltic groundwater systems. In contrast to natural systems, however, the dissolved aluminium concentration remained relatively high along the entire flow path. The reactive fluid was undersaturated with respect to basaltic glass and carbonate minerals, but supersaturated with respect to zeolites, clays, and Fe hydroxides. Basaltic glass dissolution in the CO2-charged water was closer to stoichiometry than in pure water. The mobility of metals increased significantly in the reactive fluid and the concentration of some metals, including Mn, Fe, Cr, Al, and As exceeded the WHO (World Health Organisation) allowable drinking water limits. Iron was mobile and the aqueous Fe2+/Fe3+ ratio increased along the flow path. Basaltic glass dissolution in the CO2-charged water did not overcome the pH buffer capacity of the fluid. The pH rose only from an initial pH of 3.4 to 4.5 along the first 18.5 cm of the column, then remained constant during the remaining 2.1 meters of the flow path. Increasing the temperature of the CO2-charged fluid from 22 to 50 ° C increased the relative amount of dissolved divalent iron along the flow path. After a significant initial increase along the first metre of the column, the dissolved aluminium concentration decreased consistent with its incorporation into secondary minerals. The dissolved chromium concentration evolution mimicked that of Al at 50 ° C, suggesting substitution of trivalent Cr for Al in secondary phases. According to PHREEQC calculations, the CO2-charged fluid was always undersaturated with respect to carbonate minerals within the column, but supersaturated with respect to clays and Fe hydroxides at 22 ° C and with respect to clays and Al hydroxides at 50 ° C. Substantial differences were found between modelled and measured dissolved element concentrations in the fluids during the experiments. These differences underscore the need to improve computational models before they can be used to predict with confidence the fate and consequences of carbon dioxide injected into the subsurface.
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USDA-ARS?s Scientific Manuscript database
Interaction and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in lake systems. Thus, coagulation and fractionation of plant-derived DOM by di- and tri-valent Ca, Al, and Fe ions were investigated. Metal ion-induc...
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Cummings, David E.; March, Anthony W.; Bostick, Benjamin; Spring, Stefan; Caccavo, Frank; Fendorf, Scott; Rosenzweig, R. Frank
2000-01-01
Mining-impacted sediments of Lake Coeur d'Alene, Idaho, contain more than 10% metals on a dry weight basis, approximately 80% of which is iron. Since iron (hydr)oxides adsorb toxic, ore-associated elements, such as arsenic, iron (hydr)oxide reduction may in part control the mobility and bioavailability of these elements. Geochemical and microbiological data were collected to examine the ecological role of dissimilatory Fe(III)-reducing bacteria in this habitat. The concentration of mild-acid-extractable Fe(II) increased with sediment depth up to 50 g kg−1, suggesting that iron reduction has occurred recently. The maximum concentrations of dissolved Fe(II) in interstitial water (41 mg liter−1) occurred 10 to 15 cm beneath the sediment-water interface, suggesting that sulfidogenesis may not be the predominant terminal electron-accepting process in this environment and that dissolved Fe(II) arises from biological reductive dissolution of iron (hydr)oxides. The concentration of sedimentary magnetite (Fe3O4), a common product of bacterial Fe(III) hydroxide reduction, was as much as 15.5 g kg−1. Most-probable-number enrichment cultures revealed that the mean density of Fe(III)-reducing bacteria was 8.3 × 105 cells g (dry weight) of sediment−1. Two new strains of dissimilatory Fe(III)-reducing bacteria were isolated from surface sediments. Collectively, the results of this study support the hypothesis that dissimilatory reduction of iron has been and continues to be an important biogeochemical process in the environment examined. PMID:10618217
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Selective sequential precipitation of dissolved metals in mine drainage from coal mine
NASA Astrophysics Data System (ADS)
Yim, Giljae; Bok, Songmin; Ji, Sangwoo; Oh, Chamteut; Cheong, Youngwook; Han, Youngsoo; Ahn, Joosung
2017-04-01
In abandoned mines in Korea, a large amount of mine drainage continues to flow out and spread pollution. In purification of the mine drainage a massive amount of sludge is generated as waste. Since this metal sludge contains high Fe, Al and Mn oxides, developing the treatment method to recover homogeneous individual metal with high purity may beneficial to recycle waste metals as useful resources and reduce the amount of sludge production. In this regard, we established a dissolved metals selective precipitation process to treat Waryong Industry's mine drainage. The process that selectively precipitates metals dissolved in mine drainage is a continuous Fe-buffer-Al process, and each process consists of the neutralization tank, the coagulation tank, and the settling tank. Based on this process, this study verified the operational applicability of the Fe and Al selective precipitation. Our previous study revealed that high-purity Fe and Al precipitates could be recovered at a flow rate of 1.5 ton/day, while the lower purity was achieved when the rate was increased to about 3 ton/day due to the difficulty in reagent dosage control. In the current study was conducted to increase the capacity of the system to recover Fe and Al as high-purity precipitates at a flow rate of 10 ton/day with the ensured continuous operations by introducing an automatic reagent injection system. The previous study had a difficulty in controlling the pH and operating system continuously due to the manually controlled reagent injection system. To upgrade this and ensure the optimal pH in a stable way, a continuous reagent injection system was installed. The result of operation of the 10 ton/day system confirmed that the scaled-up process could maintain the stable recovery rates and purities of precipitates on site.
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NASA Technical Reports Server (NTRS)
Johnson, M. S.; Meskhidze, N.
2013-01-01
Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.
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NASA Astrophysics Data System (ADS)
Knappett, P.; Myers, K.; Jewell, K.; Berube, M.; Datta, S.; Hossain, A.; Hosain, A.; Lipsi, M.; Ahmed, K. M.
2017-12-01
River stage fluctuations drives river water, rich oxidants, into riverbanks aquifers. When these aquifers are rich in dissolved iron (Fe), iron oxides (FeOOH) precipitate, creating a reactive surface upon which toxic elements such as arsenic (As) may sorb. These Permeable Natural Reactive Barriers (PNRBs) have been studied on the Meghna River. The lack of understanding of what controls their formation and fate could result in dangerous consequences. Pumping of riverbank aquifers for irrigation could re-mobilize toxic concentrations of As into drinking water aquifers. It is important to understand the hydrological, geochemical and biological processes controlling the properties of PNRBs. To this end, monitoring wells and drive-point piezometers were installed orthogonal to the Meghna River in Bangladesh. The dimensions of the shallow aquifer was mapped with Electrical Resistivity Tomography (ERT). The monitoring wells and a river gage were instrumented with pressure transducers to record water level fluctuations. Groundwater flows towards the river for most of the year but reverses under the influence of local irrigation pumping in the late dry season and rapidly rising river stage in the early monsoon. Semi-diurnal tides in the dry season have an amplitude of 80 cm. Declining concentrations of conservative dissolved ions towards the river indicated a zone of dilution from river water extending up to 50 m from the river's dry season edge. Dissolved As was produced as groundwater passed through this dilution zone until the final 20 m where As was abruptly removed from solution. This location coincided with a PNRB with enriched solid-phase Fe and Mn within the upper 3 m of sediment. 16S bacterial community DNA was sequenced from the wells and drive-point piezometers to map the distribution of Fe and As reducers and oxidizers. The richest overall biodiversity was found within the PNRB zone. It contained the most oxidizing and reducing species. This evidence suggests that transient river levels drive mixing between oxidizing and reducing agents in Hyporheic Zones (HZs). When the shallow aquifers are rich in dissolved concentrations of Fe and As, this mixing results in the accumulation of solid-phase Fe and As. This is likely a general process affecting other oxide-forming metals and toxic elements they bind.
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Leachable particulate iron in the Columbia River, estuary, and near-field plume
NASA Astrophysics Data System (ADS)
Lippiatt, Sherry M.; Brown, Matthew T.; Lohan, Maeve C.; Berger, Carolyn J. M.; Bruland, Kenneth W.
2010-03-01
This study examines the distribution of leachable particulate iron (Fe) in the Columbia River, estuary, and near-field plume. Surface samples were collected during late spring and summer of 2004-2006 as part of four River Influence on Shelf Ecosystems (RISE) cruises. Tidal amplitude and river flow are the primary factors influencing the estuary leachable particulate Fe concentrations, with greater values during high flow and/or spring tides. Near the mouth of the estuary, leachable particulate Fe [defined as the particulate Fe solubilized with a 25% acetic acid (pH 2) leach containing a weak reducing agent to reduce Fe oxyhydroxides and a short heating step to access intracellular Fe] averaged 770 nM during either spring tide or high flow, compared to 320 nM during neap tide, low flow conditions. In the near-field Columbia River plume, elevated leachable particulate Fe concentrations occur during spring tides and/or higher river flow, with resuspended shelf sediment as an additional source to the plume during periods of coastal upwelling and spring tides. Near-field plume concentrations of leachable particulate Fe (at a salinity of 20) averaged 660 nM during either spring tide or high flow, compared to 300 nM during neap tide, low flow conditions. Regardless of tidal amplitude and river flow, leachable particulate Fe concentrations in both the river/estuary and near-field plume are consistently one to two orders of magnitude greater than dissolved Fe concentrations. The Columbia River is an important source of reactive Fe to the productive coastal waters off Oregon and Washington, and leachable particulate Fe is available for solubilization following biological drawdown of the dissolved phase. Elevated leachable Fe concentrations allow coastal waters influenced by the Columbia River plume to remain Fe-replete and support phytoplankton production during the spring and summer seasons.
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Impacts of flocculation on the distribution and diagenesis of iron in boreal estuarine sediments
NASA Astrophysics Data System (ADS)
Jilbert, Tom; Asmala, Eero; Schröder, Christian; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Virtasalo, Joonas J.; Kotilainen, Aarno; Peltola, Pasi; Ekholm, Päivi; Hietanen, Susanna
2018-03-01
Iron (Fe) plays a key role in sedimentary diagenetic processes in coastal systems, participating in various redox reactions and influencing the burial of organic carbon. Large amounts of Fe enter the marine environment from boreal river catchments associated with dissolved organic matter (DOM) and as colloidal Fe oxyhydroxides, principally ferrihydrite. However, the fate of this Fe pool in estuarine sediments has not been extensively studied. Here we show that flocculation processes along a salinity gradient in an estuary of the northern Baltic Sea efficiently transfer Fe and OM from the dissolved phase into particulate material that accumulates in the sediments. Flocculation of Fe and OM is partially decoupled. This is likely due to the presence of discrete colloidal ferrihydrite in the freshwater Fe pool, which responds differently from DOM to estuarine mixing. Further decoupling of Fe from OM occurs during sedimentation. While we observe a clear decline with distance offshore in the proportion of terrestrial material in the sedimentary particulate organic matter (POM) pool, the distribution of flocculated Fe in sediments is modulated by focusing effects. Labile Fe phases are most abundant at a deep site in the inner basin of the estuary, consistent with input from flocculation and subsequent focusing. The majority of the labile Fe pool is present as Fe (II), including both acid-volatile sulfur (AVS)-bound Fe and unsulfidized phases. The ubiquitous presence of unsulfidized Fe (II) throughout the sediment column suggests Fe (II)-OM complexes derived from reduction of flocculated Fe (III)-OM, while other Fe (II) phases are likely derived from the reduction of flocculated ferrihydrite. Depth-integrated rates of Fe (II) accumulation (AVS-Fe + unsulfidized Fe (II) + pyrite) for the period 1970-2015 are greater in the inner basin of the estuary with respect to a site further offshore, confirming higher rates of Fe reduction in near-shore areas. Mössbauer 57Fe spectroscopy shows that refractory Fe is composed largely of superparamagnetic Fe (III), high-spin Fe (II) in silicates, and, at one station, also oxide minerals derived from past industrial activities. Our results highlight that the cycling of Fe in boreal estuarine environments is complex, and that the partial decoupling of Fe from OM during flocculation and sedimentation is key to understanding the role of Fe in sedimentary diagenetic processes in coastal areas.
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Acidity and Alkalinity in mine drainage: Practical considerations
Cravotta, III, Charles A.; Kirby, Carl S.
2004-01-01
In this paper, we emphasize that the Standard Method hot peroxide treatment procedure for acidity determination (hot acidity) directly measures net acidity or net alkalinity, but that more than one water-quality measure can be useful as a measure of the severity of acid mine drainage. We demonstrate that the hot acidity is related to the pH, alkalinity, and dissolved concentrations of Fe, Mn, and Al in fresh mine drainage. We show that the hot acidity accurately indicates the potential for pH to decrease to acidic values after complete oxidation of Fe and Mn, and it indicates the excess alkalinity or that required for neutralization of the sample. We show that the hot acidity method gives consistent, interpretable results on fresh or aged samples. Regional data for mine-drainage quality in Pennsylvania indicated the pH of fresh samples was predominantly acidic (pH 2.5 to 4) or near neutral (pH 6 to 7); approximately 25 percent of the samples had intermediate pH values. This bimodal frequency distribution of pH was distinctive for fully oxidized samples; oxidized samples had acidic or near-neutral pH, only. Samples that had nearneutral pH after oxidation had negative hot acidity; samples that had acidic pH after oxidation had positive hot acidity. Samples with comparable pH values had variable hot acidities owing to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. The hot acidity was comparable to net acidity computed on the basis of initial pH and concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity computed from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was comparable to that computed on the basis of aqueous species and FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the hot acidities were comparable for fresh and aged samples. Thus, meaningful “net” acidity can be determined from a measured hot acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. Together, these water-quality data can be useful for evaluating the potential for toxicity, corrosion, or encrustation and can be helpful for determining the appropriate remediation. By demonstrating the measurements on fresh and aged samples, we hope to encourage (1) consistent use of the hot peroxide treatment procedure for acidity determination and (2) consistent reporting of negative acidity values.
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Solubility of iron from combustion source particles in acidic media linked to iron speciation.
Fu, Hongbo; Lin, Jun; Shang, Guangfeng; Dong, Wenbo; Grassian, Vichi H; Carmichael, Gregory R; Li, Yan; Chen, Jianmin
2012-10-16
In this study, iron solubility from six combustion source particles was investigated in acidic media. For comparison, a Chinese loess (CL) dust was also included. The solubility experiments confirmed that iron solubility was highly variable and dependent on particle sources. Under dark and light conditions, the combustion source particles dissolved faster and to a greater extent relative to CL. Oil fly ash (FA) yielded the highest soluble iron as compared to the other samples. Total iron solubility fractions measured in the dark after 12 h ranged between 2.9 and 74.1% of the initial iron content for the combustion-derived particles (Oil FA > biomass burning particles (BP) > coal FA). Ferrous iron represented the dominant soluble form of Fe in the suspensions of straw BP and corn BP, while total dissolved Fe presented mainly as ferric iron in the cases of oil FA, coal FA, and CL. Mössbauer measurements and TEM analysis revealed that Fe in oil FA was commonly presented as nanosized Fe(3)O(4) aggregates and Fe/S-rich particles. Highly labile source of Fe in corn BP could be originated from amorphous Fe form mixed internally with K-rich particles. However, Fe in coal FA was dominated by the more insoluble forms of both Fe-bearing aluminosilicate glass and Fe oxides. The data presented herein showed that iron speciation varies by source and is an important factor controlling iron solubility from these anthropogenic emissions in acidic solutions, suggesting that the variability of iron solubility from combustion-derived particles is related to the inherent character and origin of the aerosols themselves. Such information can be useful in improving our understanding on iron solubility from combustion aerosols when they undergo acidic processing during atmospheric transport.
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Iron-rich colloids as carriers of phosphorus in streams: A field-flow fractionation study.
Baken, Stijn; Regelink, Inge C; Comans, Rob N J; Smolders, Erik; Koopmans, Gerwin F
2016-08-01
Colloidal phosphorus (P) may represent an important fraction of the P in natural waters, but these colloids remain poorly characterized. In this work, we demonstrate the applicability of asymmetric flow field-flow fractionation (AF4) coupled to high resolution ICP-MS for the characterization of low concentrations of P-bearing colloids. Colloids from five streams draining catchments with contrasting properties were characterized by AF4-ICP-MS and by membrane filtration. All streams contain free humic substances (2-3 nm) and Fe-bearing colloids (3-1200 nm). Two soft water streams contain primary Fe oxyhydroxide-humic nanoparticles (3-6 nm) and aggregates thereof (up to 150 nm). In contrast, three harder water streams contain larger aggregates (40-1200 nm) which consist of diverse associations between Fe oxyhydroxides, humic substances, clay minerals, and possibly ferric phosphate minerals. Despite the diversity of colloids encountered in these contrasting streams, P is in most of the samples predominantly associated with Fe-bearing colloids (mostly Fe oxyhydroxides) at molar P:Fe ratios between 0.02 and 1.5. The molar P:Fe ratio of the waters explains the partitioning of P between colloids and truly dissolved species. Waters with a high P:Fe ratio predominantly contain truly dissolved species because the Fe-rich colloids are saturated with P, whereas waters with a low P:Fe ratio mostly contain colloidal P species. Overall, AF4-ICP-MS is a suitable technique to characterize the diverse P-binding colloids in natural waters. Such colloids may increase the mobility or decrease the bioavailability of P, and they therefore need to be considered when addressing the transport and environmental effects of P in catchments. Copyright © 2016 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Lipka, Marko; Schneider, Jonas; Schmiedinger, Iris; Westphal, Julia; Escher, Peter; Sültenfuß, Jürgen; Dellwig, Olaf; Winde, Vera; Böttcher, Michael E.
2017-04-01
Submarine ground water discharge (SGD) into coastal ecosystems is perceived as an important source of fresh water and solutes (nutrients, metabolites, trace elements) in marine biogeochemical cycles. Less is known about its significance for the German coastal zone. We present here the results of hydrogeochemical and stable isotope geochemical studies in an area that is affected by SGD into the southern Baltic Sea. Anoxic groundwaters emerging as springs at the shore zone of the southern Baltic Sea are windows into the composition of subterrestrial ground water composition. They were investigated on a seasonal base for about five years. Water samples were analyzed for the concentrations of major and trace elements, pH, and the stable isotope ratios of water, DIC and sulfate. Newly formed precipitates in the stream bed were characterized via SEM-EDX and the stable isotope composition, as well as chemically extracted for the determination of the solid composition. The springs emerge in small pits yielding discharges of about 10 l/min each. Surrounding sediments are sandy with gravels found at depth and corresponding high permeabilities. The positions of different springs on the shore zone were geostationary during the investigation period while their shape varied due to wind- and wave action. The 2H and 18O contents of the spring waters indicate the ground water to originate from relatively young mixed meteoric waters. Dating by means of tritium and noble gases (3H, 3He, 4He, Ne) yields an age of the spring waters of about 25-32 years, with different mixing proportions of tritium-free waters. The springs are hydrogeochemically characterized by dissolved Ca, Mg, Na, bicarbonate, and sulfate, mainly reflecting the water-rock interaction with aquifer material in the recharge area. The isotope signature of DIC indicates the uptake of biogenic CO2 in the soil zone followed by the dissolution of carbonate minerals in the soil/ aquifer system. The oxygen-free ground water is rich in dissolved iron (Fe) and phosphorous (P). Iron(oxyhydr)oxide precipitates in the stream beds acting as a sink for dissolved PO4 and minor Ca. The investigation reveals that the surface precipitation on the beach leads to the formation of submarine groundwater discharge essentially free of dissolved Fe and PO4. The formation of Fe-phases in the subterranean estuary is supposed at depth influencing the release of nutrients and metals into the coastal ecosystem. Before the water passes to underground drainage into a subterranean mixing zone with brackish Baltic Sea waters, the above ground draining streams degas carbon dioxide and take up oxygen in contact with the atmosphere. Iron(oxyhydr)oxide precipitates in the stream beds acting as a sink for dissolved phosphate. Residues of Fe- oxidizing bacteria were found in the stream bed rust indicating an involvement of microbes to catalyze the dissolved Fe removal. The investigation reveals that the surface precipitation on the beach leads to the formation of submarine groundwater discharge essentially free of dissolved iron and phosphate. The formation of Fe-phases in the subterranean estuary is also supposed to take place at depth thereby influencing the release of nutrients and metals into the Baltic Sea coastal ecosystem. This work was supported by the BONUS+ project AMBER, the Leibniz IOW and the Graduiertenkolleg BALTIC TRANSCOAST.
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Iron Cycling in Sediment of the North Atlantic: Preliminary Results from R/V Knorr Expedition 223
NASA Astrophysics Data System (ADS)
Anderson, C. H.; Estes, E. R.; Dyar, M. D.; Murray, R. W.; Spivack, A. J.; Sauvage, J.; McKinley, C. C.; Present, T. M.; Homola, K.; Pockalny, R. A.; D'Hondt, S.
2015-12-01
Iron (Fe) in marine sediments is a significant microbial electron acceptor [Fe(III)] in suboxic conditions and is an electron donor [Fe(II)] in oxic conditions. In the transition from oxic to suboxic sediment, a portion of solid Fe is reduced and mobilized as soluble Fe(II) into interstitial water during the oxidation of organic matter. The presence of Fe and its oxidation state in oxic sediment provides insight into an important metabolic and mineral reaction pathway in subseafloor sediment. We recovered bulk sediment and interstitial water at western North Atlantic sites during Expedition 223 on the R/V Knorr in November, 2014. The expedition targeted regions with predominantly oxic sediment and regions with predominantly anoxic sediment, ideal for investigating redox Fe cycling between solid and aqueous phases. At Site 10 (14.4008N, 50.6209W, 4455m water depth), interstitial dissolved oxygen is depleted within the upper few meters of sediment. At Site 12 (29.6767N, 58.3285W, 5637m water depth), interstitial dissolved oxygen is present throughout the cored sediment column (10s of meters). Here we present total solid Fe concentration for 45 bulk sediment samples and total aqueous Fe and Mn concentrations for 50 interstitial water samples analyzed via ICP-ES. We additionally present Fe(II) and Fe(III) speciation results from 10 solid sediment samples determined by Mossbauer spectroscopy. We trace downcore fluctuations in Fe in solid and aqueous phases to understand Fe cycling in oxic, suboxic, and transitional regimes. Our preliminary data indicate that solid Fe concentration ranges from 4-6 wt % at the oxic site; aqueous Fe ranges from below detection to 20μM and aqueous Mn ranges from 1 to 125 μM at the anoxic site. In the anoxic sediment (Site 10), 86-90% of the total Fe is oxidized [Fe(III)] and 10-14% as reduced [Fe(II)], compared to 3-6% as reduced [Fe(II)] at the oxic site (Site 12), even in sediment as old as 25 million years.
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Implementing Cleaner Printed Wiring Board Technologies: Surface Finishes
This document describes the problems, solutions, and time and effort involved in implementing alternative surface finish technologies, and this guide is produced as part of the DfE Printed Wiring Board Project
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Aharonovich, Marius; Arnon, Shlomi
2005-08-01
Optical wireless communication (OWC) systems use the atmosphere as a propagation medium. However, a common problem is that from time to time moderate cloud and fog emerge between the receiver and the transmitter. These adverse weather conditions impose temporal broadening and power loss on the optical signal, which reduces the digital signal-to-noise ratio (DSNR), produces significant intersymbol interference (ISI), and degrades the communication system's bit error rate (BER) and throughput. We propose and investigate the use of a combined adaptive bandwidth mechanism and decision feedback equalizer (DFE) to mitigate these atmospheric multipath effects. Based on theoretical analysis and simulations of DSNR penalties, BER, and optimum system bandwidths, we show that a DFE improves the outdoor OWC system immunity to ISI in foggy weather while maintaining high throughput and desired low BER.
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Baken, Stijn; Verbeeck, Mieke; Verheyen, Dries; Diels, Jan; Smolders, Erik
2015-03-15
Redox reactions involving iron (Fe) strongly affect the mobility of phosphorus (P) and its migration from agricultural land to freshwater. We studied the transfer of P from groundwater to open drainage ditches in an area where, due to Fe(II) rich groundwater, the sediments of these ditches contain accumulated Fe oxyhydroxides. The average P concentrations in the groundwater feeding two out of three studied drainage ditches exceeded environmental limits for freshwaters by factors 11 and 16, but after passing through the Fe-rich sediments, the P concentrations in the ditch water were below these limits. In order to identify the processes which govern Fe and P mobility in these systems, we used diffusive equilibration in thin films (DET) to measure the vertical concentration profiles of P and Fe in the sediment pore water and in the ditchwater. The Fe concentrations in the sediment pore water ranged between 10 and 200 mg L(-1) and exceeded those in the inflowing groundwater by approximately one order of magnitude, due to reductive dissolution of Fe oxyhydroxides in the sediment. The dissolved P concentrations only marginally increased between groundwater and sediment pore water. In the poorly mixed ditchwater, the dissolved Fe concentrations decreased towards the water surface due to oxidative precipitation of fresh Fe oxyhydroxides, and the P concentrations decreased more sharply than those of Fe. These observations support the view that the dynamics of Fe and P are governed by reduction reactions in the sediment and by oxidation reactions in the ditchwater. In the sediment, reductive dissolution of P-containing Fe oxyhydroxides causes more efficient solubilization of Fe than of P, likely because P is buffered by adsorption on residual Fe oxyhydroxides. Conversely, in the ditchwater, oxidative precipitation causes more efficient immobilization of P than of Fe, due to ferric phosphate formation. The combination of these processes yields a natural and highly efficient sink for P. It is concluded that, in Fe-rich systems, the fate of P at the sediment-water interface is determined by reduction and oxidation of Fe. Copyright © 2015 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Gunnars, Anneli; Blomqvist, Sven; Johansson, Peter; Andersson, Christian
2002-03-01
The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.
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NASA Astrophysics Data System (ADS)
Suresh Babu, S.
2016-12-01
Forty two samples were acquired from the surface and bottom water profiles along 5 transects spread over Bahia Magdalena lagoon, Baja California Sur to assess the behavior of trace metals in a high influenced upwelling region on the Pacific coast. To elaborate the fate of metals, also the physico-chemical parameters (pH, temperature, salinity, conductivity, dissolved oxygen). Determination of the concentrations of trace metals (Fe, Mn, Cr, Cu, Co, Pb, Ni, Zn, Cd As, Hg) were measured using Atomic absorption spectrometry. The results demonstrated high values of As, Ni and Co which is attributed to the local geology and phosphate deposits. Low values of Fe and Mn are attested to the oxic conditions of the lagoon which are responsible for the oxidation of Fe and Mn. The region witnesses raised temperatures (28.92ºC) and salinities of 35.2 PSU for its arid climatic conditions and high rates of evaporation. In general, the region presented minor quantities of dissolved trace metals due to dispersion and high intense interaction with the open sea. The results were also compared with other studies to understand the enrichment pattern in this side of the pacific coast which experiences various geothermal activities and upwelling phenomenon.
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Annealing Behavior of 57Fe Implanted in ZrO2(Y)
NASA Astrophysics Data System (ADS)
Zhang, G. L.; Yu, F. H.; Weng, H. M.; Zhang, H. H.
1998-12-01
Using conversion electron Mossbauer spectroscopy(CEMS) and slow positron beam, the chemical states of the implanted 57Fe (100KeV,3 × 10 16 ions/cm 2) in ZrO2 containing 3 mol% Y 2O 3( ZY 3) and its thermodynamic behavior during annealing process with the temperature from 200 to 500°C were studied. After annealing at 400°C the complex of Fe3+-V has been mostly dissolved, and the prior phase to α-Fe and α-Fe nano-crystalline cluster were present in the sample. Meanwhile the mixed conducting of oxygen-ions and electrons in the ZY3 containing Fe sample appeared.
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Agrawal, Abinash; Ferguson, William J; Gardner, Bruce O; Christ, John A; Bandstra, Joel Z; Tratnyek, Paul G
2002-10-15
The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.
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Jung, Hun Bok; Charette, Matthew A.; Zheng, Yan
2009-01-01
A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(II) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows towards the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80~90% Fe(III)) are 734±232 mg kg-1, sedimentary phosphate extractable As (90~100% As(V)) are 316±111 μg kg-1, and are linearly correlated. Batch adsorption of As(III) onto orange, brown and gray sediments follows Langmuir isotherms, and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site specific isotherms should be established for Kd or SCM based models. PMID:19708362
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Runkel, R.L.; Kimball, B.A.
2002-01-01
A reactive transport model based on one-dimensional transport and equilibrium chemistry is applied to synoptic data from an acid mine drainage stream. Model inputs include streamflow estimates based on tracer dilution, inflow chemistry based on synoptic sampling, and equilibrium constants describing acid/base, complexation, precipitation/dissolution, and sorption reactions. The dominant features of observed spatial profiles in pH and metal concentration are reproduced along the 3.5-km study reach by simulating the precipitation of Fe(III) and Al solid phases and the sorption of Cu, As, and Pb onto freshly precipitated iron-(III) oxides. Given this quantitative description of existing conditions, additional simulations are conducted to estimate the streamwater quality that could result from two hypothetical remediation plans. Both remediation plans involve the addition of CaCO3 to raise the pH of a small, acidic inflow from ???2.4 to ???7.0. This pH increase results in a reduced metal load that is routed downstream by the reactive transport model, thereby providing an estimate of post-remediation water quality. The first remediation plan assumes a closed system wherein inflow Fe(II) is not oxidized by the treatment system; under the second remediation plan, an open system is assumed, and Fe(II) is oxidized within the treatment system. Both plans increase instream pH and substantially reduce total and dissolved concentrations of Al, As, Cu, and Fe(II+III) at the terminus of the study reach. Dissolved Pb concentrations are reduced by ???18% under the first remediation plan due to sorption onto iron-(III) oxides within the treatment system and stream channel. In contrast, iron(III) oxides are limiting under the second remediation plan, and removal of dissolved Pb occurs primarily within the treatment system. This limitation results in an increase in dissolved Pb concentrations over existing conditions as additional downstream sources of Pb are not attenuated by sorption.
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Thanh-Nho, Nguyen; Strady, Emilie; Nhu-Trang, Tran-Thi; David, Frank; Marchand, Cyril
2018-04-01
Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log K D values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Effect of adsorbent addition on floc formation and clarification.
Younker, Jessica M; Walsh, Margaret E
2016-07-01
Adding adsorbent into the coagulation process is an emerging treatment solution for targeting hard-to-remove dissolved organic compounds from both drinking water and industrial wastewater. The impact of adding powdered activated carbon (PAC) or organoclay (OC) adsorbents with ferric chloride (FeCl3) coagulant was investigated in terms of potential changes to the coagulated flocs formed with respect to size, structure, and breakage and regrowth properties. The ability of dissolved air flotation (DAF) and sedimentation (SED) clarification processes to remove hybrid adsorbent-coagulant flocs was also evaluated through clarified water quality analysis of samples collected in bench-scale jar test experiments. The jar tests were conducted using both a synthetic fresh water and oily wastewater test water spiked with dissolved aromatic compounds phenol and naphthalene. Results of the study demonstrated that addition of adsorbent reduced the median coagulated floc size by up to 50% but did not affect floc strength or regrowth potential after application of high shear. Experimental results in fresh water demonstrated that sedimentation was more effective than DAF for clarification of both FeCl3-PAC and FeCl3-OC floc aggregates. However, experimental tests performed on the synthetic oily wastewater showed that coagulant-adsorbent floc aggregates were effectively removed with both DAF and sedimentation treatment, with lower residual turbidity achieved in clarified water samples than with coagulation treatment alone. Addition of OC or PAC into the coagulation process resulted in removals of over half, or nearly all of the dissolved aromatics, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Metal discharges by Sinaloa Rivers to the coastal zone of NW Mexico.
Frías-Espericueta, M G; Mejía-Cruz, R; Osuna López, I; Muy-Rangel, M D; Rubio-Carrasco, W; Aguilar-Juárez, M; Voltolina, D
2014-02-01
The aim of this work was to survey the discharges of dissolved and particulate Cd, Cu, Fe, Mn, Pb and Zn of the eight main rivers of Sinaloa State to the Mexican coastal environment. Zn was the most abundant dissolved metal and Fe was the most abundant particulate (8.02-16.90 and 51.8-1,140.3 μg/L, respectively). Only particulate Mn had significantly (p = 0.028) higher values in summer-fall (rainy season), whereas the significantly (p = 0.036) higher values of dissolved Zn were observed in winter and spring. The highest annual total discharges to Sinaloa coastal waters were those of the rivers San Lorenzo and Piaxtla (>2 × 10(3) m.t.) and the lowest those of rivers Baluarte and El Fuerte (349 and 119 m.t., respectively). Pb concentrations may become of concern, because they are higher than the value recommended for the welfare of aquatic communities of natural waters.
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NASA Astrophysics Data System (ADS)
Oleinikova, Olga V.; Drozdova, Olga Yu.; Lapitskiy, Sergey A.; Demin, Vladimir V.; Bychkov, Andrey Yu.; Pokrovsky, Oleg S.
2017-08-01
Photochemical degradation of dissolved organic matter (DOM) is recognized as the major driver of CO2 emission to the atmosphere from the inland waters of high latitudes. In contrast to numerous studies of photo-induced DOM transformation, the behavior of trace element (TE) during photodegradation of boreal DOM remains virtually unknown. Towards a better understanding of concentration, size fractionation and speciation change of DOM and TE in boreal waters subjected to solar radiation, we conducted on-site photo-degradation experiments in stream and bog water collected from a pristine zone of the Northern Karelia (Russian subarctic). The removal of Fe and Al occurred only in the bog water (90% and 50% respectively, over 5 days of reaction), whereas no detectable decrease of dissolved (<0.22 μm) Al and Fe concentration was observed in the boreal stream. A number of low-soluble TE linked to Fe-rich organo-mineral colloids followed the behavior of Fe during bog water exposure to sunlight: Al, P, Ti, V, Cr, As, Y, Zr, REEs, Hf, Th, Pb and U. The second group of elements (Li, B, Mg, Ca, Sr, Ba, Na, K, Rb, Si, Mn, Ni, Cu, Co, Cd, Sb) was indifferent to photodegradation of DOM and exhibited a non-systematic variation (±10-15% from the control) of <0.22 μm fraction in the course of sunlight exposure. The bog water insolation yielded a factor of 3 ± 1 increase of low molecular weight (LMW < 1 kDa) fraction of organic carbon, Al, Fe, U, Mg, Ca, Mn, Co, Ni, Sr, Cd and Ba after 200 h of sunlight exposure compared to the dark control. The LMW< 1 kDa fraction was preferentially enriched in Fe, Al, Ca, Mg and other divalent metals relative to Corg. The climate warming leading to water temperature rise in the boreal zone will intensify the Fe and Al hydroxide coagulation while increasing the production of LMW organic ligands and free metals and metal - organic complexes.
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Safer Choice Partner of the Year Awards Application Form
EPA's Design for the Environment program developed the Safer Product Labeling Program Partner of the Year Award program to recognize DfE stakeholders that have furthered the safer chemistry goals of the program
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The kinetics of the oxidation of ferrous iron in synthetic and natural waters
NASA Astrophysics Data System (ADS)
Davison, W.; Seed, G.
1983-01-01
The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six. The present data, together with a comprehensive survey of the literature, are used to suggest a 'universal' rate constant of ca. 2 × 10 13 M -2 atm -1 min -1 (range 1.5-3 × 10 13) in the rate law -d[Fe II]/dt = k[Fe II]pO 2 (OH-) 2 for natural freshwaters in the pH range 6.5-7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.
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Effect of iron on inhibition of acid demineralisation of bovine dental enamel in vitro.
Buzalaf, Marília Afonso Rabelo; de Moraes Italiani, Flávia; Kato, Melissa Thiemi; Martinhon, Cleide Cristina Rodrigues; Magalhães, Ana Carolina
2006-10-01
Iron ions (Fe(2+)) have been shown to be cariostatic in many studies particularly by their ability to reduce bacterial metabolism. Nevertheless, the role of iron ions on dissolution of enamel is unexplored. The aim of the present study was therefore to investigate the protective effect of increasing concentrations (0-120mmol/L) of Fe(2+) on the dissolution of enamel. Enamel powder was subjected to acetic acid made with increasing concentrations with respect to FeSO(4)x7H(2)O. In order to determine the amount of enamel dissolved, the phosphate released in the medium was analysed spectrophotometrically using the Fiske-Subarrow method. Data were tested using Kruskall-Wall and Dunn's tests (p<0.05). The degree of protection was found to approach maximum at about 15mmol/L Fe(2+). Higher concentrations of Fe(2+) did not have an extra effect on inhibition of dissolution of enamel powder. In the next step, the protective effect of 15mmol/L Fe(2+) against mineral dissolution of the bovine enamel was evaluated using a simple abiotic model system. Enamel blocks were exposed to a sequence of seven plastic vials, each containing 1mL of 10mmol/L acetic acid. The acid in vial 4 was made 15mmol/L with respect to FeSO(4)x7H(2)O. The mineral dissolved during each challenge was thus determined by phosphate released as described above. Data were tested using two-way ANOVA (p<0.05). Lower demineralisation (around 45%) was found in vial 4 (with Fe) that continued stable until vial 7. Thus, our data suggest that Fe(2+) can be effective on inhibition of dissolution of enamel and that this effect may be durable.
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Cr(VI) removal by FeS-coated alumina, silica, and natural sand
NASA Astrophysics Data System (ADS)
Park, M.; Lee, S.; Jeong, H. Y.
2014-12-01
Removal of Cr(VI) was investigated using mackinawite (FeS)-coated mineral sorbents under anoxic conditions. The sorbents included alumina (Al), silica (WS), and natural sand (NS). By analysis of both solution and solid phases, all FeS-coated sorbents were found to reduce Cr(VI) into Cr(III). The sorption extent and mechanism of Cr(VI) strongly depended on the pH conditions. Only at pH 4.5, significant amounts of the dissolved Cr remained in the solution. Titration of dissolved Cr(III) and Fe(III) by NaOH solutions indicated that no bulk-phase precipitation occurred at pH 4.5. Also, the removal of Cr(VI) at pH 4.5 was the greatest by FeS-coated NS. Consistent with these, Cr-K edge EXAFS revealed that Cr was removed by FeS-coated NS via surface precipitation, and that it was immobilized by FeS-coated WS and Al by forming surface clusters. Regardless of FeS-coated sorbents, at pH 7.0 and pH 9.5, the initially added Cr(VI) was quantitatively removed from the solution phase. By EXAFS analysis, the Cr sorption by FeS-coated Al was mainly due to the bulk-phase precipitation of Cr(OH)3(s) or [Cr, Fe](OH)3(s). In case of FeS-coated WS and NS, the short Cr-Cr distance (~2.6 Å) at pH 7.0 and pH 9.5 was not simply accounted for by the bulk precipitation as either hydroxide (rCr-Cr ~ 3.0 Å), and it would rather result from the surface precipitation. Such a difference in the coordination structure among FeS-coated sorbents was likely due to in the lower surface area of the former available for the surface precipitation.
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Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Cleasby, T.E.; McCleskey, R. Blaine
2005-01-01
Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters. Copyright ?? 2005 Elsevier Ltd.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Katherine Barbeau
2007-04-10
Recent mesoscale iron fertilization studies in the Southern Ocean (e.g. SOIREE, EisenEx, SOFeX) have demonstrated the importance of iron as a limiting factor for phytoplankton growth in these high nutrient, low-chlorophyll (HNLC) waters. Results of these experiments have demonstrated that factors which influence the biological availability of the iron supplied to phytoplankton are crucial in bloom development, longevity, and generation of carbon export flux. These findings have important implications for the future development of iron fertilization protocols to enhance carbon sequestration in high-latitude oceans. In particular, processes which lead to the mobilization and retention of iron in dissolved form inmore » the upper ocean are important in promoting continued biological availability of iron. Such processes can include photochemical redox cycling, which leads to the formation of soluble reduced iron, Fe(II), within iron-enriched waters. Creation of effective fertilization schemes will thus require more information about Fe(II) photoproduction in Southern Ocean waters as a means to retain new iron within the euphotic zone. To contribute to our knowledge base in this area, this project was funded by DOE with a goal of characterizing the production and retention of dissolved Fe as Fe(II) in an area of the southern Drake Passage near the Shackleton Transverse Ridge, a region with a strong recurrent chlorophyll gradient which is believed to be a site of natural iron enrichment in the Southern Ocean. This area was the focus of a multidisciplinary NSF/OPP-funded investigation in February 2004 (OPP02-30443, lead PI Greg Mitchell, SIO/UCSD) to determine the influence of mesoscale circulation and iron transport with regard to the observed patterns in sea surface chlorophyll in the region near the Shackleton Transverse Ridge. A number of parameters were assessed across this gradient in order to reveal interactions between plankton community structure and iron distributions. As a co-PI in the NSF/OPP-funded project, I was responsible for iron addition incubation and radiotracer experiments, and analysis of iron chemistry, including iron-organic speciation. This final technical report describes the results of my DOE funded project to analyse reduced iron species using an FeLume flow injection analysis chemiluminescence system as an extension of my work on the NSF/OPP project. On the cruise in 2004, spatial and temporal gradients in Fe(II) were determined, and on-board incubations were conducted to study Fe(II) lifetime and production. Following the cruise a further series of experiments was conducted in my laboratory to study Fe(II) lifetimes and photoproduction under conditions typical of high latitude waters. The findings of this study suggest that, in contrast to results observed during mesoscale iron addition experiments, steady-state levels of Fe(II) are likely to remain low (below detection) even within a significant gradient in dissolved Fe concentrations produced as a result of natural iron enrichment processes. Fe(II) is likely to be produced, however, as a reactive intermediate associated with photochemical reactions in surface waters. While Fe(II) lifetimes measured in the field in this study were commensurate with those determined in previously published Southern Ocean work, Fe(II) lifetimes reflective of realistic Southern Ocean environmental conditions have proven difficult to determine in a laboratory setting, due to contamination by trace levels of H2O2. Laboratory experiments demonstrated that direct ligand-to-metal charge transfer reactions of strong Fe(III)-organic complexes do appear to be a viable source of available Fe(II) in Antarctic waters, and further studies are needed to characterize the temperature dependence of this phenomenon.« less
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NASA Astrophysics Data System (ADS)
Yang, YuQi; Si, HengGang; Yang, Hao; Zhang, Lan; Huang, DongFang; Chen, BaiYi; Xu, Fang; Hu, YongMei; Han, BaoJun
2018-01-01
According to the decoupling hypothesis for magnetic grains, the coercivity in sintered Nd-Fe-B magnets is increased after Cu doping, which is due to the formation of non-magnetic grain boundaries. However, this method partially fails, and ferromagnetic Fe-segregation occurs at the grain boundary. We discovered both experimentally and through calculation that the Fe content at the grain boundaries can be tuned across a wide range by introducing another element of Ag. Segregated Fe at high temperature at the grain boundary re-dissolves into Nd2Fe14B grains during annealing at low temperature. Both configurable and magnetic entropies contribute a large driving force for the formation of nonmagnetic grain boundaries. Almost zero Fe content could be achieved at the grain boundaries of sintered Nd-Fe-B magnet.
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NASA Astrophysics Data System (ADS)
Cen, Huoshi; Nan, Zhaodong
2018-10-01
Zn-doped Fe3O4 can be used as a catalyst in the photo-Fenton process to degrade dye molecules dissolved in water, in which cluster-shaped Zn-doped Fe3O4 (CSZnFe) was synthesized. To enhance the catalytic activity, monodisperse Zn-doped Fe3O4 (MZnFe) was facilely synthesized by a modified solvothermal method through replacement of sodium acetate by urea as a base. The particle size of MZnFe was about 9-16 nm. MZnFe exhibits a larger surface area and higher photo-Fenton catalytic activity for degradation of rhodamine B in water than CSZnFe. Additionally, MZnFe exhibits high saturation magnetization (about 80 emu/g), which is very convenient for separation of MZnFe from solution by a magnet. The growth processes for MZnFe were proposed on the basis of results from in situ calorimetry and other techniques, which indicated different formation mechanisms for MZnFe and CSZnFe.
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Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi
2017-02-15
Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.
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Dynamic characteristics of sulfur, iron and phosphorus in coastal polluted sediments, north China.
Sun, Qiyao; Sheng, Yanqing; Yang, Jian; Di Bonito, Marcello; Mortimer, Robert J G
2016-12-01
The cycling of sulfur (S), iron (Fe) and phosphorus (P) in sediments and pore water can impact the water quality of overlying water. In a heavily polluted river estuary (Yantai, China), vertical profiles of fluxes of dissolved sulfide, Fe 2+ and dissolved reactive phosphorus (DRP) in sediment pore water were investigated by the Diffusive Gradients in Thin films technique (DGT). Vertical fluxes of S, Fe, P in intertidal sediment showed the availability of DRP increased while the sulfide decreased with depth in surface sediment, indicating that sulfide accumulation could enhance P release in anoxic sediment. In sites with contrasting salinity, the relative dominance of iron and sulfate reduction was different, with iron reduction dominant over sulfate reduction in the upper sediment at an intertidal site but the reverse true in a freshwater site, with the other process dominating at depth in each case. Phosphate release was largely controlled by iron reduction. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Adsorption of Heavy Metals in Industrial Wastewater by Magnetic Nano-particles
NASA Astrophysics Data System (ADS)
Tu, Y.; You, C.
2010-12-01
Industrial wastewater containing heavy metals is of great concern because of their toxic impact to living species and environments. Removal of metal ions from industrial effluent using nano-particles is an area of extensive research. This study collected wastewaters and effluents from 11 industrial companies in tanning, electronic plating, printed circuit board manufacturing, semi-conductor, and metal surface treatment industry and studied in detailed the major and trace element compositions to develop potential fingerprinting technique for pollutant source identification. The results showed that electronic plating and metal surface treatment industry produce high Fe, Mn, Cr, Zn, Ni and Mo wastewater. The tanning industry and the printed circuit board manufacturing industry released wastewater with high Fe and Cr, Cu and Ni, respectively. For semi-conductor industry, significant dissolved In was detected in wastewater. The absorption experiments to remove heavy metals in waters were conducted using Fe3O4 nano-particles. Under optimal conditions, more than 99 % dissolved metals were removed in a few minutes.
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Zhu, Zhixiang; Wang, Jian; Qiu, Keqing; Liu, Chengyuan; Qi, Fei; Pan, Yang
2014-04-01
A novel vacuum ultraviolet (VUV) light source assembly (VUVLSA) for enhancing the ionization efficiency of photoionization mass spectrometer has been described. The VUVLSA composes of a Krypton lamp and a pair of disk electrodes with circular center cavities. The two interior surfaces that face the photoionization region were aluminum-coated. VUV light can be reflected back and forth in the photoionization region between the electrodes, thus the photoionization efficiency can be greatly enhanced. The performances of two different shaped electrodes, the coated double flat electrodes (DFE), and double conical electrodes, were studied. We showed that the signal amplification of coated DFE is around 4 times higher than that of uncoated electrodes without VUV light reflection. The relationship between the pressure of ionization chamber and mass signal enhancement has also been studied.
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Afterslip, tremor, and the Denali fault earthquake
Gomberg, Joan; Prejean, Stephanie; Ruppert, Natalia
2012-01-01
We tested the hypothesis that afterslip should be accompanied by tremor using observations of seismic and aseismic deformation surrounding the 2002 M 7.9 Denali fault, Alaska, earthquake (DFE). Afterslip happens more frequently than spontaneous slow slip and has been observed in a wider range of tectonic environments, and thus the existence or absence of tremor accompanying afterslip may provide new clues about tremor generation. We also searched for precursory tremor, as a proxy for posited accelerating slip leading to rupture. Our search yielded no tremor during the five days prior to the DFE or in several intervals in the three months after. This negative result and an array of other observations all may be explained by rupture penetrating below the presumed locked zone into the frictional transition zone. While not unique, such an explanation corroborates previous models of megathrust and transform earthquake ruptures that extend well into the transition zone.
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NASA Astrophysics Data System (ADS)
Revels, Brandi N.; Zhang, Ruifeng; Adkins, Jess F.; John, Seth G.
2015-10-01
Iron (Fe) is an essential nutrient for life on land and in the oceans. Iron stable isotope ratios (δ56Fe) can be used to study the biogeochemical cycling of Fe between particulate and dissolved phases in terrestrial and marine environments. We have investigated the dissolution of Fe from natural particles both to understand the mechanisms of Fe dissolution, and to choose a leach appropriate for extracting labile Fe phases of marine particles. With a goal of finding leaches which would be appropriate for studying dissolved-particle interactions in an oxic water column, three particle types were chosen including oxic seafloor sediments (MESS-3), terrestrial dust (Arizona Test Dust - A2 Fine), and ocean sediment trap material from the Cariaco basin. Four leaches were tested, including three acidic leaches similar to leaches previously applied to marine particles and sediments (25% acetic acid, 0.01 N HCl, and 0.5 N HCl) and a pH 8 oxalate-EDTA leach meant to mimic the dissolution of particles by organic complexation, as occurs in natural seawater. Each leach was applied for three different times (10 min, 2 h, 24 h) at three different temperatures (25 °C, 60 °C, 90 °C). MESS-3 was also leached under various redox conditions (0.02 M hydroxylamine hydrochloride or 0.02 M hydrogen peroxide). For all three sample types tested, we find a consistent relationship between the amount of Fe leached and leachate δ56Fe for all of the acidic leaches, and a different relationship between the amount of Fe leached and leachate δ56Fe for the oxalate-EDTA leach, suggesting that Fe was released through proton-promoted dissolution for all acidic leaches and by ligand-promoted dissolution for the oxalate-EDTA leach. Fe isotope fractionations of up to 2‰ were observed during acidic leaching of MESS-3 and Cariaco sediment trap material, but not for Arizona Test Dust, suggesting that sample composition influences fractionation, perhaps because Fe isotopes are greatly fractionated during leaching of silicates and clays but only minimally fractionated during dissolution of Fe oxyhydroxides. Two different analytical models were developed to explain the relationship between amount of Fe leached and δ56Fe, one of which assumes mixing between two Fe phases with different δ56Fe and different dissolution rates, and the other of which assumes dissolution of a single phase with a kinetic isotope effect. We apply both models to fit results from the acidic leaches of MESS-3 and find that the fit for both models is very similar, suggesting that isotope data will never be sufficient to distinguish between these two processes for natural materials. Next, we utilize our data to choose an optimal leach for application to marine particles. The oxalate-EDTA leach is well-suited to this purpose because it does not greatly fractionate Fe isotopes for a diversity of particle types over a wide variety of leaching conditions, and because it approximates the conditions by which particulate Fe dissolves in the oceans. We recommend a 2 h leach at 90 °C with 0.1 M oxalate and 0.05 M EDTA at pH 8 to measure labile ;ligand-leachable; particulate δ56Fe on natural marine materials with a range of compositions.
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Sulfide Melts and Chalcophile Element Behavior in High Temperature Systems
NASA Astrophysics Data System (ADS)
Wood, B. J.; Kiseeva, K.
2016-12-01
We recently found that partition coefficients (Di) of many weakly and moderately chalcophile elements (e.g., Cd, Zn, Co, Cr, Pb, Sb, In) between sulfide and silicate melts are simple functions of the FeO content of the silicate liquid: logDi A-Blog[FeO] where [FeO] is the FeO concentration in the silicate, A and B are constants and the latter is related to the valency of the element of interest. In contrast, some strongly chalcophile (e.g Cu, Ni, Ag) and lithophile elements (e.g Mn) show marked deviations from linearity on a plot of logDi vs log[FeO]. More recent experiments show that linear behavior is confined to elements whose affinities for S and O are similar to those of Fe. In the case of elements more strongly lithophile than Fe (Ti, U, REE, Zr, Nb, Ta, Mn) a plot of logDi versus log[FeO] describes a U-shape with the element partitioning strongly into the sulfide at very low FeO and again at very high FeO content of the silicate melt. In contrast, strongly chalcophile elements (Cu, Ni, Ag) describe an n-shape on the plot of logD vs log[FeO]. The result is that lithophile elements such as Nb become more "chalcophile" than Cu at very low and very high FeO contents of the silicate melt. The reasons for this surprising behavior are firstly that, at very low FeO contents the silicate melt dissolves substantial amounts of sulfur, which drives down the activity of FeO and, from mass-action "pulls" the lihophile element into the sulfide. At high FeO contents of the silicate the sulfide itself starts to dissolve substantial amounts of oxygen and lithophile elements follow the oxygen into the sulfide. Given the principles which we have established, we are able to describe the patterns of chalcophile element behavior during partial melting and fractional crystallisation on Earth and also on bodies such as Mercury and Mars which are, respectively, strongly reduced relative to Earth and more oxidised than Earth.
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Smith, Kathleen S.; Ranville, James F.; Lesher, Emily K.; Diedrich, Daniel J.; McKnight, Diane M.; Sofield, Ruth M.
2014-01-01
This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.
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Distinguishing iron-reducing from sulfate-reducing conditions
Chapelle, F.H.; Bradley, P.M.; Thomas, M.A.; McMahon, P.B.
2009-01-01
Ground water systems dominated by iron- or sulfate-reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe2+) and sulfide (sum of H2S, HS-, and S= species and denoted here as "H2S"). This approach is based on the observation that concentrations of Fe2+ and H2S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe2+ concentrations are high, H2S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe2+ with H2S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron- and the sulfate-reducing microorganisms that catalyze the production of Fe2+ and H 2S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe2+ and H 2S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H2) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe2+/H2S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H2 ???0.2 to 0.8 nM). Conversely, if the Fe 2+/H2S ratio was less than 0.30, consistent sulfate-reducing (H2 ???1 to 5 nM) conditions were observed over time. Concomitantly high Fe2+ and H2S concentrations were associated with H2 concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron- and sulfate-reducing zones or concomitant iron and sulfate reduction under nonelectron donor-limited conditions. These observations suggest that Fe2+/H2S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems. ?? 2009 National Ground Water Association.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Ondrej Linda; Dumidu Wijayasekara; Milos Manic
Resiliency and improved state-awareness of modern critical infrastructures, such as energy production and industrial systems, is becoming increasingly important. As control systems become increasingly complex, the number of inputs and outputs increase. Therefore, in order to maintain sufficient levels of state-awareness, a robust system state monitoring must be implemented that correctly identifies system behavior even when one or more sensors are faulty. Furthermore, as intelligent cyber adversaries become more capable, incorrect values may be fed to the operators. To address these needs, this paper proposes a Fuzzy-Neural Data Fusion Engine (FN-DFE) for resilient state-awareness of control systems. The designed FN-DFEmore » is composed of a three-layered system consisting of: 1) traditional threshold based alarms, 2) anomalous behavior detector using self-organizing fuzzy logic system, and 3) artificial neural network based system modeling and prediction. The improved control system state-awareness is achieved via fusing input data from multiple sources and combining them into robust anomaly indicators. In addition, the neural network based signal predictions are used to augment the resiliency of the system and provide coherent state-awareness despite temporary unavailability of sensory data. The proposed system was integrated and tested with a model of the Idaho National Laboratory’s (INL) hybrid energy system facility know as HYTEST. Experimental results demonstrate that the proposed FN-DFE provides timely plant performance monitoring and anomaly detection capabilities. It was shown that the system is capable of identifying intrusive behavior significantly earlier than conventional threshold based alarm systems.« less
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Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems
Wang, Hongmei; Gong, Linfeng; Cravotta,, Charles A.; Yang, Xiaofen; Tuovinen, Olli H.; Dong, Hailiang; Fu, Xiang
2013-01-01
Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO3)2 was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0–24.2 mM Pb(II) added as Pb(NO3)2. Anglesite (PbSO4) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe3(SO4)2(OH)6) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9–17.6 μM regardless of the concentrations of Pb(NO3)2 added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO3)2 addition even when anglesite was removed before inoculation. Experiments with 0–48 mM KNO3 demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO3)2 addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans.
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Weiss, David M; Casten, Robin J; Leiby, Benjamin E; Hark, Lisa A; Murchison, Ann P; Johnson, Deiana; Stratford, Shayla; Henderer, Jeffrey; Rovner, Barry W; Haller, Julia A
2015-09-01
African American individuals are at high risk of diabetes mellitus and diabetic retinopathy but have suboptimal rates of dilated fundus examinations (DFEs). Early intervention is crucial for the prevention of diabetic retinopathy in this high-risk population. To test the efficacy of behavioral activation for diabetic retinopathy prevention on rates of DFEs in older African American individuals with diabetes mellitus. Masked randomized clinical trial at 2 urban medical centers from October 1, 2010, to May 31, 2014. Participants included 206 African American individuals 65 years and older with diabetes mellitus who had not obtained a DFE in the preceding 12 months. Participants were randomized to either behavioral activation for diabetic retinopathy prevention, a behavioral intervention designed to provide education, facilitate identifying and addressing health care barriers, and promote goal setting to improve rates of DFEs, or supportive therapy, a control condition. The primary outcome was medical documentation of a DFE at 6 months' follow-up. Secondary outcomes included the Risk Perceptions and Risk Knowledge Survey of Diabetes Mellitus, Diabetes Self-Care Inventory, Patient Health Questionnaire 9, and National Eye Institute Vision Function Questionnaire 25 scores and hemoglobin A1c levels. More participants in the behavioral activation for diabetic retinopathy prevention group (87.9%) obtained a DFE compared with those in the supportive therapy group (34.1%) by the 6-month follow-up assessment (P < .001). Overall, participants in the behavioral activation for diabetic retinopathy prevention group were 2.5 times more likely to obtain a DFE compared with those in the supportive therapy group (risk ratio = 2.58; 95% CI, 1.91-3.48; P < .001). The intervention had no short-term effect on secondary outcomes of hemoglobin A1c levels, depression, or the Risk Perceptions and Risk Knowledge Survey of Diabetes Mellitus or National Eye Institute Vision Function Questionnaire 25 composite scores; however, both groups had improved adherence to diabetes mellitus self-care behaviors from baseline to 6-month follow-up. Behavioral activation for diabetic retinopathy prevention significantly increased rates of DFEs in older African American individuals with diabetes mellitus. Behavioral interventions may have the potential to positively affect screening for diabetic retinopathy in at-risk populations. clinicaltrials.gov Identifier: NCT01179555.
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Han, Baisui; Altansukh, Batnasan; Haga, Kazutoshi; Stevanović, Zoran; Jonović, Radojka; Avramović, Ljiljana; Urosević, Daniela; Takasaki, Yasushi; Masuda, Nobuyuki; Ishiyama, Daizo; Shibayama, Atsushi
2018-06-15
Sulfide copper mineral, typically Chalcopyrite (CuFeS 2 ), is one of the most common minerals for producing metallic copper via the pyrometallurgical process. Generally, flotation tailings are produced as a byproduct of flotation and still consist of un‒recovered copper. In addition, it is expected that more tailings will be produced in the coming years due to the increased exploration of low‒grade copper ores. Therefore, this research aims to develop a copper recovery process from flotation tailings using high‒pressure leaching (HPL) followed by solvent extraction. Over 94.4% copper was dissolved from the sample (CuFeS 2 as main copper mineral) by HPL in a H 2 O media in the presence of pyrite, whereas the iron was co‒dissolved with copper according to an equation given as C Cu = 38.40 × C Fe . To avoid co‒dissolved iron giving a negative effect on the subsequent process of electrowinning, solvent extraction was conducted on the pregnant leach solution for improving copper concentration. The result showed that 91.3% copper was recovered in a stripped solution and 98.6% iron was removed under the optimal extraction conditions. As a result, 86.2% of copper was recovered from the concentrate of flotation tailings by a proposed HPL‒solvent extraction process. Copyright © 2018 Elsevier B.V. All rights reserved.
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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.
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Photolytic Release of Dissolved Vanadium and Copper from Resuspended Coastal Marine Sediments
NASA Astrophysics Data System (ADS)
Skrabal, S. A.; Hammaker, S. N.; McBurney, A. W.; Avery, G. B., Jr.; Kieber, R. J.; Mead, R. N.
2016-02-01
Sunlight photolysis engenders release of dissolved vanadium (V), copper (Cu), and dissolved organic carbon (DOC) from a wide variety of resuspendable coastal marine sediments. Net photoreleases after 6 h of simulated sunlight were as high as 12 nM for Cu and as high as 15 nM for V. Release of Cu significantly correlated with sediment Cu. Photoreleased Cu (but not V) correlated with sediment Fe content, suggesting that photoreduction of Fe oxide carrier phases may be an important photoproduction mechanism for Cu. Longer term experiments showed continued release of metals that were not immediately readsorbed back onto sediments after 24 h of irradiation suggesting that photoproduced metals persist in the dissolved phase and are not immediately scavenged onto particles. Experiments utilizing differing total suspended sediment (TSS) levels show that, although higher TSS causes more photoproduction of Cu and V, the amount produced per mass of sediment is greatest at the lowest TSS. Vanadium photoproduction increased in Macondo oil-amended sediments compared to controls after a one-month incubation period suggesting that the oil may be a source of this metal to the water column. These results imply that photoproduction is an unrecognized source of the micronutrient metals Cu and V to coastal waters.
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Varol, Memet
2013-10-01
Water samples were collected at monthly intervals during 1 year of monitoring from Kralkızı, Dicle and Batman dam reservoirs in the Tigris River basin to assess the concentrations of dissolved heavy metals and to determine their spatial and seasonal variations. The results indicated that dissolved heavy metal concentrations in the reservoirs were very low, reflecting the natural background levels. The lowest total metal concentrations in the three dam reservoirs were detected at sampling sites close to the dam wall. However, the highest total concentrations were observed at sites, which are located at the entrance of the streams to the reservoirs. Fe, Cr and Ni were the most abundant elements in the reservoirs, whereas Cd and As were the less abundant. The mean concentrations of dissolved metals in the dam reservoirs never exceeded the maximum permitted concentrations established by EC (European Community), WHO and USEPA drinking water quality guidelines. All heavy metals showed significant seasonal variations. As, Cd, Cr, Cu, Fe, Ni and Pb displayed higher values in the dry season, while higher values for Zn in the wet season. Cluster analysis grouped all ten sampling sites into three clusters. Clusters 1 and 2, and cluster 3 corresponded to relatively low polluted and moderate polluted regions, respectively. PCA/FA demonstrated the dissolved metals in the dam reservoirs controlled by natural sources. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Localized zones of denitrification in a floodplain aquifer in southern Wisconsin, USA
NASA Astrophysics Data System (ADS)
Craig, Laura; Bahr, Jean M.; Roden, Eric E.
2010-12-01
A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O2, Cl-, NO{3/-}, SO{4/2-}, dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ15NNO3 and δ18ONO3 composition. Samples in which NO{3/-} was too low for stable isotope analysis were analyzed for excess dissolved N2. Groundwater NO{3/-} concentrations declined between the agricultural field and the discharge point. Chloride and δ15NNO3/δ18ONO3 data indicated that the drop in NO{3/-} was caused primarily by dilution of shallow NO{3/-}-rich water with deeper, NO{3/-}-depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ15NNO3 and δ18ONO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N2. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO{3/-} is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.
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Modern Dust Deposition and Dissolved Iron Residence Times in the Eastern Tropical Pacific Ocean
NASA Astrophysics Data System (ADS)
Vivancos, S. M.; Anderson, R. F.; Pavia, F. J.; Fleisher, M. Q.; Lu, Y.; Zhang, P.; Cheng, H.; Edwards, R. L.
2016-02-01
We use dissolved 230Th and 232Th data along the U.S. GEOTRACES Equatorial Pacific Zonal Transect (EPZT) from Peru to Tahiti to quantify dust input to the region. Dust in the global oceans is a mineral ballast that helps carry organic matter to depth, a reactive particle surface that scavenges trace metals such as Th and Pa from the water column, and through its dissolution dust provides essential micronutrients, such as iron, that stimulate productivity. When integrating Th inventories from the sea surface to 500 meters water depth (Hayes et al., Earth Planet. Sci. Lett., 383 (2013) 16-25), we find that dust fluxes along the EPZT are an order of magnitude lower (0.18-1.61 g/m2/yr) than along the U.S. GEOTRACES Atlantic Transect (Mauritania to Bermuda; 3.22 to 10.56 g/m2/yr). Dust fluxes decrease with distance away from the dust source (i.e., the continents). Using an Fe/Th ratio of 2660 g/g for dust and assuming a Fe/Th solubility ratio of 1.0 (Hayes et al., Geochim. Cosmochim. Acta, 169 (2015) 1-16), we calculate a dissolved iron flux of 12.06 to 109.88 µmol/m2/yr to the EPZT region. Utilizing dissolved iron data along the EPZT (Resing et al., Nature, 523 (2015) 200-203), we calculate a dissolved iron residence time integrated from the sea surface to 500 meters water depth of 4 to 11 years.
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NASA Technical Reports Server (NTRS)
Brown, I. I.; Bryant, D. A.; Thomas,-Keprta, K. L.; Tringe, S. G.; Sarkisova, S. A.; Galindo, C., Jr.; Malley, K.; Sosa, O.; Garrison, D. H.; McKay, David S.
2010-01-01
Verifying the links between genomie features in living organisms and their mineralization/demineralization activity will help to reveal traces of life on Earth and beyond. Among contemporary environments, iron-depositing hot springs (IDHS) may represent one of the most appropriate natural models for insights into ancient life since organisms may have originated on Earth and possibly Mars in association with hydrothennal activity and high [Fe(2+)]. Siderophilic or "iron-loving" cyanobacteria (CB) inhabiting IDHS may have genomic features and properties similar to those of ancient organisms because abundant Fe(2+) in IDHS has a strong potential to increase the magnitude of oxidative stress. That is why specific and/or additional proteins involved in Fe mineralization by siderophilic CB are expected. Inorganic polyphosphates (PPi) are known to increase the viability of prokaryotes Linder heavy metal concentrations and UV stress conditions. PPi have also been proposed as biosignatures. Ancient CB could have also been stressed by occasional migrations from the Fe(2+) rich Ocean to the basaltic land which was almost devoid of dissolved Fe(2+). Thus, the study of the adaptation reactions of siderophilic CB to fluctuation of dissolved Fe level may shed light on the paleophysiology of ancient oxygenic prokaryotes. Moreover, bioweathered Fe, Al, P, Cu, Ti and rare earth elements can be thought of as candidate organomarkers that document the effects of or ganic molecules in weathered rocks. However, the molecular mechanisms of the maintenance of Fe homeostasis in siderophilic CB, the role of PPi for this process and bioweathering activities are poorly understood. Here we present preliminary results describing a new mechanism of Fe mineralization in siderophilic CB, the effect of Fe on the generation of PPi bodies in siderophilic CB, their bioweathering activity and preliminary analysis of the diversity of proteins involved in the prevention of oxidative stress in phototrophs inhabiting IDHS.
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Seasonal changes in Fe along a glaciated Greenlandic fjord.
NASA Astrophysics Data System (ADS)
Hopwood, Mark; Connelly, Douglas; Arendt, Kristine; Juul-Pedersen, Thomas; Stinchcombe, Mark; Meire, Lorenz; Esposito, Mario; Krishna, Ram
2016-03-01
Greenland's ice sheet is the second largest on Earth, and is under threat from a warming Arctic climate. An increase in freshwater discharge from Greenland has the potential to strongly influence the composition of adjacent water masses with the largest impact on marine ecosystems likely to be found within the glaciated fjords. Here we demonstrate that physical and chemical estuarine processes within a large Greenlandic fjord are critical factors in determining the fate of meltwater derived nutrients and particles, especially for non-conservative elements such as Fe. Concentrations of Fe and macronutrients in surface waters along Godthåbsfjord, a southwest Greenlandic fjord with freshwater input from 6 glaciers, changed markedly between the onset and peak of the meltwater season due to the development of a thin (<10 m), outflowing, low-salinity surface layer. Dissolved (<0.2 µm) Fe concentrations in meltwater entering Godthåbsfjord (200 nM), in freshly melted glacial ice (mean 38 nM) and in surface waters close to a land terminating glacial system (80 nM) all indicated high Fe inputs into the fjord in summer. Total dissolvable (unfiltered at pH <2.0) Fe was similarly high with concentrations always in excess of 100 nM throughout the fjord and reaching up to 5.0 µM close to glacial outflows in summer. Yet, despite the large seasonal freshwater influx into the fjord, Fe concentrations near the fjord mouth in the out-flowing surface layer were similar in summer to those measured before the meltwater season. Furthermore, turbidity profiles indicated that sub-glacial particulate Fe inputs may not actually mix into the outflowing surface layer of this fjord. Emphasis has previously been placed on the possibility of increased Fe export from Greenland as meltwater fluxes increase. Here we suggest that in-fjord processes may be effective at removing Fe from surface waters before it can be exported to coastal seas.
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The Rusty Sink: Iron Promotes the Preservation of Organic Matter in Sediments
NASA Astrophysics Data System (ADS)
Lalonde, K. M.; Mucci, A.; Moritz, A.; Ouellet, A.; Gelinas, Y.
2011-12-01
The biogeochemical cycles of iron (Fe) and organic carbon (OC) are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved Fe [1], whereas in soils, solid Fe phases provide a sheltering and preservative effect for organic matter [2]. Until now however, the role of iron in the preservation of OC in sediments has not been clearly established. Here we show that 21.5 ± 8.6% of the OC in sediments is directly bound to reactive iron phases, which promote the preservation of OC in sediments. Iron-bound OC represents a global mass of 19 to 45 × 10^15 g of OC in surface marine sediments. This pool of OC is different from the rest of sedimentary OC, with 13C and nitrogen-enriched organic matter preferentially bound to Fe which suggests that biochemical fractionation occurs with OC-Fe binding. Preferential binding also affects the recovery of high molecular weight lipid biomarkers and acidic lignin oxidation products, changing the environmental message of proxies derived from these biomarkers. [1] Johnson, K. S., Gordon, R. M. & Coale, K. H. What controls dissolved iron in the world ocean? Marine Chemistry 57, 137-161 (1997). [2] Kaiser, K. & Guggenberger, G. The role of DOM sorption to mineral surfaces in the preservation of organic matter in soils. Organic Geochemistry 31, 711-725 (2000).
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The long-term effectiveness of a FeSO4 + Na2S2O4 reductant solution blend for in situ saturated zone treatment of dissolved and solid phase Cr(VI) in a high pH chromite ore processing solid waste (COPSW) fill material was investigated. Two field pilot injection studies were cond...
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NASA Astrophysics Data System (ADS)
Masset, Patrick J.
2008-09-01
The thermal stability of FeS2 cathode material for thermal batteries is investigated in the LiCl-KCl eutectic containing up to 10 wt% Li2O (used as anti-peak). The results show that the decomposition of pyrite shifts to higher temperatures in the presence of molten salts as the S2 gas is repressed by the liquid phase. For high lithium oxide contents the decomposition temperature of pyrite decreases by 100 °C. In addition Li2FeS2 as reaction product is evidenced whereas Li3Fe2S4 is expected from literature data.
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Transformation of organo-ferric peat colloids by a heterotrophic bacterium
NASA Astrophysics Data System (ADS)
Oleinikova, Olga V.; Shirokova, Liudmila S.; Gérard, Emmanuele; Drozdova, Olga Yu.; Lapitskiy, Sergey A.; Bychkov, Andrey Yu.; Pokrovsky, Oleg S.
2017-05-01
Bacterial mineralization of allochthonous (soil) dissolved organic matter (DOM) in boreal waters governs the CO2 flux from the lakes and rivers to the atmosphere, which is one of the main factor of carbon balance in high latitudes. However, the fate of colloidal trace element (TE) during bacterial processing of DOM remains poorly constrained. We separated monoculture of Pseudomonas saponiphila from a boreal creek and allowed it to react with boreal Fe-rich peat leachate of approximate colloidal (3 kDa-0.45 μm) composition C1000Fe12Al3.3Mg2Ca3.7P1.2Mn0.1Ba0.5 in nutrient-free media. The total net decrease of Dissolved Organic Carbon (DOC) concentration over 4 day of exposure was within 5% of the initial value, whereas the low molecular weight fraction of Corg (LMW<3 kDa) yielded a 16%-decrease due to long-term bio-uptake or coagulation. There was a relative depletion in Fe over Corg of 0.45 μm, colloidal and LMW fraction in the course of peat leachate interaction with P. saponiphila. Al, Mn, Ni, Cu, Ga, REEs, Y, U were mostly affected by bacterial presence and exhibited essentially the adsorption at the cell surface over first hours of reaction, in contrast to Fe, Ti, Zr, and Nb that showed both short-term adsorption and long-term removal by physical coagulation/coprecipitation with Fe hydroxide. The low molecular weight fraction (LMW<3 kDa) of most TE was a factor of 2-5 less affected by microbial presence via adsorption or removal than the high molecular weight (HMW) colloidal fractions (<0.45 μm and <50 kDa). The climate change-induced acceleration of heterotrophic bacterial activity in boreal and subarctic waters may lead to preferential removal of Fe over DOC from conventionally dissolved fraction and the decrease of the proportion of LMW < 3 kDa fraction and the increase of HMW colloids. Enhanced heterotrophic mineralization of organo-ferric colloids under climate warming scenario may compensate for on-going "browning" of surface waters.
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NASA Astrophysics Data System (ADS)
Cánovas, C. R.; Macías, F.; Olías, M.; López, R. Pérez; Nieto, J. M.
2017-07-01
Fluxes of acidity and contaminants from acid mine drainage (AMD) sources to the receiving surface water bodies were studied in a mining-impacted watershed (Meca River, SW Spain) using a novel methodology based on the joint application of EMMA and MIX codes. The application of EMMA and elemental ratios allowed delimiting the end-members responsible for water quality variations at a catchment scale. The further application of MIX quantified the significant impact of AMD on the river quality; less than 10% of AMD relative contribution is enough to maintain acidic conditions during most of the year. The mixing model also provided information about the element mobility, distinguishing those elements with a quasi-conservative behavior (e.g., Cu, Zn, Al, Co or Ni) from those affected by mineral precipitation/dissolution (e.g., K, Si, Na, Sr, Ca, Fe, Pb, or As). Floods are the main driver of dissolved and, mainly particulate, contaminants in the catchment. Thus, the first rainfall events in November only accounted for 19% of the annual Meca flow but yielded between 26 and 43% of the net acidity and dissolved metal loads (mainly, Fe, As and Pb). Concerning particulate transport, around 332 tons of particulate Fe, 49 tons of Al, 0.79 tons of As and 0.37 tons of Pb were recorded during these first floods. The particulate As concentration can be up to 34 times higher than the dissolved one during floods and between 2 and 4 times higher for Fe, Pb and Cr. This integrated modeling approach could be a promising and useful tool to face future restoration plans in derelict mines worldwide. This approach would allow prioritizing remedial measures, achieving an environmental and cost-effective restoration of degraded areas.
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NASA Astrophysics Data System (ADS)
von Brömssen, Mattias; Häller Larsson, Sara; Bhattacharya, Prosun; Hasan, M. Aziz; Ahmed, Kazi Matin; Jakariya, M.; Sikder, Mohiuddin A.; Sracek, Ondra; Bivén, Annelie; Doušová, Barbora; Patriarca, Claudio; Thunvik, Roger; Jacks, Gunnar
2008-07-01
High arsenic (As) concentrations in groundwater pose a serious threat to the health of millions of people in Bangladesh. Reductive dissolution of Fe(III)-oxyhydroxides and release of its adsorbed As is considered to be the principal mechanism responsible for mobilisation of As. The distribution of As is extremely heterogeneous both laterally and vertically. Groundwater abstracted from oxidised reddish sediments, in contrast to greyish reducing sediments, contains significantly lower amount of dissolved arsenic and can be a source of safe water. In order to study the sustainability of that mitigation option, this study describes the lithofacies and genesis of the sediments within 60 m depth and establishes a relationship between aqueous and solid phase geochemistry. Oxalate extractable Fe and Mn contents are higher in the reduced unit than in the oxidised unit, where Fe and Mn are present in more crystalline mineral phases. Equilibrium modelling of saturation indices suggest that the concentrations of dissolved Fe, Mn and PO43--tot in groundwater is influenced by secondary mineral phases in addition to redox processes. Simulating AsIII adsorption on hydroferric oxides using the Diffuse Layer Model and analytical data gave realistic concentrations of dissolved and adsorbed AsIII for the reducing aquifer and we speculate that the presence of high PO43--tot in combination with reductive dissolution results in the high-As groundwater. The study confirms high mobility of As in reducing aquifers with typically dark colour of sediments found in previous studies and thus validates the approach for location of wells used by local drillers based on sediment colour. A more systematic and standardised colour description and similar studies at more locations are necessary for wider application of the approach.
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Mn cycling in marine biofilms: effect on the rate of localized corrosion.
Dexter, S C; Xu, K; Luther, G L
2003-04-01
Microelectrodes of the Au-Hg amalgam type have been used together with square wave voltammetry to measure profiles of oxygen, peroxide, Fe, Mn and sulfur chemical species through the thickness of natural assemblage marine biofilms grown on stainless steel alloy Nitronic 50 (UNS S20910). The data show Mn+2 and peroxide together at locations where the dissolved oxygen concentration was low. Oxidized species of Fe were also found at some locations. Sulfur species (predominantly S-2) was often found at locations where the dissolved oxygen concentration was below the detectable limit. Confocal scanning laser microscopy was used to image the microbial assemblage at the locations of the chemical profile data. Organisms with a filamentous morphology were found in consortia with rod and coccoidal shaped microbes at locations where dissolved Mn and peroxide were measured. The filamentous forms were usually absent at locations where Mn was not detected. It is suggested that the filamentous organisms may be Mn metabolizers, and that peroxidatic Mn re-oxidation may be taking place within the biofilm.
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Kent, D.B.; Fox, P.M.
2004-01-01
We examined the chemical reactions influencing dissolved concentrations, speciation, and transport of naturally occurring arsenic (As) in a shallow, sand and gravel aquifer with distinct geochemical zones resulting from land disposal of dilute sewage effluent. The principal geochemical zones were: (1) the uncontaminated zone above the sewage plume [350 ??M dissolved oxygen (DO), pH 5.9]; (2) the suboxic zone (5 ??M DO, pH 6.2, elevated concentrations of sewage-derived phosphate and nitrate); and (3) the anoxic zone [dissolved iron(II) 100-300 ??M, pH 6.5-6.9, elevated concentrations of sewage-derived phosphate]. Sediments are comprised of greater than 90% quartz but the surfaces of quartz and other mineral grains are coated with nanometer-size iron (Fe) and aluminum (Al) oxides and/or silicates, which control the adsorption properties of the sediments. Uncontaminated groundwater with added phosphate (620 ??M) was pumped into the uncontaminated zone while samples were collected 0.3 m above the injection point. Concentrations of As(V) increased from below detection (0.005 ??M) to a maximum of 0.07 ??M during breakthrough of phosphate at the sampling port; As(III) concentrations remained below detection. These results are consistent with the hypothesis that naturally occurring As(V) adsorbed to constituents of the coatings on grain surfaces was desorbed by phosphate in the injected groundwater. Also consistent with this hypothesis, vertical profiles of groundwater chemistry measured prior to the tracer test showed that dissolved As(V) concentrations increased along with dissolved phosphate from below detection in the uncontaminated zone to approximately 0.07 and 70 ??M, respectively, in the suboxic zone. Concentrations of As(III) were below detection in both zones. The anoxic zone had approximately 0.07 ??M As(V) but also had As(III) concentrations of 0.07-0.14 ??M, suggesting that release of As bound to sediment grains occurred by desorption by phosphate, reductive dissolution of Fe oxides, and reduction of As(V) to As(III), which adsorbs only weakly to the Fe-oxide-depleted material in the coatings. Results of reductive extractions of the sediments suggest that As associated with the coatings was relatively uniformly distributed at approximately 1 nmol/g of sediment (equivalent to 0.075 ppm As) and comprised 20%-50% of the total As in the sediments, determined from oxidative extractions. Quartz sand aquifers provide high-quality drinking water but can become contaminated when naturally occurring arsenic bound to Fe and Al oxides or silicates on sediment surfaces is released by desorption and dissolution of Fe oxides in response to changing chemical conditions. ?? 2004 American Institute of Physics.
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Cravotta, C.A.
2008-01-01
Water-quality data for discharges from 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania reveal complex relations among the pH and dissolved solute concentrations that can be explained with geochemical equilibrium models. Observed values of pH ranged from 2.7 to 7.3 in the coal-mine discharges (CMD). Generally, flow rates were smaller and solute concentrations were greater for low-pH CMD samples; pH typically increased with flow rate. Although the frequency distribution of pH was similar for the anthracite and bituminous discharges, the bituminous discharges had smaller median flow rates; greater concentrations of SO4, Fe, Al, As, Cd, Cu, Ni and Sr; comparable concentrations of Mn, Cd, Zn and Se; and smaller concentrations of Ba and Pb than anthracite discharges with the same pH values. The observed relations between the pH and constituent concentrations can be attributed to (1) dilution of acidic water by near-neutral or alkaline ground water; (2) solubility control of Al, Fe, Mn, Ba and Sr by hydroxide, sulfate, and/or carbonate minerals; and (3) aqueous SO4-complexation and surface-complexation (adsorption) reactions. The formation of AlSO4+ and AlHSO42 + complexes adds to the total dissolved Al concentration at equilibrium with Al(OH)3 and/or Al hydroxysulfate phases and can account for 10-20 times greater concentrations of dissolved Al in SO4-laden bituminous discharges compared to anthracite discharges at pH of 5. Sulfate complexation can also account for 10-30 times greater concentrations of dissolved FeIII concentrations at equilibrium with Fe(OH)3 and/or schwertmannite (Fe8O8(OH)4.5(SO4)1.75) at pH of 3-5. In contrast, lower Ba concentrations in bituminous discharges indicate that elevated SO4 concentrations in these CMD sources could limit Ba concentrations by the precipitation of barite (BaSO4). Coprecipitation of Sr with barite could limit concentrations of this element. However, concentrations of dissolved Pb, Cu, Cd, Zn, and most other trace cations in CMD samples were orders of magnitude less than equilibrium with sulfate, carbonate, and/or hydroxide minerals. Surface complexation (adsorption) by hydrous ferric oxides (HFO) could account for the decreased concentrations of these divalent cations with increased pH. In contrast, increased concentrations of As and, to a lesser extent, Se with increased pH could result from the adsorption of these oxyanions by HFO at low pH and desorption at near-neutral pH. Hence, the solute concentrations in CMD and the purity of associated "ochres" formed in CMD settings are expected to vary with pH and aqueous SO4 concentration, with potential for elevated SO4, As and Se in ochres formed at low pH and elevated Cu, Cd, Pb and Zn in ochres formed at near-neutral pH. Elevated SO4 content of ochres could enhance the adsorption of cations at low pH, but decrease the adsorption of anions such as As. Such information on environmental processes that control element concentrations in aqueous samples and associated precipitates could be useful in the design of systems to reduce dissolved contaminant concentrations and/or to recover potentially valuable constituents in mine effluents.
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X-ray photoelectron spectroscopic evidence for bacteria-enhanced dissolution of hornblende
NASA Astrophysics Data System (ADS)
Kalinowski, B. E.; Liermann, L. J.; Brantley, S. L.; Barnes, A.; Pantano, C. G.
2000-04-01
An Arthrobacter species capable of extracting Fe from hornblende was isolated from a soil from the Adirondacks, NY (USA). This bacteria isolate, used in batch experiments with hornblende, accelerated the release of Fe from hornblende without measurably affecting Al release. The isolate produces both low molecular weight organic acids (LMWOA) and a catecholate siderophore. Polished hornblende (glass and crystal) discs were analyzed with X-ray photoelectron spectroscopy (XPS) before and after incubation with growing Arthrobacter sp. to investigate whether the bacteria caused a distinguishable chemical signature on the upper 100 Å of mineral surface. After removal of the arthrobacter grown on hornblende crystal or glass substrates using lysozyme, XPS revealed surface depletion of Fe for samples grown for several days in buffered (crystal) and unbuffered (crystal and glass) media. Fe/Si ratios of hornblende surfaces dissolved under biotic conditions are significantly lower than Fe/Si ratios on surfaces dissolved under abiotic conditions for similar amounts of time. Enhanced Fe release and the formation of Fe-depleted surfaces is inferred to be caused by catechol complexation at the mineral surface. Because natural siderophore was not isolated in sufficient quantities to run bacteria-free leaching experiments, parallel investigations were run with a commercially available siderophore (desferrioxamine B). Desferrioxamine B was observed to enhance release of Fe, Si, and Al from hornblende both with and without added bacteria. Formation of desferrioxamine-Fe surface complexes were probed by studying the multiple splitting and shift in intensities of the N 1s line analyzed by XPS on siderophore ± Fe on gold surfaces and siderophore + hornblende crystal surfaces. Based upon the observed formation of an hydroxamate (desferrioxamine) surface complex on hornblende, we infer that catecholate siderophores, such as those produced by the arthrobacter, also complex on the hornblende surface. Surface complexation is favored because of the extremely high association constants for siderophore + Fe(III). X-ray photoelectron spectroscopic data is therefore consistent with a model wherein enhanced Fe release by these bacteria or desferrioxamine B is caused by Fe-siderophore complexation at the silicate surface. Such complexation presumably weakens bonds between the Fe and the oxide lattice, causing enhanced Fe leaching and an Fe-depleted surface. Some leaching may also be due to LMWOA, although this is interpreted to be of secondary importance.
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Gankanda, Aruni; Coddens, Ellen M; Zhang, Yaping; Cwiertny, David M; Grassian, Vicki H
2016-12-08
Recent atmospheric field and modeling studies have highlighted a lack of understanding of the processes responsible for high levels of sulfate aerosol in the atmosphere, ultimately arising from a dearth of experimental data on such processes. Here we investigated the effect of temperature and simulated solar radiation on the catalytic oxidation of S(iv) to S(vi) (i.e., sulfite to sulfate) in aqueous suspensions of several metal-containing, atmospherically relevant particles including coal fly ash (FA), Arizona test dust (ATD) and an iron oxide (γ-Fe 2 O 3 ). The effect of temperature and light on S(iv) oxidation was found to be very different for these three samples. For example, in the presence of FA and γ-Fe 2 O 3 the temporal evolution of dissolved Fe(ii) (formed via reductive particle dissolution) correlated with S(iv) oxidation. Accordingly, we propose that S(iv) oxidation in most of these systems initially occurs primarily at the particle surface (i.e., a heterogeneous reaction pathway), although a solution-phase (i.e., homogeneous) catalytic pathway also contributes over later timescales due to the formation and accumulation of dissolved Fe(iii) (generated via oxidation of dissolved Fe(ii) by O 2 ). It is likely that the homogeneous reaction pathway is operative at initial times in the presence of γ-Fe 2 O 3 at 25 °C. In contrast, S(iv) oxidation in the presence of ATD appears to proceed entirely via a heterogeneous reaction, which notably does not lead to any iron dissolution. In fact, the greater overall rate of S(iv) loss in the presence of ATD compared to FA and γ-Fe 2 O 3 suggests that other factors, including greater adsorption of sulfite, transition metal ion (TMI) catalysis by other metal ions (e.g., Ti), or different species of iron in ATD, play a role. Overall these studies suggest that the rate, extent and products of atmospheric S(iv) oxidation can be highly variable and dependent upon the nature of aerosol sources and ambient conditions (e.g., temperature and irradiance). Ultimately, such complexity precludes simple, broadly generalized schemes for this reaction when modeling atmospheric processes involving diverse components of different mineral dust aerosol as well as other metal-containing aerosol.
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Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts
NASA Astrophysics Data System (ADS)
Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.
2014-06-01
The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.
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Notification: Preliminary Research on EPA's Design for the Environment Product Labeling Program OIG
Project #OPE-FY14-4012, November 06, 2013. The Office of Inspector General (OIG) is starting preliminary research on the U.S. Environmental Protection Agency’s (EPA’s) Design for the Environment (DfE) Product Labeling Program.
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Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Ma, Teng; Liu, Yaqing; Su, Chunli; Zhu, Yapeng; Wang, Zhiqiang
2017-02-01
Severe health problems due to elevated arsenic (As) in groundwater have made it urgent to develop cost-effective technologies for As removal. This field experimental study tested the feasibility of in-situ As immobilization via As incorporation into newly formed biogenic Fe(II) sulfides in a typical As-affected strongly reducing aquifer at the central part of Datong Basin, China. After periodic supply of FeSO 4 into the aquifer for 25 d to stimulate microbial sulfate reduction, dissolved sulfide concentrations increased during the experiment, but the supplied Fe(II) reacted quickly with sulfide to form Fe(II)-sulfides existing majorly as mackinawite as well as a small amount of pyrite-like minerals in sediments, thereby restricting sulfide build-up in groundwater. After the completion of field experiment, groundwater As concentration decreased from an initial average value of 593 μg/L to 159 μg/L, with an overall As removal rate of 73%, and it further declined to 136 μg/L adding the removal rate up to 77% in 30 d after the experiment. The arsenite/As total ratio gradually increased over time, making arsenite to be the predominant species in groundwater residual As. The good correlations between dissolved Fe(II), sulfide and As concentrations, the increased abundance of As in newly-formed Fe sulfides as well as the reactive-transport modeling results all indicate that As could have been adsorbed onto and co-precipitated with Fe(II)-sulfide coatings once microbial sulfate reduction was stimulated after FeSO 4 supply. Under the strongly reducing conditions, sulfide may facilitate arsenate reduction into arsenite and promote As incorporation into pyrite or arsenopyrite. Therefore, the major mechanisms for the in-situ As-contaminated groundwater remediation can be As surface-adsorption on and co-precipitation with Fe(II) sulfides produced during the experimental period. Copyright © 2016. Published by Elsevier Ltd.
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The effect of membrane filtration on dissolved trace element concentrations
Horowitz, A.J.; Lum, K.R.; Garbarino, J.R.; Hall, G.E.M.; Lemieux, C.; Demas, C.R.
1996-01-01
The almost universally accepted operational definition for dissolved constituents is based on processing whole-water samples through a 0.45-??m membrane filter. Results from field and laboratory experiments indicate that a number of factors associated with filtration, other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample), can produce substantial variations in the 'dissolved' concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. These variations result from the inclusion/exclusion of colloidally- associated trace elements. Thus, 'dissolved' concentrations quantitated by analyzing filtrates generated by processing whole-water through similar pore- sized membrane filters may not be equal/comparable. As such, simple filtration through a 0.45-??m membrane filter may no longer represent an acceptable operational definition for dissolved chemical constituents. This conclusion may have important implications for environmental studies and regulatory agencies.
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Folate intake and the MTHFR C677T genotype influence choline status in young Mexican American women☆
Abratte, Christian M.; Wang, Wei; Li, Rui; Moriarty, David J.; Caudill, Marie A.
2009-01-01
Numerous studies have reported a relationship between folate status, the methylenetetrahydrofolate reductase (MTHFR) 677C→T variant and disease risk. Although folate and choline metabolism are inter-related, only limited data are available on the relationship between choline and folate status in humans. This study sought to examine the influences of folate intake and the MTHFR 677C→T variant on choline status. Mexican-American women (n =43; 14 CC, 12 CT and 17 TT) consumed 135 μg/day as dietary folate equivalents (DFE) for 7 weeks followed by randomization to 400 or 800 μg DFE/day for 7 weeks. Throughout the study, total choline intake remained unchanged at ∼350 mg/day. Plasma concentrations of betaine, choline, glycerophosphocholine, phosphatidylcholine and sphingomyelin were measured via LC-MS/MS for Weeks 0, 7 and 14. Phosphatidylcholine and sphingomyelin declined ( P=.001, P=.009, respectively) in response to folate restriction and increased ( P=.08, P=.029, respectively) in response to folate treatment. The increase in phosphatidylcholine occurred in response to 800 ( P=.03) not 400 ( P=.85) μg DFE/day (week×folate interaction, P=.017). The response of phosphatidylcholine to folate intake appeared to be influenced by MTHFR C677T genotype. The decline in phosphatidylcholine during folate restriction occurred primarily in women with the CC or CT genotype and not in the TT genotype (week×genotype interaction, P=.089). Moreover, when examined independent of folate status, phosphatidylcholine was higher ( P <.05) in the TT genotype relative to the CT genotype. These data suggest that folate intake and the MTHFR C677T genotype influence choline status in humans. PMID:17588738
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Paulson, Anthony J.; Balistrieri, Laurie S.
1999-01-01
Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.
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McKnight, Diane M.; Wershaw, R. L.; Bencala, K.E.; Zellweger, G.W.; Feder, G.L.
1992-01-01
Hydrous iron and aluminum oxides are deposited on the streambed in the confluence of the Snake River and Deer Creek, two streams in the Colorado Rocky Mountains. The Snake River is acidic and has high concentrations of dissolved Fe and Al. These metals precipitate at the confluence with the pristine, neutral pH, Deer Creek because of the greater pH (4.5-6.0) in the confluence. The composition of the deposited oxides changes consistently with distance downstream, with the most upstream oxide samples having the greatest Fe and organic carbon content. Fulvic acid accounts for most of the organic content of the oxides. Results indicate that streambed oxides in the confluence are not saturated with respect to their capacity to sorb dissolved humic substances from streamwater. The contents of several trace metals (Mn, Zn, Cu, Pb, Ni and Co) also decrease with distance downstream and are correlated with both the Fe and organic carbon contents. Strong metal-binding sites associated with the sorbed fulvic acid are more than sufficient to account for the trace metal content of the oxides. Complexation of trace metals by sorbed fulvic acid may explain the observed downstream decrease in trace metal content.
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Pan, Chao; Troyer, Lyndsay D; Liao, Peng; Catalano, Jeffrey G; Li, Wenlu; Giammar, Daniel E
2017-06-06
Iron-based electrocoagulation can be highly effective for Cr(VI) removal from water supplies. However, the presence of humic acid (HA) inhibited the rate of Cr(VI) removal in electrocoagulation, with the greatest decreases in Cr(VI) removal rate at higher pH. This inhibition was probably due to the formation of Fe(II) complexes with HA that are more rapidly oxidized than uncomplexed Fe(II) by dissolved oxygen, making less Fe(II) available for reduction of Cr(VI). Close association of Fe(III), Cr(III), and HA in the solid products formed during electrocoagulation influenced the fate of both Cr(III) and HA. At pH 8, the solid products were colloids (1-200 nm) with Cr(III) and HA concentrations in the filtered fraction being quite high, while at pH 6 these concentrations were low due to aggregation of small particles. X-ray diffraction and X-ray absorption fine structure spectroscopy indicated that the iron oxides produced were a mixture of lepidocrocite and ferrihydrite, with the proportion of ferrihydrite increasing in the presence of HA. Cr(VI) was completely reduced to Cr(III) in electrocoagulation, and the coordination environment of the Cr(III) in the solids was similar regardless of the humic acid loading, pH, and dissolved oxygen level.
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Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems.
Wang, Hongmei; Gong, Linfeng; Cravotta, Charles A; Yang, Xiaofen; Tuovinen, Olli H; Dong, Hailiang; Fu, Xiang
2013-01-15
Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO(3))(2) was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0-24.2 mM Pb(II) added as Pb(NO(3))(2). Anglesite (PbSO(4)) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe(3)(SO(4))(2)(OH)(6)) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9-17.6 μM regardless of the concentrations of Pb(NO(3))(2) added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO(3))(2) addition even when anglesite was removed before inoculation. Experiments with 0-48 mM KNO(3) demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO(3))(2) addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans. Copyright © 2012 Elsevier B.V. All rights reserved.
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Exhibition of veiled features in diffusion bonding of titanium alloy and stainless steel via copper
NASA Astrophysics Data System (ADS)
Thirunavukarasu, Gopinath; Kundu, Sukumar; Laha, Tapas; Roy, Deb; Chatterjee, Subrata
2017-11-01
An investigation was carried out to know the extent of influence of bonding-time on the interface structure and mechanical properties of diffusion bonding (DB) of TiA|Cu|SS. DB of Ti6Al4V (TiA) and 304 stainless steel (SS) using pure copper (Cu) of 200-μm thickness were processed in vacuum using 4-MPa bonding-pressure at 1123 K from 15 to 120 min in steps of 15 min. Preparation of DB was not possible when bonding-time was less than 60 min as the bonding at Cu|SS interface was unsuccessful in spite of effective bonding at TiA|Cu interface; however, successful DB were produced when the bonding-time was 60 min and beyond. DB processed for 60 and 75 min (classified as shorter bonding-time interval) showed distinctive characteristics (structural, mechanical, and fractural) as compared to the DB processed for 90, 105, and 120 min (classified as longer bonding-time interval). DB processed for 60 and 75 min exhibited layer-wise Cu-Ti-based intermetallics at TiA|Cu interface, whereas Cu|SS interface was completely free from reaction products. The layer-wise structure of Cu-Ti-based intermetallics were not observed at TiA|Cu interface in the DB processed for longer bonding-time; however, the Cu|SS interface had layer-wise ternary intermetallic compounds (T1, T2, and T3) of Cu-Fe-Ti-based along with σ phase depending upon the bonding-time chosen. Diffusivity of Ti-atoms in Cu-layer (DTi in Cu-layer) was much greater than the diffusivity of Fe-atoms in Cu-layer (DFe in Cu-layer). Ti-atoms reached Cu|SS interface but Fe-atoms were unable to reach TiA|Cu interface. It was observed that DB fractured at Cu|SS interface when processed for shorter bonding-time interval, whereas the DB processed for longer bonding-time interval fractured apparently at the middle of Cu-foil region predominantly due to the existence of brittle Cu-Fe-Ti-based intermetallics.
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High Temperature Oxidation of Hot-Dip Aluminized T92 Steels
NASA Astrophysics Data System (ADS)
Abro, Muhammad Ali; Hahn, Junhee; Lee, Dong Bok
2018-03-01
The T92 steel plate was hot-dip aluminized, and oxidized in order to characterize the high-temperature oxidation behavior of hot-dip aluminized T92 steel. The coating consisted of Al-rich topcoat with scattered Al3Fe grains, Al3Fe-rich upper alloy layer with scattered (Al, Al5Fe2, AlFe)-grains, and Al5Fe2-rich lower alloy layer with scattered (Al5Fe2, AlFe)-grains. Oxidation at 800 °C for 20 h formed (α-Al2O3 scale)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer), while oxidation at 900 °C for 20 h formed (α-Al2O3 scale plus some Fe2O3)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer) from the surface. During oxidation, outward migration of all substrate elements, inward diffusion of oxygen, and back and forth diffusion of Al occurred according to concentration gradients. Also, diffusion transformed and broadened AlFe and AlFe3 layers dissolved with some oxygen and substrate alloying elements. Hot-dip aluminizing improved the high-temperature oxidation resistance of T92 steel through preferential oxidation of Al at the surface.
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High Temperature Oxidation of Hot-Dip Aluminized T92 Steels
NASA Astrophysics Data System (ADS)
Abro, Muhammad Ali; Hahn, Junhee; Lee, Dong Bok
2018-05-01
The T92 steel plate was hot-dip aluminized, and oxidized in order to characterize the high-temperature oxidation behavior of hot-dip aluminized T92 steel. The coating consisted of Al-rich topcoat with scattered Al3Fe grains, Al3Fe-rich upper alloy layer with scattered (Al, Al5Fe2, AlFe)-grains, and Al5Fe2-rich lower alloy layer with scattered (Al5Fe2, AlFe)-grains. Oxidation at 800 °C for 20 h formed (α-Al2O3 scale)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer), while oxidation at 900 °C for 20 h formed (α-Al2O3 scale plus some Fe2O3)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer) from the surface. During oxidation, outward migration of all substrate elements, inward diffusion of oxygen, and back and forth diffusion of Al occurred according to concentration gradients. Also, diffusion transformed and broadened AlFe and AlFe3 layers dissolved with some oxygen and substrate alloying elements. Hot-dip aluminizing improved the high-temperature oxidation resistance of T92 steel through preferential oxidation of Al at the surface.
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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.
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Identification of an Archean marine oxygen oasis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Riding, Dr Robert E; Fralick, Dr Philip; Liang, Liyuan
2014-01-01
The early Earth was essentially anoxic. A number of indicators suggest the presence of oxygenic photosynthesis 2700 3000 million years (Ma) ago, but direct evidence for molecular oxygen (O2) in seawater has remained elusive. Here we report rare earth element (REE) analyses of 2800 million year old shallowmarine limestones and deep-water iron-rich sediments at Steep Rock Lake, Canada. These show that the seawater from which extensive shallow-water limestones precipitated was oxygenated, whereas the adjacent deeper waters where iron-rich sediments formed were not. We propose that oxygen promoted limestone precipitation by oxidative removal of dissolved ferrous iron species, Fe(II), to insolublemore » Fe(III) oxyhydroxide, and estimate that at least 10.25 M oxygen concentration in seawater was required to accomplish this at Steep Rock. This agrees with the hypothesis that an ample supply of dissolved Fe(II) in Archean oceans would have hindered limestone formation. There is no direct evidence for the oxygen source at Steep Rock, but organic carbon isotope values and diverse stromatolites in the limestones suggest the presence of cyanobacteria. Our findings support the view that during the Archean significant oxygen levels first developed in protected nutrient-rich shallow marine habitats. They indicate that these environments were spatially restricted, transient, and promoted limestone precipitation. If Archean marine limestones in general reflect localized oxygenic removal of dissolved iron at the margins of otherwise anoxic iron-rich seas, then early oxygen oases are less elusive than has been assumed.« less
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Reduction kinetics of hexavalent chromium in soils and its correlation with soil properties.
Xiao, Wendan; Zhang, Yibin; Li, Tingqiang; Chen, Bao; Wang, Huan; He, Zhenli; Yang, Xiaoe
2012-01-01
The toxicity of chromium (Cr) to biota is related to its chemical forms and consequently to the redox conditions of soils. Hexavalent Cr[Cr(VI)] may undergo natural attenuation through reduction processes. In this study, the reduction kinetics of Cr(VI) in seven soils and its relationships with soil properties were investigated with laboratory incubation experiments. The results indicate that the reduction of Cr(VI) can be described by a first-order reaction. The reduction rates of Cr(VI) in the seven soils decreased in the order: Udic Ferrisols > Stagnic Anthrosols > Calcaric Regosols > Mollisol > Typic Haplustalf > Periudic Argosols > Ustic Cambosols. Simple correlation analysis revealed that the reduction of Cr(VI) in soils was positively related to organic matter content, dissolved organic matter content, Fe(II) content, clay fraction, and to the diversity index of the bacterial community but negatively correlated with easily reducible Mn content. Using stepwise regression, the reduction of Cr(VI) in soil could be quantitatively predicted by the measurement of dissolved organic matter content, Fe(II) content, pH, and soil particle size distribution, with a fitting level of 95.5%. The results indicated that the reduction of Cr(VI) in natural soils is not controlled by a single soil property but is the result of the combined effects of dissolved organic matter, Fe(II), pH, and soil particle size distribution. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.
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40 CFR 80.1611 - Standards and requirements for certified ethanol denaturant.
Code of Federal Regulations, 2014 CFR
2014-07-01
... certified ethanol denaturant. 80.1611 Section 80.1611 Protection of Environment ENVIRONMENTAL PROTECTION....1611 Standards and requirements for certified ethanol denaturant. Producers and importers of ethanol denaturant that is suitable for the manufacture of denatured fuel ethanol (DFE) meeting federal quality...
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Silva, Felipe Thales Moreira; Moreira, Luiza Rojas; de Souza Ferreira, Juliana; Batista, Fabiana Regina Xavier; Cardoso, Vicelma Luiz
2016-01-01
Hydrogen is a promising alternative for the increased global energy demand since it has high energy density and is a clean fuel. The aim of this work was to evaluate the photo-fermentation by Rhodobacter capsulatus, using the dark fermentation effluent as substrate. Different systems were tested by changing the type of sugar in the dark fermentation, investigating the influence of supplementing DFE with sugar and adding alternate and periodically lactose and glucose throughout the process. The supplementation of the DFE with sugar resulted in higher H2 productivity and the replacement of the sugars repeatedly during the photo-fermentation process was important to maintain the cell culture active. By controlling the residual amount of sugar, bacteria inhibition was avoided; lactic acid, that was toxic to the biomass, was consumed and the metabolic route of butyric acid production was predominant. Under optimum conditions, the H2 productivity reached 208.40mmolH2/Ld in 52h. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO2 suspensions.
Sharma, Virender K; Graham, Nigel J D; Li, Xiang-Zhong; Yuan, Bao-Ling
2010-02-01
Photocatalytic oxidation using UV irradiation of TiO(2) has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e(-)(cb)) with electron holes (h(vb)(+)) on the irradiated TiO(2) surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO(4)(2-)) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO(2) photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e(-)(cb) and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate. The paper reviews the published results of laboratory experiments designed to follow the photocatalytic degradation of selected contaminants of environmental significance and the influence of the experimental conditions (e.g. pH, reactant concentrations and dissolved oxygen). The specific compounds are as follows: ammonia, cyanate, formic acid, bisphenol-A, dibutyl- and dimethyl-phthalate and microcystin-LR. The principal focus in these studies has been on the rates of reaction rather than on reaction pathways and products. The presence of UV/TiO(2) accelerates the chemical reduction of ferrate, and the reduction rate decreases with pH owing to deprotonation of ferrate ion. For all the selected contaminant substances, the photocatalytic oxidation rate was greater in the presence of ferrate, and this was believed to be synergistic rather than additive. The presence of dissolved oxygen in solution reduced the degradation rate of dimethyl phthalate in the ferrate/photocatalysis system. In the study of microcystin-LR, it was evident that an optimal ferrate concentration exists, whereby higher Fe(VI) concentrations above the optimum leads to a reduction in microcystin-LR degradation. In addition, the rate of microcystin-LR degradation was found to be strongly dependent on pH and was greatest at pH 6. The initial rate of photocatalytic reduction under different conditions was analysed using a Langmuirian form. Decrease in rates in the presence of dissolved oxygen may be due to competition between oxygen and ferrate as electron scavengers and to non-productive radical species interactions. The reaction between ferrate(VI) and microcystins-LR in the pH range of 6.0-10.0 is most likely controlled by the protonated Fe(VI) species, HFeO(4)(-). The photocatalytic oxidation of selected, recalcitrant contaminants was found to be significantly greater in the presence of ferrate, arising from the role of ferrate in inhibiting the h(vb)(+)-e(-)(cb) pair recombination on TiO(2) surfaces and the corresponding generation of highly oxidative Fe(V) species. The performance of the ferrate/photocatalysis system is strongly influenced by the reaction conditions, particularly the pH and dissolved oxygen concentration, arising from the complex nature of the interactions between the catalyst and the solution. Overall, the treatment performance of the Fe(VI)-TiO(2)-UV system is generally superior to alternative chemical oxidation methods. The formation of intermediate Fe(V) species in the photocatalytic reduction of ferrate(VI) requires confirmation, and a method involving electron paramagnetic resonance spectroscopy could be applied for this. The reactivity of Fe(V) with the selected contaminants is required in order to better understand the role of ferrate in the Fe(VI)-TiO(2)-UV oxidation system. To increase the practical utility of the system, it is recommended that future studies involving the photocatalytic oxidation of pollutants in the presence of ferrate(VI) should focus on developing modified TiO(2) surfaces that are photocatalytic under visible light conditions.
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NMR Express-analyser for quality monitoring of motor fuel
NASA Astrophysics Data System (ADS)
Protasov, E. A.; Protasov, D. E.
2016-09-01
A method for the rapid analysis of motor fuel quality was developed by artificial increase of the octane number through dissolving ferrocene in a low-octane gasoline (C10H10Fe). Measurements of the spin-lattice relaxation time of nuclear magnetic resonance is used for determination of ferrocene presence in standardized and real fuel from gas stations. The results of measurements of the relaxation characteristics among certain grades of motor fuel with dissolving ferrocene therein are presented.
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NASA Astrophysics Data System (ADS)
Sherman, David M.
2013-10-01
Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.
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Verplanck, P.L.; Mueller, S.H.; Goldfarb, R.J.; Nordstrom, D. Kirk; Youcha, E.K.
2008-01-01
Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2-3??vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca-HCO3 to Ca-SO4 type, and ranges from dilute (specific conductance of 48????S/cm) to more concentrated (specific conductance as high as 2070????S/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO4 reduction). Waters with the highest Fe concentrations, as high as 10.7??mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160????g/L, with a median value of 146????g/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO3, Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59????g/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.
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Kay, R.T.; Groschen, G.E.; Cygan, G.; Dupre, David H.
2011-01-01
Diel variations in the concentrations of a number of constituents have the potential to substantially affect the appropriate sampling regimen in acidic streams. Samples taken once during the course of the day cannot adequately reflect diel variations in water quality and may result in an inaccurate understanding of biogeochemical processes, ecological conditions, and of the threat posed by the water to human health and the associated wildlife. Surface water and groundwater affected by acid drainage were sampled every 60 to 90. min over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, near Hegeler, Illinois. Diel variations related to water quality in the aquifer were not observed in groundwater. Diel variations were observed in the temperature, pH, and concentration of dissolved oxygen, nitrite, barium, iron, lead, vanadium, and possibly uranium in surface water. Temperature, dissolved oxygen, nitrite, barium, lead, and uranium generally attained maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally attained minimum values during the afternoon and maximum values during the night. Concentrations of dissolved oxygen were affected by the intensity of photosynthetic activity and respiration, which are dependent upon insolation. Nitrite, an intermediary in many nitrogen reactions, may have been formed by the oxidation of ammonium by dissolved oxygen and converted to other nitrogen species as part of the decomposition of organic matter. The timing of the pH cycles was distinctly different from the cycles found in Midwestern alkaline streams and likely was the result of the photoreduction of Fe3+ to Fe 2+ and variations in the intensity of precipitation of hydrous ferric oxide minerals. Diel cycles of iron and vanadium also were primarily the result of variations in the intensity of precipitation of hydrous ferric oxide minerals. The diel variation in the concentrations of lead, uranium, and barium may have been affected by competition with Fe+2 for sorption sites on hydrous ferric oxide minerals. ?? 2010.
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Mackinawite (FeS) Reduces Mercury(II) under Sulfidic Conditions
2015-01-01
Mercury (Hg) is a toxicant of global concern that accumulates in organisms as methyl Hg. The production of methyl Hg by anaerobic bacteria may be limited in anoxic sediments by the sequestration of divalent Hg [Hg(II)] into a solid phase or by the formation of elemental Hg [Hg(0)]. We tested the hypothesis that nanocrystalline mackinawite (tetragonal FeS), which is abundant in sediments where Hg is methylated, both sorbs and reduces Hg(II). Mackinawite suspensions were equilibrated with dissolved Hg(II) in batch reactors. Examination of the solid phase using Hg LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopy showed that Hg(II) was indeed reduced in FeS suspensions. Measurement of purgeable Hg using cold vapor atomic fluorescence spectrometry (CVAFS) from FeS suspensions and control solutions corroborated the production of Hg(0) that was observed spectroscopically. However, a fraction of the Hg(II) initially added to the suspensions remained in the divalent state, likely in the form of β-HgS-like clusters associated with the FeS surface or as a mixture of β-HgS and surface-associated species. Complexation by dissolved S(-II) in anoxic sediments hinders Hg(0) formation, but, by contrast, Hg(II)–S(-II) species are reduced in the presence of mackinawite, producing Hg(0) after only 1 h of reaction time. The results of our work support the idea that Hg(0) accounts for a significant fraction of the total Hg in wetland and estuarine sediments. PMID:25180562
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Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer
Chapelle, Francis H.; Haack, Sheridan K.; Adriaens, Peter; Henry, Mark A.; Bradley, Paul M.
1996-01-01
Measurements of oxidation-reduction potential (Eh) and concentrations of dissolved hydrogen (H2) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. Eh measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured Eh and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H2concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H2 ∼ 1-4 nM) and Fe(III)-reducing (H2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H2 concentrations were more useful for identifying anoxic redox processes than Ehmeasurements in this groundwater system. However, H2-based redox zone delineations are more reliable when H2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.
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NASA Astrophysics Data System (ADS)
Waters, L.; Lange, R. A.
2011-12-01
The extent to which degassing affects the oxidation state of arc magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of magmas, and it has been proposed that degassing may induce either oxidation or reduction depending on the initial oxidation state. A commonly proposed oxidation reaction is related to H2O degassing: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt). Another mechanism by which H2O degassing can affect the iron redox state is if dissolved water affects the activity of ferrous and/or ferric iron in the melt. Although Moore et al. (1995) presented experiments showing no evidence of an affect of dissolved water on the activity of the ferric-ferrous ratio in silicate melts, other experimental results (e.g., Baker and Rutherford, 1996; Gaillard et al., 2001; 2003) indicate that there may be such an effect in rhyolite liquids. It has long been understood that rhyolites, owing to their low total iron concentrations, are more sensitive than other magma types to degassing-induced change in redox state. Therefore, a rigorous test of whether H2O degassing affects the redox state of arc magmas is best evaluated on rhyolites. In this study, a comparison is made between the pre-eruptive (pre-degassing) Fe2+ concentrations in six, phenocryst-poor (<5%), fresh, glassy obsidian samples with their post-eruptive (post-degassing) Fe2+ concentrations. Near-liquidus co-precipitation of two Fe-Ti oxides allows the pre-eruptive oxygen fugacity and temperature to be calculated in each rhyolite using the oxygen barometer and thermometer of Ghiorso and Evans (2008). Temperatures range from 793 (± 19) to 939 (± 15) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.4 to +1.4. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1991), which relates melt composition (not including dissolved water), oxygen fugacity and temperature to melt ferric-ferrous ratios. With temperature known, the plagioclase-liquid hygrometer of Lange et al. (2009) was applied and maximum melt water concentrations range from 4.2 to 7.5 wt%. Both the oxidation state and water concentration are known prior to eruption, at the time of phenocryst growth. After eruption, the rhyolites lost nearly all of their volatiles, as indicated by the low loss on ignition values (LOI ≤ 0.7 wt%). In order to test how much oxidation of ferrous iron occurred as a consequence of that degassing, we measured the ferrous iron concentration in the bulk samples by titration, using the Wilson (1960) method, which was successfully tested again three USGS and one Canadian Geological Survey standards. Our results indicate no detectable change within analytical error between pre- and post-eruptive FeO concentrations, with an average deviation of 0.09 wt% and a maximum deviation of 0.15 wt%. Our results show that H2O degassing has no effect on the redox state of rhyolite magmas, which requires that dissolved water has no resolvable affect on the activity ratio of the iron oxide components in melt.
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Synthesis of BiFeO3 thin films by chemical solution deposition - Structural and magnetic studies
NASA Astrophysics Data System (ADS)
Angappane, S.; Kambhala, Nagaiah
2012-06-01
BiFeO3 thin films were deposited on Si (100) substrates by chemical solution deposition. A precursor solution of bismuth acetate and iron acetylacetonate dissolved in distilled water and acetic acid was spin coated on to silicon substrates at ambient conditions, followed by drying and annealing at 650 °C. The films were characterized by XRD and FESEM to study structural properties and morphology. The magnetic properties studied by SQUID magnetometer shows the ferromagnetic nature of the chemical solution deposited BiFeO3 films which are crucial for low cost device applications.
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Generation of GHS Scores from TEST and online sources
Alternatives assessment frameworks such as DfE (Design for the Environment) evaluate chemical alternatives in terms of human health effects, ecotoxicity, and fate. T.E.S.T. (Toxicity Estimation Software Tool) can be utilized to evaluate human health in terms of acute oral rat tox...
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40 CFR 80.1600 - Additional definitions for subpart O.
Code of Federal Regulations, 2014 CFR
2014-07-01
... California. Certified ethanol denaturant means ethanol denaturant that meets the requirements of § 80.1611. Certified Sulfur-FRGAS has the meaning given in § 80.1666(a)(5). Denatured fuel ethanol (DFE) means an.... Ethanol denaturant means previously certified gasoline (including previously certified blendstocks for...
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NASA Astrophysics Data System (ADS)
Trocine, Robert P.; Trefry, John H.
1988-04-01
Suspended particles were collected from an area of active hydrothermal venting at the Trans-Atlantic Geotraverse (TAG) Hydrothermal Field on the Mid-Atlantic Ridge and analyzed for Fe, Mn, Cd, Zn, Cu, V, Ni, Cr, Pb, Mg, Ca, Al and Si. Rapid advection of vent-derived precipitates produced a lens with total suspended matter (TSM) loadings of 14-60 μg/l at 200-700 m above the seafloor; TSM concentrations > 60 μg/l were observed only at near-vent sites. The distribution of suspended particles correlated well with increased dissolved Mn concentrations and particulate Fe values near the vent source. Particulate Fe values decreased linearly relative to TSM concentrations as hydrothermal precipitates mixed with background suspended matter. Near-vent precipitates were characterized by up to 35% Fe, 2% Zn, 0.6% Cu and > 100 μg/g Cd. In comparison to Fe, particulate Cd, Zn and Cu values decreased dramatically away from the vent source. This trend supports differential settling and/or dissolution of Cd-, Zn- and Cu-bearing phases. Particulate Mn and Fe values were inversely related with only 50 μg Mn/g in the near-vent particles. At near-vent sites, > 99% of the total Mn was in solution; this fraction decreased to 75-80% at background TSM values. In contrast to Cd, Zn and Cu, particulate V levels show a continuous, linear decrease with particulate Fe values. This trend is explained by adsorption of V on Fe-oxides in the vent plume. Scavenging of Cr, Pb and Mg by hydrothermal precipitates is also suggested by the data. Nickel and Al values were low in near-vent particles at < 100 and < 3 μg/g, respectively. The complementary behavior of dissolved Mn and particulate trace metals provides a useful framework for studying broad aspects of hydrothermal plume processes.
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Phase transition of Fe oxides under reducing condition and its relation with the As behavior
NASA Astrophysics Data System (ADS)
Choi, S. H.; Kim, S. H.; Jeong, G. Y.; Kim, K.
2014-12-01
Fe oxides are very common in the earth's crust and easily transform into other minerals such as magnetite and siderite under reducing conditions by microbial reactions. It is well known that As concentrations in groundwater is strongly regulated by adsorption onto Fe oxides. Even though some studies have suggested that the formation of siderite can also control the As concentration, direct evidences are not sufficient. In this study, we performed microbial incubation experiments to see the phase transition of As-rich Fe oxides under anoxic condition and to see how the water As concentrations are controlled accordingly. Three experiments were performed by changing organic carbon concentrations. Natural groundwaters and yeast extracts were used for the sources of microorganisms and organic carbon. Seven reactors were prepared for each experiment and opened one by one to observe the changes of the water chemistry and solid phases for 60 days. The formation of magnetite was observed at the early stage of each experiment. Siderite was formed at the later stage only when the dissolved organic carbon concentrations were high (donor/accepter molar ratio = 1.5). Goethite and hematite, instead of siderite, were formed from the experiment using low organic carbon concentration (donor/accepter molar ratio = 0.75). It is likely that dissolved ferrous ion adsorbs onto the Fe oxides and recrystallizes into hematite and goethite when the DOC concentration was low. As concentrations were generally very low in the water (normally 10 ug/L) and we could not find any relations with the Fe minerals formed by anoxic microbial reactions, maybe due to high Fe oxide/water ratio of our experiments. The sequential extraction analysis indicated that most of the As in solids are mostly associated with Fe-oxides and organic matters. The As bound to carbonates were very low even in the precipitates containing siderite due to low As concentrations in the water where the siderite formed. Further experiments precipitating siderite in the water with high As concentrations are required.
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NASA Astrophysics Data System (ADS)
Koo, H. Y.; Kim, J. H.; Hong, S. K.; Ko, Y. N.; Jang, H. C.; Jung, D. S.; Han, J. M.; Hong, Y. J.; Kang, Y. C.; Kang, S. H.; Cho, S. B.
2012-06-01
Fe powders as the heat pellet material for thermal batteries are prepared from iron oxide powders obtained by spray pyrolysis from a spray solution of iron nitrate with ethylene glycol. The iron oxide powders with hollow and thin wall structure produce Fe powders with elongated structure and fine primary particle size at a low reducing temperature of 615 °C. The mean size of the primary Fe powders with elongated structure decreases with increasing concentration of ethylene glycol dissolved into the spray solution. The heat pellets prepared from the fine-size Fe powders with elongated structure have good ignition sensitivities below 1 watt. The heat pellets formed from the Fe powders obtained from the spray solution with 0.5 M EG have an extremely high burn rate of 26 cms-1.
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NASA Astrophysics Data System (ADS)
Zarazua, G.; Ávila-Pérez, P.; Tejeda, S.; Barcelo-Quintal, I.; Martínez, T.
2006-11-01
The present area of study is located in the Upper Course of the Lerma River (UCLR). The Lerma is one of the most important rivers of Mexico, where it drains highly populated and industrialized regions. The aim of the present study is to determine the heavy metal concentration of Cr, Mn, Fe, Cu and Pb in dissolved and total phases of the UCLR by means of Total Reflection X-ray Fluorescence Spectrometry (TXRF). The surface water samples were collected at 8 sites distributed following the stream flow direction of the river. Four sampling campaigns were carried out in each site in a 1-year period. A sample preparation method was applied in order to obtain the total and dissolved fraction and to destroy the organic matter. The total heavy metal average concentration decrease in the following order: Fe (2566 μg/L) > Mn (300 μg/L) > Cu (66 μg/L) > Cr (21 μg/L) > Pb (15 μg/L). In general, the heavy metal concentrations in water of the UCLR are below the maximum permissible limits.
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Recovery of critical and value metals from mobile electronics enabled by electrochemical processing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tedd E. Lister; Peiming Wang; Andre Anderko
2014-10-01
Electrochemistry-based schemes were investigated as a means to recover critical and value metals from scrap mobile electronics. Mobile electronics offer a growing feedstock for replenishing value and critical metals and reducing need to exhaust primary sources. The electrorecycling process generates oxidizing agents at an anode to dissolve metals from the scrap matrix while reducing dissolved metals at the cathode. The process uses a single cell to maximize energy efficiency. E vs pH diagrams and metals dissolution experiments were used to assess effectiveness of various solution chemistries. Following this work, a flow chart was developed where two stages of electrorecycling weremore » proposed: 1) initial dissolution of Cu, Sn, Ag and magnet materials using Fe+3 generated in acidic sulfate and 2) final dissolution of Pd and Au using Cl2 generated in an HCl solution. Experiments were performed using a simulated metal mixture equivalent to 5 cell phones. Both Cu and Ag were recovered at ~ 97% using Fe+3 while leaving Au and Pd intact. Strategy for extraction of rare earth elements (REE) from dissolved streams is discussed as well as future directions in process development.« less
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Rare earth elements mobility processes in an AMD-affected estuary: Huelva Estuary (SW Spain).
Lecomte, K L; Sarmiento, A M; Borrego, J; Nieto, J M
2017-08-15
Huelva Estuary is a transition zone where REE-rich acidic waters interact with saline-alkaline seawater. This mixing process influences the geochemical and mineralogical characteristics of particulate and dissolved fractions. The Tinto River has >11,000μgL -1 dissolved REE (pH=1.66), whereas seawater only reaches 8.75·10 -2 μgL -1 dissolved REE (pH=7.87). REE-normalized patterns in "pH<6 solutions" are parallel and show similarities, diminishing their concentration as pH increases. Sequential extraction performed on the generated precipitates of mixed solutions indicates that most REE are associated to the residual phase. In a second order, REE are associated with soluble salts at pH3 and 3.5 whereas in sediments generated at pH4 and 5, they are distributed in salts (1° extraction), poorly crystallized Fe-bearing minerals (schwertmannite, 3° extraction) and well crystallized Fe-bearing minerals (goethite - hematite, 4° extraction). Finally, precipitated REE are highest at pH6 newly formed minerals with a release to solution in higher pH. Copyright © 2017 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Rotiroti, Marco; Bonomi, Tullia; Fumagalli, Letizia
2013-04-01
The present work concerns the analysis of the hydrogeology and the hydrogeochemistry of the As, Fe, Mn rich groundwater of the alluvial multi-layer aquifer in the lower Po Plain of Cremona (northern Italy). In this analysis, an integrated approach is applied in order to understand the origins (natural or anthropic) and chemical mechanisms of high groundwater As, Fe and Mn concentrations found in the study area. The study area covers a 50 km2 wide area around the urban territory of Cremona. It is located near the confluence between Adda and Po rivers. The multi-aquifer system which interests the first 200-250 m of depth is investigated. The integrated approach involves the (a) collection of historical data related to water quality, water levels and well logs; (b) storage of collected data in specific databases and geographical information systems; (c) design and execution of two field surveys of water levels and water quality, realized in July 2010 and July 2012, concerning also groundwater sampling for isotope and microbiological analysis; (d) construction of a 3D model of aquifer hydrogeological properties (deposits texture, hydraulic conductivity and effective porosity), built by means of ordinary kriging interpolation of numerical values derived from the coding of well logs; (e) analysis of the hydrodynamic properties of the system on the basis of the field measurements; (f) analysis of water quality data (both field and historical data) considering the hydrogeological and hydrodynamic properties of the aquifer system; (g) analysis of isotope and microbiological measurements; (h) implementation of a 1D reactive transport model in order to better understand the hydrogeochemical mechanisms in the system; (i) elaboration of a general hydrogeochemical conceptual model concerning possible origins and chemical mechanisms for the high groundwater As, Fe, Mn and NH4 concentrations, considering also possible anthropogenic influences; (j) development of management tools, as natural background levels (NBL) derivation, supporting groundwater resources protection by public authorities. This approach allows to assume the process of natural organic matter degradation (i.e. peat) as primary control factor on high As, Fe, Mn and NH4 concentrations. Degradation of peat is associated with the consecutive reduction of O2, NO3-, Mn(IV), Fe(III), SO42-, CO2. The reductive dissolution of Mn and Fe oxides (contained in the aquifer sediments) leads to high concentrations of dissolved Fe and Mn, but also to high concentrations of dissolved As, which is generally sorbed on Mn and Fe oxides. Dissolved As concentration can be also lowered by different processes (co-precipitation of As in iron sulfides, precipitation of arsenic sulfides, sorption of As on the remaining Fe-oxides and Mn-oxides, etc.). NH4 is released from the degradation of organic nitrogen of peat. Therefore, a natural origin of As, Fe, Mn and NH4 can be assumed. In addiction, anthropogenic influences on groundwater As, Fe, Mn and NH4 concentrations are locally identified in two sites located in the study area, that are affected by hydrocarbons and organic leachate pollution.
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Groundwater arsenic and fluoride in Rajnandgaon District, Chhattisgarh, northeastern India
NASA Astrophysics Data System (ADS)
Patel, Khageshwar Singh; Sahu, Bharat Lal; Dahariya, Nohar Singh; Bhatia, Amarpreet; Patel, Raj Kishore; Matini, Laurent; Sracek, Ondra; Bhattacharya, Prosun
2017-07-01
The groundwater of Ambagarh Chouki, Rajnandgaon, India, shows elevated levels of As and F-, frequently above the WHO guidelines. In this work, the concentrations of As, F-, Na+, Mg2+, Ca2+, Cl-, SO4 2-, HCO3 -, Fe, dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in the groundwater of Ambagarh Chouki are described. The sources of dissolved components in the groundwater are investigated using the cluster and factor analysis. Five factors have been identified and linked to processes responsible for the formation of groundwater chemistry. High concentrations of dissolved As seems to be linked to high concentrations of DOC, suggesting reductive dissolution of ferric oxyhydroxides as arsenic mobilization process. Fluoride is found in shallow depth water, presumably as a consequence of evaporation of water and removal of Ca2+ by precipitation of carbonates.
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Low biodegradability of dissolved organic matter and trace metals from subarctic waters.
Oleinikova, Olga V; Shirokova, Liudmila S; Drozdova, Olga Y; Lapitskiy, Sergey A; Pokrovsky, Oleg S
2018-03-15
The heterotrophic mineralization of dissolved organic matter (DOM) controls the CO 2 flux from the inland waters to the atmosphere, especially in the boreal waters, although the mechanisms of this process and the fate of trace metals associated with DOM remain poorly understood. We studied the interaction of culturable aquatic (Pseudomonas saponiphila) and soil (Pseudomonas aureofaciens) Gammaproteobacteria with seven different organic substrates collected in subarctic settings. These included peat leachate, pine crown throughfall, fen, humic lake, stream, river, and oligotrophic lake with variable dissolved organic carbon (DOC) concentrations (from 4 to 60mgL -1 ). The highest removal of DOC over 4days of reaction was observed in the presence of P. aureofaciens (33±5%, 43±3% and 53±7% of the initial amount in fen water, humic lake and stream, respectively). P. saponiphila degraded only 5% of DOC in fen water but did not affect all other substrates. Trace elements (TE) were essentially controlled by short-term (0-1h) adsorption on the surface of cells. Regardless of the nature of organic substrate and the identity of bacteria, the degree of adsorption ranged from 20 to 60% for iron (Fe 3+ ), 15 to 55% for aluminum (Al), 10 to 60% for manganese (Mn), 10 to 70% for nickel (Ni), 20 to 70% for copper (Cu), 10 to 60% for yttrium (Y), 30 to 80% for rare earth elements (REE), and 15 to 50% for uranium (U VI ). Rapid adsorption of organic and organo-mineral colloids on bacterial cell surfaces is novel and potentially important process, which deserves special investigation. The long-term removal of dissolved Fe and Al was generally consistent with solution supersaturation degree with respect to Fe and Al hydroxides, calculated by visual Minteq model. Overall, the biomass-normalized biodegradability of various allochthonous substrates by culturable bacteria is much lower than that of boreal DOM by natural microbial consortia. Copyright © 2017 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Fitzsimmons, J. N.; Parker, C.; Sherrell, R. M.
2016-02-01
The physicochemical speciation of trace metals in seawater influences their cycling as essential micronutrients for microorganisms or as tracers of anthropogenic influences on the marine environment. While chemical speciation affects lability, the size of metal complexes influences their ability to be accessed biologically and also influences their fate in the aggregation pathway to marine particles. In this study, we show that multiple trace metals in shelf and open ocean waters off northern California (IRN-BRU cruise, July 2014) have colloidal-sized components. Colloidal fractions were operationally defined using two ultrafiltration methods: a 0.02 µm Anopore membrane and a 10 kDa ( 0.003 µm) cross flow filtration (CFF) system. Together these two methods distinguished small (0.003 - 0.02 µm) and large (0.02 µm - 0.2 µm) colloids. As has been found previously for seawater in other ocean regimes, dissolved Fe had a broad size distribution with 50% soluble (<10 kDa) complexes and both small and large colloidal species. Dissolved Mn had no measurable colloidal component, consistent with its predicted chemical speciation as free Mn(II). Dissolved Cu, which like Fe is thought to be nearly fully organically bound in seawater, was only 25% colloidal, and these colloids were all small. Surprisingly Cd, Ni, and Pb also showed colloidal components (8-20%, 25-40%, and 10-50%) despite their hypothesized low organic speciation. Zn and Pb were nearly completely sorbed onto the Anopore membrane, making CFF the only viable ultrafiltration method for those elements. Zn suffered incomplete recovery ( 50-75%) through the CFF system but showed 30-85% colloidal contribution; thus, verifying a Zn colloidal phase with these methods is challenging. Conclusions will reveal links between the physical and chemical speciation for these metals and what role these metal colloids might have on trace metal exchange between the ocean margin and offshore waters.
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Fe-Containing Allophane and Hisingerite Dissolution and Implications for Gale Crater, Mars
NASA Technical Reports Server (NTRS)
Ralston, S. J.; Hausrath, E. M.; Tschauner, O.; Rampe, E. B.; Clark-Hogancamp, J. V.; Christoffersen, R.
2017-01-01
The mass-normalized dissolution rates measured in this study demonstrate that hisingerite and Fe-substituted allophane dissolve rapidly, much faster than crystalline phyllosilicates such as nontronite and kaolinite that have similar compositions. In addition, hisingerite dissolves more rapidly than allophane. Future work will focus on measuring dissolution rates at other pH values, so that dissolution rate laws for allophane and hisingerite can be derived. Results will be used to interpret data from Gale Crater. These initial experiments suggest that, if the liquid water present in Gale Crater was highly acidic, it was likely present for only a short time, allowing some amorphous soil-material similar to allophane to persist. Further experiments will enable us to constrain the timescales over which liquid water was present in Gale Crater and provide insight into its pH. This information is essential to assessing the potential habitability of ancient Mars.
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Removal of elevated level of chromium in groundwater by the fabricated PANI/Fe3O4 nanocomposites.
Ramachandran, Aruna; Prasankumar, T; Sivaprakash, S; Wiston, Biny R; Biradar, Santhosh; Jose, Sujin
2017-03-01
In this work, we report the reduction of chromium concentration in the polluted groundwater samples from Madurai Kamaraj University area, India, where the dissolved salts in groundwater are reported as serious health hazards for its inhabitants. The water samples have intolerable amounts of total dissolved solids (TDS) and chromium is a prominent pollutant among them. Chromium reduction was achieved by treating the polluted groundwater with PANI/Fe 3 O 4 nanocomposites synthesized by in situ polymerization method. Further experimentation showed that the nanocomposites exhibit better chromium removal characteristics upon increasing the aniline concentration during the synthesis. We were able to reduce chromium concentration in the samples from 0.295 mg L -1 to a tolerable amount of 0.144 mg L -1 . This work is expected to open doors for chromium-free groundwater in various regions of India, when improved to an industrial scale.
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Cu--Ni--Fe anode for use in aluminum producing electrolytic cell
Bergsma, S. Craig; Brown, Craig W.; Bradford, Donald R; Barnett, Robert J.; Mezner, Michael B.
2006-07-18
A method of producing aluminum in an electrolytic cell containing alumina dissolved in an electrolyte, the method comprising the steps of providing a molten salt electrolyte at a temperature of less than 900.degree. C. having alumina dissolved therein in an electrolytic cell having a liner for containing the electrolyte, the liner having a bottom and walls extending upwardly from said bottom. A plurality of non-consumable Cu--Ni--Fe anodes and cathodes are disposed in a vertical direction in the electrolyte, the cathodes having a plate configuration and the anodes having a flat configuration to compliment the cathodes. The anodes contain apertures therethrough to permit flow of electrolyte through the apertures to provide alumina-enriched electrolyte between the anodes and the cathodes. Electrical current is passed through the anodes and through the electrolyte to the cathodes, depositing aluminum at the cathodes and producing gas at the anodes.
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NASA Astrophysics Data System (ADS)
Lee, Sang Myung; Lee, Suk Kyu; Paik, Doo-Jin; Park, Joo Hyun
2017-04-01
The mechanism of iron dissolution and the effect of initial Fe content in a Zn bath on the dissolution rate of iron were investigated using a finger rotating method (FRM). When the initial iron content, [Fe]°, in the zinc bath was less than the solubility limit, the iron content in the zinc bath showed a rapid increase, whereas a moderate increase was observed when [Fe]° was close to the solubility limit. Based on Eisenberg's kinetic model, the mass transfer coefficient of iron in the present experimental condition was calculated to be k M = 1.2 × 10-5 m/s, which was similar to the results derived by Giorgi et al. under industrial practice conditions. A dissolution of iron occurred even when the initial iron content in the zinc bath was greater than the solubility limit, which was explained by the interfacial thermodynamics in conjunction with the morphology of the surface coating layer. By analyzing the diffraction patterns using TEM, the outermost dendritic-structured coating layer was confirmed as FeZn13 ( ζ). In order to satisfy the local equilibrium based on the Gibbs-Thomson equation, iron in the dendrite-structured phase spontaneously dissolved into the zinc bath, resulting in the enrichment of iron in front of the dendrite tip. Through the diffusion boundary layer in front of the dendritic-structured layer, dissolved Fe atoms diffused out and reacted with Zn and small amounts of Al, resulting in the formation of dross particles such as FeZn10Al x ( δ). It was experimentally confirmed that the smaller the difference between the initial iron content in the zinc bath and the iron solubility limit at a given temperature, the lower the number of formed dross particles.
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Wang, Yu; Pleasant, Saraya; Jain, Pradeep; Powell, Jon; Townsend, Timothy
2016-07-01
High concentrations of iron (Fe(II)) and manganese (Mn(II)) reductively dissolved from soil minerals have been detected in groundwater monitoring wells near many municipal solid waste landfills. Two in situ permeable reactive barriers (PRBs), comprised of limestone and crushed concrete, were installed downgradient of a closed, unlined landfill in Florida, USA, to remediate groundwater containing high concentrations of these metals. Influent groundwater to the PRBs contained mean Fe and Mn concentrations of approximately 30mg/L and 1.62mg/L, respectively. PRBs were constructed in the shallow aquifer (maximum depth 4.6m below land surface) and groundwater was sampled from a network of nearby monitoring wells to evaluate barrier performance in removing these metals. PRBs significantly (p<0.05) removed dissolved Fe and Mn from influent groundwater; Fe was removed from influent water at average rates of 91% and 95% (by mass) for the limestone and crushed concrete PRBs, respectively, during the first year of the study. The performance of the PRBs declined after 3years of operation, with Fe removal efficiency decreasing to 64% and 61% for limestone and concrete PRBs, respectively. A comparison of water quality in shallow and deep monitoring wells showed a more dramatic performance reduction in the deeper section of the concrete PRB, which was attributed to an influx of sediment into the barrier and settling of particulates from the upper portions of the PRBs. Although removal of Fe and Mn from redox impacts was achieved with the PRBs, the short time frame of effectiveness relative to the duration of a full-scale remediation effort may limit the applicability of these systems at some landfills because of the construction costs required. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Nakayama, Masaaki; Zhu, Wan-Jun; Watanabe, Kimio; Gibo, Ayano; Sherif, Ali M; Kabayama, Shigeru; Ito, Sadayoshi
2017-10-31
Peritoneal dialysis (PD) is used as renal replacement therapy in patients with end-stage kidney disease. However, peritoneal membrane failure remains problematic and constitutes a critical cause of PD discontinuation. Recent studies have revealed the unique biological action of molecular hydrogen (H 2 ) as an anti-oxidant, which ameliorates tissue injury. In the present study, we aimed to examine the effects of H 2 on the peritoneal membrane of experimental PD rats. Eight-week-old male Sprague-Dawley rats were divided into the following groups (n = 8-11 each) receiving different test solutions: control group (no treatment), PD group (commercially available lactate-based neutral 2.5% glucose PD solution), and H 2 PD group (PD solution with dissolved H 2 at 400 ppb). Furthermore, the influence of iron (FeCl 3 : 5 μM: inducer of oxidative cellular injury) in the respective PD solutions was also examined (Fe-PD and Fe-H 2 PD groups). The H 2 PD solution was manufactured by bathing a PD bag in H 2 -oversaturated water created by electrolysis of the water. Twenty mL of the test solutions were intraperitoneally injected once a day for 10 days. Parietal peritoneum samples and cells collected from the peritoneal surface following treatment with trypsin were subjected to analysis. In the PD group as compared to controls, a mild but significant sub-mesothelial thickening was observed, with increase in the number of cells in the peritoneal surface tissue that were positive for apoptosis, proliferation and vimentin, as seen by immunostaining. There were significantly fewer of such changes in the H 2 PD group, in which there was a dominant presence of M2 (CD163+) macrophages in the peritoneum. The Fe-PD group showed a significant loss of mesothelial cells with sub-mesothelial thickening, these changes being ameliorated in the Fe-H 2 PD group. H 2 -dissolved PD solutions could preserve mesothelial cells and peritoneal membrane integrity in PD rats. Clinical application of H 2 in PD could be a novel strategy for protection of peritoneal tissue during PD treatment.
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Generation of Alternative Assessment Scores using TEST and online data sources
Alternatives assessment frameworks such as DfE (Design for the Environment) evaluate chemical alternatives in terms of human health effects, ecotoxicity, and fate. T.E.S.T. (Toxicity Estimation Software Tool) can be utilized to evaluate human health in terms of acute oral rat tox...
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Chemistry within Molecular Clusters
1992-05-29
within van der Waals clusters. 23 They include the generation of (C2H4F 2),,>4H+ ions from 1,1- difluoroethane clusters, 24 the generation of (CH 3...fragment ions, and identification of the molecule must be made by the characteristic fragmentation pattern. The mass spectrum of 1,1- difluoroethane (DFE
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The Impact of "Achievement for All" on School Leadership
ERIC Educational Resources Information Center
Blandford, Sonia
2013-01-01
The "Achievement for All" (AfA) pilot initiative, delivered in partnership by the Department for Education (DfE), (formerly the Department for Children, Schools and Families [DCSF]), National Strategies and the National College (NCSL), aims to increase the attainment and progress of children in schools with special educational needs and…
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Federal Register 2010, 2011, 2012, 2013, 2014
2012-02-22
... Department of Justice's (DOJ's) National Motor Vehicle Title Information System (NMVTIS) Federal Advisory... announcement of a meeting of DOJ's National Motor Vehicle Title Information System (NMVTIS) Federal Advisory.... FOR FURTHER INFORMATION CONTACT: Todd Brighton, Designated Federal Employee (DFE), Bureau of Justice...
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Federal Register 2010, 2011, 2012, 2013, 2014
2013-08-21
... Department of Justice's (DOJ's) National Motor Vehicle Title Information System (NMVTIS) Federal Advisory... announcement of a meeting of DOJ's National Motor Vehicle Title Information System (NMVTIS) Federal Advisory.... FOR FURTHER INFORMATION CONTACT: Todd Brighton, Designated Federal Employee (DFE), Bureau of Justice...
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Federal Register 2010, 2011, 2012, 2013, 2014
2011-06-29
... Department of Justice's (DOJ's) National Motor Vehicle Title Information System (NMVTIS) Federal Advisory... announcement of a meeting of DOJ's National Motor Vehicle Title Information System (NMVTIS) Federal Advisory... FURTHER INFORMATION CONTACT: Alissa Huntoon, Designated Federal Employee (DFE), Bureau of Justice...
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Chen, Haihan; Grassian, Vicki H
2013-09-17
Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.
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Water quality impacts of hydraulic-fracturing chemicals observed in a permeable, quartz-sand aquifer
NASA Astrophysics Data System (ADS)
Kent, D. B.; LeBlanc, D. R.; Smith, R. L.
2012-12-01
A pilot scale experiment was conducted on western Cape Cod, Massachusetts to test the use of hydraulic fracturing (HF) for emplacing permeable reactive barriers (PRB) where the water table is too far below land surface to use standard excavation methods. Two PRB were emplaced 24 to 36 meters below land surface in a plume with low concentrations of perchloroethylene in oxic, mildly acidic groundwater with low concentrations of dissolved salts. The granular aquifer sediments consist of permeable sands and gravels. Quartz comprises greater than 90% by weight of the aquifer sediments but chemical reactivity of the sediments is controlled by micrometer-scale chlorite and illite and nanometer-scale aluminum-substituted goethite. HF fluids contained guar gum (gelling agent), cellulose enzyme and acetic acid (breakers), sodium borate (cross-linker), potassium (K) carbonate (pH adjustor), and sodium (Na) chloride (tracer). Water-quality impacts within about 20 meters of the PRB were monitored over a 1.7-year period following HF. Arrival of HF-chemicals was marked by an increase in boron (B) from ambient concentrations of 6 uM to >800 uM. B concentrations rose for approximately 50 days, much longer than the 22-day period over which HF was conducted. B concentrations subsequently decreased but remained 2-3 times above background concentrations for almost one year. Elevated Na and K concentrations in the HF fluids drove sorption (including ion exchange) reactions resulting in transient increases in naturally occurring major, minor, and trace cations up to 20 to 50 times background concentrations. Increases in dissolved organic carbon (DOC) and decreases in dissolved oxygen (DO) concentrations were observed as B concentrations increased. DOC concentration subsequently decreased but remained significantly above background. DO concentrations remained below detection. Dissolved iron (Fe) and manganese (Mn) concentrations increased as DO concentrations decreased below detection and remained elevated 1.7 years after HF. Reactions with Fe in the PRB may have contributed to the observed Fe concentrations but Mn was likely released from the aquifer sediments. Fe and Mn concentrations remained elevated throughout the sampling period. Dissolved arsenic concentrations increased after anaerobic conditions were established from below detection to 0.3-0.5 uM. HF fluids contained only a subset of the chemicals used in typical HF stimulations and aquifer sediments were likely less reactive than aquifer solids at other sites. Despite these differences, several findings have applicability to other sites. B is a potentially useful tracer of intrusion of HF fluids into aquifers, but elevated concentrations may be short-lived. Sorption reactions driven by differences in dissolved salt concentrations between HF fluids and ambient groundwater result in changes in cation concentrations, including barium and strontium. Organic compounds in HF fluids may drive aerobic aquifers anaerobic. Anaerobic conditions may lead to mobilization of naturally occurring contaminants like arsenic, whose reduced forms are more mobile than oxidized forms.
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Aher, Ashish; Papp, Joseph; Colburn, Andrew; Wan, Hongyi; Hatakeyama, Evan; Prakash, Prakhar; Weaver, Ben; Bhattacharyya, Dibakar
2017-11-01
Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (Fe x O y nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by Fe x O y functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. Fe x O y functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by Fe x O y functionalized membrane for removal of NA.
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Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.
Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G
2014-04-01
Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.
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Effects of solution chemistry on arsenic(V) removal by low-cost adsorbents.
Wang, Yuru; Tsang, Daniel C W
2013-11-01
Natural and anthropogenic arsenic (As) contamination of water sources pose serious health concerns, especially for small communities in rural areas. This study assessed the applicability of three industrial byproducts (coal fly ash, lignite, and green waste compost) as the low-cost adsorbents for As(V) removal under various field-relevant conditions (dissolved oxygen, As(V)/Fe ratio, solution pH, and presence of competing species). The physico-chemical properties of the adsorbents were characterized by XRD, XRF, FT-IR, and NMR analysis. Batch experiments demonstrated that coal fly ash could provide effective As(V) removal (82.1%-95%) because it contained high content of amorphous iron/aluminium hydroxides for As(V) adsorption and dissolvable calcium minerals for calcium arsenate precipitation. However, the addition of lignite and green waste compost was found unfavourable since they hindered the As(V) removal by 10%-42% possibly due to dissolution of organic matter and ternary arsenate-iron-organic matter complexes. On the other hand, higher concentrations of dissolved iron (comparing As(V)/Fe ratios of 1:1 and 1:10) and dissolved oxygen (comparing 0.2 and 6 mg/L) only marginally enhanced the As(V) removal at pH 6 and 8. Thus, addition of dissolved iron, water aeration, or pH adjustment became unnecessary because coal fly ash was able to provide effective As(V) removal under the natural range of geochemical conditions. Moreover, the presence of low levels of background competing (0.8 or 8 mg/L of humic acid, phosphate, and silicate) imposed little influence on As(V) removal, possibly because the high adsorption capacity of coal fly ash was far from exhaustion. These results suggested that coal fly ash was a potentially promising adsorbent that warranted further investigation.
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Transformation of mackinawite to greigite by trichloroethylene and tetrachloroethylene.
Lan, Ying; Elwood Madden, Andrew S; Butler, Elizabeth C
2016-10-12
Trichloroethylene (TCE) and tetrachloroethylene (PCE) are common ground water contaminants susceptible to reductive dechlorination by FeS (mackinawite) in anaerobic environments. The objective of this study was to characterize the mineral-associated products that form when mackinawite reacts with TCE and PCE. The dissolved products of the reaction included Cl - and Fe 2+ , and trace amounts of cis 1,2-dichloroethylene (for TCE) and TCE (for PCE). Selected area electron diffraction (SAED) analysis identified greigite as a mackinawite oxidation product formed after reaction between TCE or PCE and FeS over seven weeks. Release of Fe 2+ is consistent with the solid state transformation of mackinawite to greigite, resulting in depletion of the solid with Fe. X-ray photoelectron spectroscopy of the sulfur 2p peak showed a shift to a higher binding energy after FeS reacted with TCE or PCE, also observed in other studies of mackinawite oxidation to greigite. The results may help efforts to maintain the reactivity of FeS generated to remediate chlorinated aliphatic contaminants in ground water.
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Jeong, Sanghyun; Sathasivan, Arumugam; Kastl, George; Shim, Wang Geun; Vigneswaran, Saravanamuthu
2014-01-01
Coagulation removes colloidal matters and dissolved organic carbon (DOC) which can cause irreversible membrane fouling. However, how DOC is removed by coagulant is not well-known. Jar test was used to study the removal of hydrophobic and hydrophilic DOC fractions at various doses (0.5-8.0 mg-Fe(+3) L(-1)) of ferric chloride (FeCl3) and pH (5.0-9.0). Natural organic matter (NOM) in seawater and treated seawater were fractionated by liquid chromatography-organic carbon detector (LC-OCD). Compared to surface water, the removal of DOC in seawater by coagulation was remarkably different. Majority of DOC could be easily removed with very low coagulant dose (<5.0 mg-Fe(+3) L(-1)) and the removal efficiency did not vary with pH, but the DOC composition in treated water had significantly changed. Hydrophobic fraction (HB) was better removed at high pH while hydrophilic fraction (HF) was better removed at low pH. A modified model of Kastl et al. (2004) which assumed that the removal occurred by adsorption of un-dissociated compounds onto ferric hydroxide was formulated and successfully validated against the jar test data. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Frau, Franco; Medas, Daniela; Da Pelo, Stefania; Wanty, Richard B.; Cidu, Rosa
2015-01-01
After mine closure in the 1980s and subsequent shutdown of the dewatering system, groundwater rebound led to drainage outflow from the Casargiu gallery (Montevecchio mine, SW Sardinia, Italy) beginning in 1997. Mine drainage had pH 6.0 and dissolved concentrations of sulfate (5000 mg/L) and metals (e.g., 1000 mg/L Zn, 230 mg/L Fe, 150 mg/L Mn) much higher than those previously measured in groundwater under dewatering conditions. As compared with the first stages of rebound at Casargiu, a very high contamination level still persists after more than 15 years of flushing. Mine drainage (20–70 L/s; pH 6.0 ± 0.2; Zn-Mg-Ca-SO4 composition) flowed into the Rio Irvi. Abundant precipitation of amorphous Fe(III)-(oxy)hydroxides occurred. Moreover, sulfate-bearing green rust was observed to flocculate in the reach of the Rio Irvi where pH was still circumneutral. Water sampling along this stream for about 6 km almost to its mouth in the Mediterranean Sea showed a pH decrease from 6.0 to 4.0 and a significant removal of Fe (46 %) and As (96 %), while sulfate, Zn, Mn, Co, Ni, and Cd showed small variations downstream. Lead was initially adsorbed onto Fe(III)-(oxy)hydroxides, then desorbed as pH dropped below 5. The estimated amount of dissolved metals discharged into the Mediterranean Sea is significant (e.g., 900 kg/day Zn, 1.4 kg/day Cd, 5 kg/day Ni). In particular, a conservative estimation of the amount of Zn discharged to the sea is about 330 ton/year, which would correspond to 1.4 % of the global annual flux of dissolved Zn from uncontaminated rivers to the oceans.
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NASA Astrophysics Data System (ADS)
Cathalot, C.; Laes-Huon, A.; Pelleter, E.; Maillard, L.; Chéron, S.; Boissier, A.; Waeles, M.; Cotte, L.; Pernet-Coudrier, B.; Gayet, N.; Sarrazin, J.; Sarradin, P. M.
2016-12-01
Despite the importance of trace metals for marine ecosystems and in the global carbon cycle, dissolved metal sources in the deep ocean and their export mechanism are, today, still unconstrained. The historical view that dissolved metals are largely removed from hydrothermal plumes through precipitation of a range of iron-bearing minerals is now being challenged. Several potential mechanisms for the delivery of hydrothermally sourced metals to the open ocean have been suggested and require a thorough documentation of the early mixing processes between the hydrothermal fluids and the ambient seawater. The geochemistry of a plume, and specially the rising plume, is dictated by the nature and composition of the host rock, fluid temperature, phase separation at depth and subsurface mixing processes, and thus can vary in temperature, pH, metal and dissolved gases content between spatially close hydrothermal vents. Here, we present in situ chemical conditions during the early mixing gradient between hydrothermal fluids and seawater at the Lucky Strike site (Mid-Atlantic Ridge), using a multi proxy approach targeting both the dissolved and particulate phase and combining in situ measurements and analysis back in the lab. Indeed, in situ O2, H2S and temperature measurements were performed at a 1Hz frequency, coupled to lower frequency analysis of in situ Fe2+. In addition, particulate material filtered in situ was analyzed using Inductive Coupled Plasma - Mass Spectrometry, X-Ray Diffraction, X-Ray Fluorescence and Scanning Electron Microscopy and provided useful insights regarding the reactivity of metals during the mixing processes. Our results show different behavior within the Lucky Strike vent field. Fe and S co-precipitation through chalcopyrite formation at the newly discovered Capelinhos site seem to be the main process. At the White Caste site, on the other hand, wurzite and sphalerite precipitation seems to dominate the dilution processes, H2S being rapidly titrated with the available Zinc early in the mixing. Our results indicate a clear control by subsurface mixing processes, at a very local scale: within a single vent field, temperature outflow of the hydrothermal fluid clearly drives Cu, Fe and Zn scavenging in the particulate phase, and controlling hence the iron stability and export.
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Relevance of peat-draining rivers for the riverine input of dissolved iron into the ocean.
Krachler, Regina; Krachler, Rudolf F; von der Kammer, Frank; Süphandag, Altan; Jirsa, Franz; Ayromlou, Shahram; Hofmann, Thilo; Keppler, Bernhard K
2010-05-01
Peat bogs have the ability to produce strong chelate ligands (humic and fulvic acids) which enhance the weathering rates of iron-silicate minerals and greatly increase the solubility of the essential trace metal iron in river water. Fluvial networks link peat bogs with the ocean, and thus terrestrial-derived fulvic-iron complexes fuel the ocean's biological productivity and biological carbon pump, but understanding this role is constrained by inconsistent observations regarding the behaviour of riverine iron in the estuarine mixing zone, where precipitation reactions remove iron from the water column. We applied a characterization of the colloidal iron carriers in peatland-draining rivers in North Scotland, using field-flow fractionation (FFF), in combination with end-member mixing experiments of river water sampled near the river mouth and coastal seawater using a (59)Fe radiotracer method. According to our results, the investigated river contributed "truly dissolved" Fe concentrations of about 3300nmolL(-1) to the ocean which is nearly two orders of magnitude higher than the dissolved iron contribution of the "average world" river ( approximately 40nmolL(-1)). Thus we conclude that peatland-draining rivers are important sources of dissolved iron to the ocean margins. We propose highly electrostatic and sterical stabilized iron-organic matter complexes in the size range of <2kDa to be responsible for iron transport across the estuarine mixing zone. Copyright 2010 Elsevier B.V. All rights reserved.
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Parker, Stephen R.; Gammons, Christopher H.; Poulson, Simon R.; DeGrandpre, Michael D.
2007-01-01
Many rivers undergo diel (24-h) concentration fluctuations of pH, dissolved gases, trace metals, nutrients, and other chemical species. A study conducted in 1994 documented such behavior in the upper Clark Fork River, Montana, a stream whose headwaters have been severely impacted by historic metal mining, milling, and smelting. The purpose of the present investigation was to expand on these earlier findings by conducting simultaneous diel samplings at two sites on the upper Clark Fork River separated by 2.5 h of stream travel time. By monitoring two stations, it was possible to more closely examine the processes that control temporal and spatial gradients in stream chemistry. Another objective was to examine diel changes in the δ13C composition of dissolved inorganic C (DIC) and their relationship to biological activity in the stream. The most important findings of this study include: (1) concentrations of dissolved and particulate heavy metals increased during the night and decreased during the day, in agreement with previous work; (2) these changes were positively correlated to diel changes in pH, dissolved O2, and water temperature; (3) dissolved concentrations increased during the night at the lower site, but showed the opposite behavior at the upper site; and (4) diel changes in δ13C-DIC were noted at both sites, although the timing and magnitudes of the cycles differed. Hypotheses to explain the first two observations include: cyclic co-precipitation of divalent metals with carbonate minerals; pH- and temperature-dependent sorption of metal cations onto the streambed and suspended particles; or photosynthetically enhanced oxidation and removal of Fe and Mn oxides at biofilm surfaces during the daytime. The latter model explains the majority of the field observations, including night-time increases in particulate forms of Fe and other elements.
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Hong, Jun; Lu, Sijia; Zhang, Caixiang; Qi, Shihua; Wang, Yanxin
2011-09-01
A new Vis-Fe(0)-H(2)O(2)-citrate-O(2) system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L(-1) of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L(-1) of H(2)O(2), 12.6g of Fe(0) and 1.0 mmol L(-1) of citrate at pH 7.5. Results showed that, in 1h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe(0) surface was found to be at a very low level as <5.4 μmol L(-1). Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe(0)-H(2)O(2)-citrate-O(2) system, which accounted for 75% of substrate removal in 3h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe(0)>H(2)O(2)>citrate>Vis>O(2). This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations. Copyright © 2011 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Hein, James R.; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe J.; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah R.; Till, Claire P.
2017-11-01
Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, and HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ˜15 Myr ago.
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Sarin, P; Snoeyink, V L; Bebee, J; Jim, K K; Beckett, M A; Kriven, W M; Clement, J A
2004-03-01
Iron release from corroded iron pipes is the principal cause of "colored water" problems in drinking water distribution systems. The corrosion scales present in corroded iron pipes restrict the flow of water, and can also deteriorate the water quality. This research was focused on understanding the effect of dissolved oxygen (DO), a key water quality parameter, on iron release from the old corroded iron pipes. Corrosion scales from 70-year-old galvanized iron pipe were characterized as porous deposits of Fe(III) phases (goethite (alpha-FeOOH), magnetite (Fe(3)O(4)), and maghemite (alpha-Fe(2)O(3))) with a shell-like, dense layer near the top of the scales. High concentrations of readily soluble Fe(II) content was present inside the scales. Iron release from these corroded pipes was investigated for both flow and stagnant water conditions. Our studies confirmed that iron was released to bulk water primarily in the ferrous form. When DO was present in water, higher amounts of iron release was observed during stagnation in comparison to flowing water conditions. Additionally, it was found that increasing the DO concentration in water during stagnation reduced the amount of iron release. Our studies substantiate that increasing the concentration of oxidants in water and maintaining flowing conditions can reduce the amount of iron release from corroded iron pipes. Based on our studies, it is proposed that iron is released from corroded iron pipes by dissolution of corrosion scales, and that the microstructure and composition of corrosion scales are important parameters that can influence the amount of iron released from such systems.
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Kong, Yanli; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Fan, Leitao
2017-01-01
The influence of humic acid (HA) on the removal of arsenic by FeCl 3 was systematically studied in this paper. Jar tests were performed to investigate the influence on arsenic during FeCl 3 coagulation of the pH adjusting method, the initial As/Fe ratio, the equilibrium As concentration, and co-occurring anions and cations. Compared with results in HA-free systems, the removal trends of arsenic in HA solutions were quite different. It was found that As(V) removal was higher at low equilibrium concentration, yet the opposite was true for As(III) removal. The presence of HA influenced the effective number of active sites for arsenic removal by FeCl 3 flocculation. In addition, in the presence of HA, the impacts of co-existing solutions on arsenic removal were also different from that of an HA-free system. This study examined the influence of co-occurring anions, such as phosphate, sulfate, and silicate on arsenic removal, depending on their ability to compete for sorption sites and to hinder or facilitate the aggregation of ferric hydroxide flocs. The presence of Ca 2+ or Cd 2+ significantly increased arsenic removal at higher pH. Low concentrations of dissolved HA and high concentrations of colloid affected the adsorption of arsenic onto iron oxide. The influence of HA on the adsorption of arsenic onto iron oxide primarily depended on the relative content of the dissolved and mineral combination states of HA and the interface combination forms.
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Hein, James; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah; Till, Claire P.
2017-01-01
Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits.The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ∼15 Myr ago.
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Rahman, Safiur; Gagnon, Graham A
2014-01-01
Corrosion control strategies are important for many utilities in maintaining water quality from the water treatment plant to the customers' tap. In drinking water with low alkalinity, water quality can become significantly degraded in iron-based pipes if water utilities are not diligent in maintaining proper corrosion control. This article reports on experiments conducted in bicarbonate buffered (5 mg-C/L) synthetic water to determine the effects of corrosion control (pH and phosphate) and dissolved organic matter (DOM) on the rate constants of the Fe(II) oxidation process. A factorial design approach elucidated that pH (P = 0.007, contribution: 42.5%) and phosphate (P = 0.025, contribution: 22.7%) were the statistically significant factors in the Fe(II) oxidation process at a 95% confidence level. The comprehensive study revealed a significant dependency relationship between the Fe(II) oxidation rate constants (k) and phosphate-to- Fe(II) mole ratio. At pH 6.5, the optimum mole ratio was found to be 0.3 to reduce the k values. Conversely, the k values were observed to increase for the phosphate-to- Fe(II) mole ratio > 1. The factorial design approach revealed that chlorine and DOM for the designated dosages did not cause a statistically significant (α = 0.05, P > 0.05)change in rate constants. However, an increment of the chlorine to ferrous iron mole ratio by a factor of ∼ 2.5 resulted in an increase k values by a factor of ∼ 10. This study conclusively demonstrated that the lowest Fe(II) oxidation rate constant was obtained under low pH conditions (pH ≤ 6.5), with chlorine doses less than 2.2 mg/L and with a phosphate-to-Fe(II) mole ratio ≈ 0.3 in the iron water systems.
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Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan
2014-01-01
To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 g/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater.
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Yang, Qiang; Culbertson, Charles W; Nielsen, Martha G; Schalk, Charles W; Johnson, Carole D; Marvinney, Robert G; Stute, Martin; Zheng, Yan
2015-02-01
To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 mg/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ(18)O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. Copyright © 2014 Elsevier B.V. All rights reserved.
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Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan
2014-01-01
To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 µg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70–100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93–99%) in particulates (>0.45 µm). These particulates and those settled after a 16-day batch experiment contain 560–13,000 mg/kg of As and 14–35% weight/weight of Fe. As/Fe ratios (2.5–20 mmole/mole) and As partitioning ratios (adsorbed/dissolved [As], 20,000–100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1,300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. PMID:24842411
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Horowitz, A.J.; Lum, K.R.; Garbarino, J.R.; Hall, G.E.M.; Lemieux, C.; Demas, C.R.
1996-01-01
Field and laboratory experiments indicate that a number of factors associated with filtration other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample) can produce significant variations in the 'dissolved' concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. The bulk of these variations result from the inclusion/exclusion of colloidally associated trace elements in the filtrate, although dilution and sorption/desorption from filters also may be factors. Thus, dissolved trace element concentrations quantitated by analyzing filtrates generated by processing whole water through similar pore-sized filters may not be equal or comparable. As such, simple filtration of unspecified volumes of natural water through unspecified 0.45-??m membrane filters may no longer represent an acceptable operational definition for a number of dissolved chemical constituents.
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Language Trends 2010 Secondary (CILT, ALL, ISMLA) Data Report
ERIC Educational Resources Information Center
CILT, the National Centre for Languages, 2011
2011-01-01
This survey has been carried out annually since 2002 to track developments in language provision and take up in secondary schools. The following sections are included in this analysis of key results from the Secondary Language Trends survey: (1) Survey background, methodology and sample design; (2) DfE (Department for Education) data trends of…
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Reframing the English Grammar Schools Debate
ERIC Educational Resources Information Center
Morris, Rebecca; Perry, Thomas
2017-01-01
In October 2015 the Department for Education (DfE) permitted a grammar school in Tonbridge, Kent, to open up an annexe in Sevenoaks, 10 miles away. Amidst claims that the annexe was essentially a new grammar school, the decision reignited an old debate about the value of academically-selective "grammar" schools in England. The intensity…
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Using Space to Inspire and Engage Children
ERIC Educational Resources Information Center
Clements, Allan
2015-01-01
The European Space Education Resources Office (ESERO-UK) is a project of the European Space Agency (ESA) and national partners including the Department for Education (DfE), The UK Space Agency (UKSA) and the Science and Technology Facilities Council (STFC). The key objective of the project is to promote space as an exciting inspirational context…
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Cereal Box Design: An Interdisciplinary Graphics Activity
ERIC Educational Resources Information Center
Fitzgerald, Mike; Tsosie, Teri
2004-01-01
This article describes cereal box design, an interdisciplinary graphics activity. The cereal box design activity is intriguing both for its simplicity and the resourcefulness that it can generate in young people. It lends itself to a variety of curriculums. It covers both consumerism and Design for the Environment (DfE) concepts broadly and in…
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Evaluating proposed alternative chemical structures to support the design of safer chemicals and products is an important component of EPA's Green Chemistry and Design for the Environment (DfE) Programs. As such, science-based alternatives assessment is essential to support EPA's...
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ERIC Educational Resources Information Center
Smith, Peter K.; Madsen, Kirsten C.
This poster presentation outlines the work of the DFE Anti-bullying project. In the first part of the poster the results of a large scale survey in the United Kingdom are presented. The results show the extent and nature of bullying. The questionnaire survey was administered to students from 24 schools in and around Sheffield, a northern…
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"Old Poems Have Heart": Teenage Students Reading Early Modern Poetry
ERIC Educational Resources Information Center
Naylor, Amanda
2013-01-01
The proposals for the revised National Curriculum in English suggest limiting the pre-twentieth century poetry that GCSE pupils read to "representative Romantic poetry" (Department for Education [DFE], 2013, p. 4). This paper argues that poetry of the early modern period is challenging and enriching study for adolescent pupils and that…
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3D facial expression recognition using maximum relevance minimum redundancy geometrical features
NASA Astrophysics Data System (ADS)
Rabiu, Habibu; Saripan, M. Iqbal; Mashohor, Syamsiah; Marhaban, Mohd Hamiruce
2012-12-01
In recent years, facial expression recognition (FER) has become an attractive research area, which besides the fundamental challenges, it poses, finds application in areas, such as human-computer interaction, clinical psychology, lie detection, pain assessment, and neurology. Generally the approaches to FER consist of three main steps: face detection, feature extraction and expression recognition. The recognition accuracy of FER hinges immensely on the relevance of the selected features in representing the target expressions. In this article, we present a person and gender independent 3D facial expression recognition method, using maximum relevance minimum redundancy geometrical features. The aim is to detect a compact set of features that sufficiently represents the most discriminative features between the target classes. Multi-class one-against-one SVM classifier was employed to recognize the seven facial expressions; neutral, happy, sad, angry, fear, disgust, and surprise. The average recognition accuracy of 92.2% was recorded. Furthermore, inter database homogeneity was investigated between two independent databases the BU-3DFE and UPM-3DFE the results showed a strong homogeneity between the two databases.
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Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter
Lindsey, M.E.; Tarr, M.A.
2000-01-01
Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.
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Persistence of deeply sourced iron in the Pacific Ocean.
Horner, Tristan J; Williams, Helen M; Hein, James R; Saito, Mak A; Burton, Kevin W; Halliday, Alex N; Nielsen, Sune G
2015-02-03
Biological carbon fixation is limited by the supply of Fe in vast regions of the global ocean. Dissolved Fe in seawater is primarily sourced from continental mineral dust, submarine hydrothermalism, and sediment dissolution along continental margins. However, the relative contributions of these three sources to the Fe budget of the open ocean remains contentious. By exploiting the Fe stable isotopic fingerprints of these sources, it is possible to trace distinct Fe pools through marine environments, and through time using sedimentary records. We present a reconstruction of deep-sea Fe isotopic compositions from a Pacific Fe-Mn crust spanning the past 76 My. We find that there have been large and systematic changes in the Fe isotopic composition of seawater over the Cenozoic that reflect the influence of several, distinct Fe sources to the central Pacific Ocean. Given that deeply sourced Fe from hydrothermalism and marginal sediment dissolution exhibit the largest Fe isotopic variations in modern oceanic settings, the record requires that these deep Fe sources have exerted a major control over the Fe inventory of the Pacific for the past 76 My. The persistence of deeply sourced Fe in the Pacific Ocean illustrates that multiple sources contribute to the total Fe budget of the ocean and highlights the importance of oceanic circulation in determining if deeply sourced Fe is ever ventilated at the surface.
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Wingenter, Oliver W; Haase, Karl B; Strutton, Peter; Friederich, Gernot; Meinardi, Simone; Blake, Donald R; Rowland, F Sherwood
2004-06-08
Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (CO(2)) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH(4)), isoprene (C(5)H(8)), methyl bromide (CH(3)Br), dimethyl sulfide, and oxygen (O(2)), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH(3)I), and CO(2) observed during the Southern Ocean Iron Enrichment Experiments.
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Iron-mediated soil carbon response to water-table decline in an alpine wetland
NASA Astrophysics Data System (ADS)
Wang, Yiyun; Wang, Hao; He, Jin-Sheng; Feng, Xiaojuan
2017-06-01
The tremendous reservoir of soil organic carbon (SOC) in wetlands is being threatened by water-table decline (WTD) globally. However, the SOC response to WTD remains highly uncertain. Here we examine the under-investigated role of iron (Fe) in mediating soil enzyme activity and lignin stabilization in a mesocosm WTD experiment in an alpine wetland. In contrast to the classic `enzyme latch' theory, phenol oxidative activity is mainly controlled by ferrous iron [Fe(II)] and declines with WTD, leading to an accumulation of dissolvable aromatics and a reduced activity of hydrolytic enzyme. Furthermore, using dithionite to remove Fe oxides, we observe a significant increase of Fe-protected lignin phenols in the air-exposed soils. Fe oxidation hence acts as an `iron gate' against the `enzyme latch' in regulating wetland SOC dynamics under oxygen exposure. This newly recognized mechanism may be key to predicting wetland soil carbon storage with intensified WTD in a changing climate.
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Air pollution-aerosol interactions produce more bioavailable iron for ocean ecosystems.
Li, Weijun; Xu, Liang; Liu, Xiaohuan; Zhang, Jianchao; Lin, Yangting; Yao, Xiaohong; Gao, Huiwang; Zhang, Daizhou; Chen, Jianmin; Wang, Wenxing; Harrison, Roy M; Zhang, Xiaoye; Shao, Longyi; Fu, Pingqing; Nenes, Athanasios; Shi, Zongbo
2017-03-01
It has long been hypothesized that acids formed from anthropogenic pollutants and natural emissions dissolve iron (Fe) in airborne particles, enhancing the supply of bioavailable Fe to the oceans. However, field observations have yet to provide indisputable evidence to confirm this hypothesis. Single-particle chemical analysis for hundreds of individual atmospheric particles collected over the East China Sea shows that Fe-rich particles from coal combustion and steel industries were coated with thick layers of sulfate after 1 to 2 days of atmospheric residence. The Fe in aged particles was present as a "hotspot" of (insoluble) iron oxides and throughout the acidic sulfate coating in the form of (soluble) Fe sulfate, which increases with degree of aging (thickness of coating). This provides the "smoking gun" for acid iron dissolution, because iron sulfate was not detected in the freshly emitted particles and there is no other source or mechanism of iron sulfate formation in the atmosphere.
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NASA Astrophysics Data System (ADS)
Syverson, D. D.; Ono, S.; Seyfried, W. E., Jr.
2017-12-01
The rate of exchange and multiple S isotope fractionation between pyrite and dissolved H2S and SO4 was determined at 300°C and 500 bars at physiochemical conditions indicative of natural MOR hydrothermal systems by using the flexible gold cell reactor system [1]. A 34S enriched solution was designed to track reaction progress and to not significantly perturb mass dependent relationships between 33S and 36S, allowing for observations of natural mass dependent fractionation between pyrite and dissolved species during dissolution and recrystallization. The experimental data are compared with previously determined experimental constraints of S isotope exchange between fluid species [2] and with Fe and S isotope experiments conducted at higher temperature and where pyrite was precipitated rapidly from solution at 300 and 350°C and 500 bars [3, 4]. Briefly, the 34S isotope data indicate that the rate of exchange between pyrite and dissolved aqueous species is sluggish, where insignificant exchange occurred after the course of 4000 hours at 300°C, approximately 4%. Furthermore, the 33,36S mineral-fluid data indicate that upon pyrite dissolution, the light isotopes are preferentially removed into solution and incorporated as H2S and SO4-. These data are consistent with natural observations of pyrite-dissolved S disequilibrium and provide important insight towards mineral reactivity and retentiveness of recording mineral formation conditions. [1] Seyfried Jr., W.E., Janecky, D.R. & Berndt, M.E. 1987 Rocking autoclaves for hydrothermal experiments: II. The flexible reaction-cell system. Hydrothermal Experimental Techniques 216-239. [2] Ohmoto, H. & Lasaga, A.C. 1982 Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems. Geochimica et Cosmochimica Acta 46, 1727-1745. [3] Syverson, D.D., Borrok, D.M. & Seyfried Jr., W.E. 2013 Experimental determination of equilibrium Fe isotopic fractionation between pyrite and dissolved Fe under hydrothermal conditions. Geochimica et Cosmochimica Acta 122, 170-183. [4] Syverson, D.D., Ono, S., Shanks, W.C. & Seyfried Jr., W.E. 2015 Multiple sulfur isotope fractionation and mass transfer processes during pyrite precipitation and recrystallization: An experimental study at 300 and 350°C. Geochimica et Cosmochimica Acta 165, 418-434.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared
Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethitemore » or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially localizes on the (100) face of goethite, independent of the number of redox cycles goethite undergoes. This work demonstrates that under oxic conditions, solid Fe(II) associated with goethite resulting from rapid redox cycling is reactive and available for electron transfer to Cr(VI), suggesting Fe(III) (hydr)oxides may act as reservoirs of reactive electron density, even in oxygen saturated environments.« less
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Hamad, Samera Hussein; Schauer, James Jay; Shafer, Martin Merrill; Abed Al-Raheem, Esam; Satar, Hyder
2012-01-01
The distribution of dissolved and particulate forms of 49 elements was investigated along transect of the Tigris River (one of the major rivers of the world) within Baghdad city and in its major tributary (Diyala River) from 11 to 28 July 2011. SF-ICP-MS was used to measure total and filterable elements at 17 locations along the Tigris River transect, two samples from the Diyala River, and in one sample from the confluence of the two rivers. The calculated particulate forms were used to determine the particle-partition coefficients of the metals. No major changes in the elements concentrations down the river transect. Dissolved phases dominated the physical speciation of many metals (e.g., As, Mo, and Pt) in the Tigris River, while Al, Fe, Pb, Th, and Ti were exhibiting high particulate fractions, with a trend of particle partition coefficients of [Ti(40) > Th(35) > Fe(15) > Al(13) > Pb(4.5)] ∗ 106 L/kg. Particulate forms of all metals exhibited high concentrations in the Diyala River, though the partition coefficients were low due to high TSS (~270 mg/L). A comparison of Tigris with the major rivers of the world showed that Tigris quality in Baghdad is comparable to Seine River quality in Paris. PMID:23304083
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Persistence of deeply sourced iron in the Pacific Ocean
Horner, Tristan J.; Williams, Helen M.; Hein, James R.; Saito, Mak A.; Burton, Kevin W.; Halliday, Alex N.; Nielsen, Sune G.
2015-01-01
Biological carbon fixation is limited by the supply of Fe in vast regions of the global ocean. Dissolved Fe in seawater is primarily sourced from continental mineral dust, submarine hydrothermalism, and sediment dissolution along continental margins. However, the relative contributions of these three sources to the Fe budget of the open ocean remains contentious. By exploiting the Fe stable isotopic fingerprints of these sources, it is possible to trace distinct Fe pools through marine environments, and through time using sedimentary records. We present a reconstruction of deep-sea Fe isotopic compositions from a Pacific Fe−Mn crust spanning the past 76 My. We find that there have been large and systematic changes in the Fe isotopic composition of seawater over the Cenozoic that reflect the influence of several, distinct Fe sources to the central Pacific Ocean. Given that deeply sourced Fe from hydrothermalism and marginal sediment dissolution exhibit the largest Fe isotopic variations in modern oceanic settings, the record requires that these deep Fe sources have exerted a major control over the Fe inventory of the Pacific for the past 76 My. The persistence of deeply sourced Fe in the Pacific Ocean illustrates that multiple sources contribute to the total Fe budget of the ocean and highlights the importance of oceanic circulation in determining if deeply sourced Fe is ever ventilated at the surface. PMID:25605900
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Weingarten, Evan; Chen, Qijia; McAdams, Maxwell; Yi, Jessica; Hepler, Justin; Albarracín, Dolores
2016-05-01
A meta-analysis assessed the behavioral impact of and psychological processes associated with presenting words connected to an action or a goal representation. The average and distribution of 352 effect sizes (analyzed using fixed-effects and random-effects models) was obtained from 133 studies (84 reports) in which word primes were incidentally presented to participants, with a nonopposite control group, before measuring a behavioral dependent variable. Findings revealed a small behavioral priming effect (dFE = 0.332, dRE = 0.352), which was robust across methodological procedures and only minimally biased by the publication of positive (vs. negative) results. Theory testing analyses indicated that more valued behavior or goal concepts (e.g., associated with important outcomes or values) were associated with stronger priming effects than were less valued behaviors. Furthermore, there was some evidence of persistence of goal effects over time. These results support the notion that goal activation contributes over and above perception-behavior in explaining priming effects. In summary, theorizing about the role of value and satisfaction in goal activation pointed to stronger effects of a behavior or goal concept on overt action. There was no evidence that expectancy (ease of achieving the goal) moderated priming effects. (PsycINFO Database Record (c) 2016 APA, all rights reserved).
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Weingarten, Evan; Chen, Qijia; McAdams, Maxwell; Yi, Jessica; Hepler, Justin; Albarracin, Dolores
2018-01-01
A meta-analysis assessed the behavioral impact of and psychological processes associated with presenting words connected to an action or a goal representation. The average and distribution of 352 effect sizes (analyzed using fixed-effects and random-effects models) was obtained from 133 studies (84 reports) in which word primes were incidentally presented to participants, with a non-opposite control group, prior to measuring a behavioral dependent variable. Findings revealed a small behavioral priming effect (dFE = 0.332, dRE = 0.352), which was robust across methodological procedures and only minimally biased by the publication of positive (vs. negative) results. Theory testing analyses indicated that more valued behavior or goal concepts (e.g., associated with important outcomes or values) were associated with stronger priming effects than were less valued behaviors. Furthermore, there was some evidence of persistence of goal effects over time. These results support the notion that goal activation contributes over and above perception-behavior in explaining priming effects. In sum, theorizing about the role of value and satisfaction in goal activation pointed to stronger effects of a behavior or goal concept on overt action. There was no evidence that expectancy (ease of achieving the goal) moderated priming effects. PMID:26689090
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The marine diatom and diazotroph under future climate: Role of Iron
NASA Astrophysics Data System (ADS)
Li, Xuefeng; Fonseca-batista, Debany; Brouwers, Julie; Roevros, Nathalie; Dehairs, Frank; Chou, Lei
2016-04-01
Diatoms constitute a major group of phytoplankton, accounting for one quarter of the world's net primary productivity. Diazotrophs provide the largest input of new nitrogen (N) to the ocean and control the marine N budgets. It has been shown that iron (Fe) can be the limiting factor for diatom growth, in particular, in the HNLC (High Nutrient Low Chlorophyll) regions. This trace element can also govern the development of marine diazotrophs due to the high Fe demand necessary for biological N2 fixation. Iron plays thus an essential role in governing the marine primary productivity and the efficiency of biological carbon pump. Ocean systems are undergoing continuous modifications at varying rates and magnitudes as a result of changing climate. The objectives of our research is to evaluate 1) how climate change (dust deposition, ocean warming and acidification) can affect Fe biogeochemistry and the growth of diatoms and diazotrophs, and 2) the role of Fe in the control of biological N2 fixation under future climate scenarios. Laboratory culture experiments using Chaetoceros socialis were examined at two temperatures (13°C and 18°C) and two CO2 conditions (400 μatm and 800 μatm). The present study demonstrates clearly the influence of ocean acidification on the release of Fe upon dust deposition. It also shows that dust particles could provide a readily utilizable source of Fe and other macronutrients (dissolved phosphate and silicate) for phytoplankton growth. Elevated pCO2 concentrations may have adverse impact on the diatom growth; seawater warming may cause poleward shifts in the biogeographic distribution of diatoms. The impact of Fe on the natural N2 fixation was tested via field incubation experiments using natureal phytoplankton assemblage in the Bay of Biscay and along the Iberian Margin. N2 fixation rates in oligotrophic waters were greatly stimulated through the addition of dissolved Fe compared to the control, demonstrating the limitation of N2 fixation by Fe. Numerous factors can affect the extent of N2 fixation, but a better understanding of the major controlling factors is highly required. Semi-continuous dilution culture experiments were conducted on Trichodesmium IMS-101 under future high pCO2 and warming seawater conditions. Additionally, special attention has been given to studying the effects of mineral dust deposition which is believed to promote N2 fixation through increasing Fe availability.
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Zahid, A.; Hassan, M.Q.; Balke, K.-D.; Flegr, M.; Clark, D.W.
2008-01-01
Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25-33 m) and deep (191-318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl- and higher proportions of Na+ relative to Ca2+, Mg2+, and K+ in groundwater suggest the influence by a source of Na+ and Cl-. Use of chemical fertilizers may cause higher concentrations of NH 4+ and PO 43- in shallow well samples. In general, most ions are positively correlated with Cl-, with Na+ showing an especially strong correlation with Cl-, indicating that these ions are derived from the same source of saline waters. The relationship between Cl-/HCO 3- ratios and Cl- also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO 3- reflect the degree of water-rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO 42- and NO 3- and high concentrations of dissolved Fe and PO 43- and NH 4+ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO 42- and NO 3- but correlate weakly with Mo, Fe concentrations and positively with those of P, PO 43- and NH 4+ ions. ?? 2007 Springer-Verlag.
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Liang, Chenju; Lee, I-Ling
2008-09-10
In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.
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Redox processes as revealed by voltammetry in the surface sediments of the Gotland Basin, Baltic Sea
NASA Astrophysics Data System (ADS)
Yücel, Mustafa; Dale, Andy; Sommer, Stefan; Pfannkuche, Olaf
2014-05-01
Sulfur cycling in marine sediments undergoes dramatic changes with changing redox conditions of the overlying waters. The upper sediments of the anoxic Gotland Basin, central Baltic Sea represent a dynamic redox environment with extensive mats of sulfide oxidizing bacteria covering the seafloor beneath the chemocline. In order to investigate sulfur redox cycling at the sediment-water interface, sediment cores were sampled over a transect covering 65 - 174 m water depth in August-September 2013. High resolution (0.25 mm minimum) vertical microprofiles of electroactive redox species including dissolved sulfide and iron were obtained with solid state Au-Hg voltammetric microelectrodes. This approach enabled a fine-scale comparison of porewater profiles across the basin. The steepest sulfide gradients (i.e. the highest sulfide consumption) occurred within the upper 10 mm in sediments covered by surficial mats (2.10 to 3.08 mmol m-2 day-1). In sediments under permanently anoxic waters (>140m), voltammetric signals for Fe(II) and aqueous FeS were detected below a subsurface maximum in dissolved sulfide, indicating a Fe flux originating from older, deeper sedimentary layers. Our results point to a unique sulfur cycling in the Gotland basin seafloor where sulfide accumulation is moderated by sulfide oxidation at the sediment surface and by FeS precipitation in deeper sediment layers. These processes may play an important role in minimizing benthic sulfide fluxes to bottom waters around the major basins of the Baltic Sea.
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Stollenwerk, Kenneth G.
1994-01-01
Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO4, 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer.The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H+ by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO2 to Fe(III), which then precipitated as Fe(OH)3. Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH)3 at pH < 4.7 and as AlOHSO4 at pH < 4.7. Aqueous Ca and SO4were close to equilibrium with gypsum.After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO4concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H+ desorbed from Fe(OH)3, pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO4 and elevated aqueous Al.
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Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.
Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying
2015-11-01
Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential for rapid (re)formation of dissolved Cr(vi) above regulatory levels.
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Survival of the fittest: phosphorus burial in the sulfidic deep Black Sea
NASA Astrophysics Data System (ADS)
Kraal, Peter; Dijkstra, Nikki; Behrends, Thilo; Slomp, Caroline
2016-04-01
The Black Sea is characterized by permanently anoxic and sulfidic deep waters. Studies of the mechanisms of P burial in such a setting can be used to improve our understanding of P cycling in modern coastal systems undergoing eutrophication and ancient oceans during periods of anoxia in Earth's past. Here, we present phosphorus and iron (Fe) pools as determined in surface sediments along a transect from oxic shallow waters to sulfidic deep waters in the northwestern Black Sea, using a combination of bulk chemical analyses and micro-scale X-ray fluorescence (μXRF) and X-ray absorption spectroscopy (μXAS). We show that under oxic bottom water conditions, ferric iron oxides (Fe(III)ox) in surficial sediment efficiently scavenge dissolved phosphate from pore waters. Under these conditions, Fe(III)ox-bound P constitutes the main P pool at the sediment surface, but rapidly declines with depth in the sediment due to anoxic diagenesis. The transition from shallow (oxic) to deep (sulfidic) waters along the depth transect is reflected in a slight increase in the fraction of organic P. We also show evidence for authigenic calcium phosphate formation under sulfidic conditions at relatively low dissolved PO4 concentrations. Furthermore, we provide spectroscopic evidence for the presence of Fe(II)-Mn(II)-Mg-P minerals in sediments of the sulfidic deep basin. We hypothesize that these minerals are formed as a result of input of Fe(III)ox-P from shallower waters and subsequent transformation in either the water column or sediment. This finding suggests an unexpected strength of Fe-P shuttling from the shelf to the deep basin. While the presence of Fe-P species in such a highly sulfidic environment is remarkable, further analysis suggests that this P pool may not be quantitatively significant. In fact, our results indicate that some of the P that is interpreted as Fe-bound P based on chemical extraction may in fact be Ca-associated PO4 consisting of a combination of fish debris and adsorbed P.
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Fu, Chaoqun; Xu, Lijun; Dan, Zhenhua; Makino, Akihiro; Hara, Nobuyoshi; Qin, Fengxiang; Chang, Hui
2017-01-01
Nanoporous electrodes have been fabricated by selectively dissolving the less noble α-Fe crystalline phase from nanocrystalline Fe85.2B14–xPxCu0.8 alloys (x= 0, 2, 4 at.%). The preferential dissolution is triggered by the weaker electrochemical stability of α-Fe nanocrystals than amorphous phase. The final nanoporous structure is mainly composed of amorphous residual phase and minor undissolved α-Fe crystals and can be predicted from initial microstructure of nanocrystalline precursor alloys. The structural inheritance is proved by the similarity of the size and outlines between nanopores formed after dealloying in 0.1 M H2SO4 and α-Fe nanocrystals precipitated after annealing of amorphous Fe85.2B14−xPxCu0.8 (x = 0, 2, 4 at.%) alloys. The Redox peak current density of the nanoporous electrodes obtained from nanocrystalline Fe85.2B10P4Cu0.8 alloys is more than one order higher than those of Fe plate electrode and its counterpart nanocrystalline alloys due to the large surface area and nearly-amorphous nature of ligaments. PMID:28594378
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DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rudisill, T. S.; Pierce, R. A.
2012-07-02
The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu upmore » to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.05-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a “standard” 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 °C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ~11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The data also indicate that lower KF concentrations would yield dissolution rates for B comparable to those observed with Gd at the same HNO{sub 3} concentration and dissolution temperature. To confirm that the optimal conditions identified by the dissolution rate measurements can be used to dissolve Pu metal up to 6.75 g/L in the presence of representative concentrations of Fe and Gd or B, a series of experiments was performed to demonstrate the flowsheets. In three of the five experiments, the offgas generation rate during the dissolution was measured and samples were analyzed for hydrogen gas (H{sub 2}). The use of 10 M HNO{sub 3} containing 0.03-0.05 M KF, 0.5-1.0 g/L Gd, and 1.9 g/L Fe resulted in complete dissolution of the metal in 2.0-3.5 h. When B was used as the neutron poison, 10 M HNO{sub 3} solutions containing 0.05-0.1 M KF, 1.9 g/L Fe, and 1 g/L B resulted in complete dissolution of the metal in 0.75-2.0 h. Dissolution rates estimated using data from the flowsheet demonstrations agreed reasonably well with the measured rates; although, a discrepancy was observed in the Gd system. The presence of 1 g/L Gd or B in the dissolving solution had about the same effect on the dissolution rate. The predominant Pu valence in the dissolving solution was Pu(IV). The concentration of Pu(VI) was evaluated by UV-visible spectroscopy and was estimated to be significantly less than 1 wt %. The offgas generation rates and H{sub 2} concentrations measured in the offgas from experiments performed using 10 M HNO{sub 3} containing 0.05 M KF, 1.9 g/L Fe and either 1 g/L Gd or B were approximately the same. These data support the conclusion that the presence of either 1 g/L Gd or B had the same general effect on the dissolution rate. The calculated offgas generation during the dissolutions was 0.6 mol offgas/mol of Pu. The H{sub 2} concentration measured in the offgas from the dissolution using Gd as the neutron poison was approximately 0.5 vol %. In the B system, the H{sub 2} ranged from nominally 0.8 to 1 vol % which is about the same as measured in the Gd system within the uncertainty of the analysis. The offgas generation rate for the dissolution performed using 10 M HNO{sub 3} containing 0.03 M KF, 0.5 g/L Gd, and 1.9 g/L Fe was approximately a factor of two less than produced in the other dissolutions; however, the concentration of H{sub 2} measured in the offgas was higher. The adjusted concentration ranged from 2.7 to 8.8 vol % as the dissolution proceeded. Higher concentrations of H{sub 2} occur when the Pu dissolution proceeds by a metal/acid reaction rather than nitrate oxidation. The higher H{sub 2} concentration could be attributed to the reduced activity of the fluoride due to complexation with Pu as the dissolution progressed. Dissolution of Pu metal at 20 °C in 10 M HNO{sub 3} containing 0.05 M KF showed that the Pu metal dissolves slowly without any visible gas generation. As the Pu metal dissolves, it forms a more-dense Pu-bearing solution which sank to the bottom of the dissolution vessel. The dissolved Pu did not form a boundary layer around the sample and failed to distribute homogeneously due to minimal (thermally-induced) mixing. This indicates that in the H-Canyon dissolver insert, the Pu will diffuse out of the insert into the bulk dissolver solution where it will disperse. At 35 °C, the Pu metal dissolved without visible gas generation. However, due to thermal currents caused by maintaining the solution at 35 °C, the dissolved Pu distributed evenly throughout the dissolver solution. It did not form a boundary layer around the sample.« less
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Effect of membrane filtration artifacts on dissolved trace element concentrations
Horowitz, Arthur J.; Elrick, Kent A.; Colberg, Mark R.
1992-01-01
Among environment scientists, the current and almost universally accepted definition of dissolved constituents is an operational one; only those materials which pass through a 0.45-??m membrane filter are considered to be dissolved. Detailed laboratory and field studies on Fe and Al indicate that a number of factors associated with filtration, other than just pore size, can substantially alter 'dissolved' trace element concentrations; these include: filter type, filter diameter, filtration method, volume of sample processed, suspended sediment concentration, suspended sediment grain-size distribution, concentration of colloids and colloidally associated trace elements and concentration of organic matter. As such, reported filtered-water concentrations employing the same pore size filter may not be equal. Filtration artifacts may lead to the production of chemical data that indicate seasonal or annual 'dissolved' chemical trends which do not reflect actual environmental conditions. Further, the development of worldwide averages for various dissolved chemical constituents, the quantification of geochemical cycles, and the determination of short- or long-term environmental chemical trends may be subject to substantial errors, due to filtration artifacts, when data from the same or multiple sources are combined. Finally, filtration effects could have a substantial impact on various regulatory requirements.
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The effect of membrane filtration artifacts on dissolved trace element concentrations
Horowitz, A.J.; Elrick, K.A.; Colberg, M.R.
1992-01-01
Among environment scientists, the current and almost universally accepted definition of dissolved constituents is an operational one only those materials which pass through a 0.45-??m membrane filter are considered to be dissolved. Detailed laboratory and field studies on Fe and Al indicate that a number of factors associated with filtration, other than just pore size, can substantially alter 'dissolved' trace element concentrations; these include: filter type, filter diameter, filtration method, volume of sample processed, suspended sediment concentration, suspended sediment grain-size distribution, concentration of colloids and colloidally-associated trace elements and concentration of organic matter. As such, reported filtered-water concentrations employing the same pore size filter may not be equal. Filtration artifacts may lead to the production of chemical data that indicate seasonal or annual 'dissolved' chemical trends which do not reflect actual environmental conditions. Further, the development of worldwide averages for various dissolved chemical constituents, the quantification of geochemical cycles, and the determination of short- or long-term environmental chemical trends may be subject to substantial errors, due to filtration artifacts, when data from the same or multiple sources are combined. Finally, filtration effects could have a substantial impact on various regulatory requirements.
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Ng, Gene-Hua Crystal.; Bekins, Barbara A.; Cozzarelli, Isabelle M.; Baedecker, Mary Jo; Bennett, Philip C.; Amos, Richard T.; Herkelrath, William N.
2015-01-01
Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O2 and elevated concentrations of Mn2+, Fe2+, CH4, and Ca2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH4 and CO2 gas phases, and sorption of Fe, Mn, and H+. Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.
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Atmospheric hydrogen peroxide and Eoarchean iron formations.
Pecoits, E; Smith, M L; Catling, D C; Philippot, P; Kappler, A; Konhauser, K O
2015-01-01
It is widely accepted that photosynthetic bacteria played a crucial role in Fe(II) oxidation and the precipitation of iron formations (IF) during the Late Archean-Early Paleoproterozoic (2.7-2.4 Ga). It is less clear whether microbes similarly caused the deposition of the oldest IF at ca. 3.8 Ga, which would imply photosynthesis having already evolved by that time. Abiological alternatives, such as the direct oxidation of dissolved Fe(II) by ultraviolet radiation may have occurred, but its importance has been discounted in environments where the injection of high concentrations of dissolved iron directly into the photic zone led to chemical precipitation reactions that overwhelmed photooxidation rates. However, an outstanding possibility remains with respect to photochemical reactions occurring in the atmosphere that might generate hydrogen peroxide (H2 O2 ), a recognized strong oxidant for ferrous iron. Here, we modeled the amount of H2 O2 that could be produced in an Eoarchean atmosphere using updated solar fluxes and plausible CO2 , O2 , and CH4 mixing ratios. Irrespective of the atmospheric simulations, the upper limit of H2 O2 rainout was calculated to be <10(6) molecules cm(-2) s(-1) . Using conservative Fe(III) sedimentation rates predicted for submarine hydrothermal settings in the Eoarchean, we demonstrate that the flux of H2 O2 was insufficient by several orders of magnitude to account for IF deposition (requiring ~10(11) H2 O2 molecules cm(-2) s(-1) ). This finding further constrains the plausible Fe(II) oxidation mechanisms in Eoarchean seawater, leaving, in our opinion, anoxygenic phototrophic Fe(II)-oxidizing micro-organisms the most likely mechanism responsible for Earth's oldest IF. © 2014 John Wiley & Sons Ltd.
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Ng, Gene-Hua Crystal; Bekins, Barbara A.; Cozzarelli, Isabelle M.; Baedecker, Mary Jo; Bennett, Philip C.; Amos, Richard T.
2014-01-01
Secondary water quality impacts can result from a broad range of coupled reactions triggered by primary groundwater contaminants. Data from a crude-oil spill research site near Bemidji, MN provide an ideal test case for investigating the complex interactions controlling secondary impacts, including depleted dissolved oxygen and elevated organic carbon, inorganic carbon, CH4, Mn, Fe, and other dissolved ions. To better understand these secondary impacts, this study began with an extensive data compilation of various data types, comprising aqueous, sediment, gas, and oil phases, covering a 260 m cross-sectional domain over 30 years. Mass balance calculations are used to quantify pathways that control secondary components, by using the data to constrain the sources and sinks for the important redox processes. The results show that oil constituents other than BTEX (benzene, toluene, ethylbenzene, o-, m- and p-xylenes), including n-alkanes and other aromatic compounds, play significant roles in plume evolution and secondary water quality impacts. The analysis underscores previous results on the importance of non-aqueous phases. Over 99.9% of the Fe2+ plume is attenuated by immobilization on sediments as Fe(II) and 85–95% of the carbon biodegradation products are outgassed. Gaps identified in carbon and Fe mass balances and in pH buffering mechanisms are used to formulate a new conceptual model. This new model includes direct out-gassing of CH4 and CO2 from organic carbon biodegradation, dissolution of directly produced CO2, and sorption with H+ exchange to improve pH buffering. The identification of these mechanisms extends understanding of natural attenuation of potential secondary impacts at enhanced reductive dechlorination sites, particularly for reduced Fe plumes, produced CH4, and pH perturbations.
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NASA Astrophysics Data System (ADS)
Ng, G.-H. Crystal; Bekins, Barbara A.; Cozzarelli, Isabelle M.; Baedecker, Mary Jo; Bennett, Philip C.; Amos, Richard T.
2014-08-01
Secondary water quality impacts can result from a broad range of coupled reactions triggered by primary groundwater contaminants. Data from a crude-oil spill research site near Bemidji, MN provide an ideal test case for investigating the complex interactions controlling secondary impacts, including depleted dissolved oxygen and elevated organic carbon, inorganic carbon, CH4, Mn, Fe, and other dissolved ions. To better understand these secondary impacts, this study began with an extensive data compilation of various data types, comprising aqueous, sediment, gas, and oil phases, covering a 260 m cross-sectional domain over 30 years. Mass balance calculations are used to quantify pathways that control secondary components, by using the data to constrain the sources and sinks for the important redox processes. The results show that oil constituents other than BTEX (benzene, toluene, ethylbenzene, o-, m- and p-xylenes), including n-alkanes and other aromatic compounds, play significant roles in plume evolution and secondary water quality impacts. The analysis underscores previous results on the importance of non-aqueous phases. Over 99.9% of the Fe2 + plume is attenuated by immobilization on sediments as Fe(II) and 85-95% of the carbon biodegradation products are outgassed. Gaps identified in carbon and Fe mass balances and in pH buffering mechanisms are used to formulate a new conceptual model. This new model includes direct out-gassing of CH4 and CO2 from organic carbon biodegradation, dissolution of directly produced CO2, and sorption with H+ exchange to improve pH buffering. The identification of these mechanisms extends understanding of natural attenuation of potential secondary impacts at enhanced reductive dechlorination sites, particularly for reduced Fe plumes, produced CH4, and pH perturbations.
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NASA Technical Reports Server (NTRS)
Brown, I. I.; Bryant, D.; Sarkisova, S.; Shen, G.; Garrison, D.; McKay, D. S.
2009-01-01
Of all extant environments, iron-depositing hot springs may constitute the most appropriate natural models (Pierson and Parenteau, 2000) for analysis of the ecophysiology of ancient cyanobacteria (CB) which may have emerged in association with hydrothermal activity (Brown et al., 2007) and elevated levels of environmental Fe (Rouxel et al., 2005). Elevated environmental Fe2+ posed a significant challenge to the first oxygenic phototrophs - CB - because reduced Fe2+ induces toxic Fenton reactions (Wiedenheft et al., 2005). Ancient CB could have also been stressed by occasional migrations from the Fe2+-rich Ocean to the basaltic land which was almost devoid of dissolved Fe2+. That is why the study of the adaptation reactions of siderophilic CB, which inhabit iron-depositing hot springs, to up and down shifts in levels of dissolved Fe may shed light on the paleophysiology of ancient oxygenic prokaryotes. Methods. Siderophilic CB (Brown et al., 2007) were cultivated in media with different concentrations of added Fe3+. In some cases basaltic rocks were used as a source of Fe and trace elements. The processes of Fe mineralization and rock dissolution were studied using TEM, SEM and EDS techniques. Fluorescence spectroscopy was used for checking chlorophyll-protein complexes. Results. It was found that five siderophilic isolates Chroogloeocystis siderophila, JSC-1, JSC-3, JSC-11 and JSC-12 precipitated Fe-bearing phases on the exopolymeric sheaths of their cells if [Fe3+] was approx. 400-600 M (high Fe). Same [Fe3+] was most optimal one for the cultures proliferation rate (Brown et al., 2005; Brown et al., 2007). Higher concentrations of Fe3+ repressed the growth of some siderophilic CB (Brown et al., 2005). No mineralized Fe3+ was observed on the sheath of freshwater isolates Synechocystis sp. PCC 6803 and Phormidium aa. Scanning TEM in conjunction with thin-window energy dispersive X-ray spectroscopy (EDS) revealed intracellular Fe-rich phases within all three isolates studied JSC-1, JSC-3 and JSC-11. The elemental composition of the Fe-rich precipitates indicates P, Fe, and O as the major elements with minor amounts of Al and Ca. It was also found that the PSI:PSII ratio is higher in JSC-1 and JSC-3 isolates than in CB without detectable ability to mineralize Fe. SEM-EDS studies of the interaction of siderophilic cyanobacteria with Fe-rich minerals and rocks revealed, for the first time, their ability to leach ilmenite, olivine, FeS, ZnS and ferrosilicates, perhaps because the cyanobacteria studied can secrete 2-oxo-glutarate and malate which possess chelating properties. The draft of Cyanobacterium JSC-1 is currently being completed. This will help to verify the molecular mechanisms of Fe mineralization and Fe-rich minerals by siderophilic CB. Conclusions. The results obtained suggest that colloidal Fe3+ is transported in CB cytoplasm most likely through ABC-type Fe3+ transport system (Braun et al., 2004). The prevalence of PSI components over PSII in some species of siderophilic CB may indirectly support the Y. Cohen s hypothesis that PSI in cyanobacteria can be involved in Fe2+ oxidation (Cohen, 1984; 1989). The ability of siderophilic CB to mineralize Fe within their cytoplasms could be a protective survival mechanism induced by high levels of [Fe2+] and UV radiation, while the ability to leach Fe-rich minerals could have supported the expansion of ancient CB onto basaltic land.
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Grotti, Marco; Soggia, Francesco; Ardini, Francisco; Magi, Emanuele; Becagli, Silvia; Traversi, Rita; Udisti, Roberto
2015-11-01
From January to December 2010, surface snow samples were collected with monthly resolution at the Concordia station (75°06'S, 123°20'E), on the Antarctic plateau, and analysed for major and trace elements in both dissolved and particulate (i.e. insoluble particles, >0.45 μm) phase. Additional surface snow samples were collected with daily resolution, for the determination of sea-salt sodium and not-sea-salt calcium, in order to support the discussion on the seasonal variations of trace elements. Concentrations of alkaline and alkaline-earth elements were higher in winter (April-October) than in summer (November-March) by a factor of 1.2-3.3, in agreement with the higher concentration of sea-salt atmospheric particles reaching the Antarctic plateau during the winter. Similarly, trace elements were generally higher in winter by a factor of 1.2-1.5, whereas Al and Fe did not show any significant seasonal trend. Partitioning between dissolved and particulate phases did not change with the sampling period, but it depended only on the element: alkaline and alkaline-earth elements, as well as Co, Cu, Mn, Pb and Zn were for the most part (>80%) in the dissolved phase, whereas Al and Fe were mainly associated with the particulate phase (>80%) and Cd, Cr, V were nearly equally distributed between the phases. Finally, the estimated marine and crustal enrichment factors indicated that Cd, Cr, Cu, Pb and Zn have a dominant anthropogenic origin, with a possible contribution from the Concordia station activities. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Hydrothermal sediments are a source of water column Fe and Mn in the Bransfield Strait, Antarctica
NASA Astrophysics Data System (ADS)
Aquilina, Alfred; Homoky, William B.; Hawkes, Jeffrey A.; Lyons, Timothy W.; Mills, Rachel A.
2014-07-01
Short sediment cores were collected from ∼1100 m water depth at the top of Hook Ridge, a submarine volcanic edifice in the Central Basin of the Bransfield Strait, Antarctica, to assess Fe and Mn supply to the water column. Low-temperature hydrothermal fluids advect through these sediments and, in places, subsurface H2S is present at high enough concentrations to support abundant Sclerolinum sp., an infaunal tubeworm that hosts symbiotic thiotrophic bacteria. The water column is fully oxic, and oxygen penetration depths at all sites are 2-5 cmbsf. Pore water Fe and Mn content is high within the subsurface ferruginous zone (max. 565 μmol Fe L-1, >3-7 cmbsf)-14-18 times higher than values measured at a nearby, background site of equivalent water depth. Diffusion and advection of pore waters supply significant Fe and Mn to the surface sediment. Sequential extraction of the sediment demonstrates that there is a significant enrichment in a suite of reactive, authigenic Fe minerals in the upper 0-5 cm of sediment at one site characterised by weathered crusts at the seafloor. At a site with only minor authigenic mineral surface enrichment we infer that leakage of pore water Fe and Mn from the sediment leads to enriched total dissolvable Fe and Mn in bottom waters. An Eh sensor mounted on a towed package mapped a distinct Eh signature above this coring site which is dispersed over several km at the depth of Hook Ridge. We hypothesise that the main mechanism for Fe and Mn efflux from the sediment is breach of the surface oxic layer by the abundant Sclerolinum sp., along with episodic enhancements by physical mixing and resuspension of sediment in this dynamic volcanic environment. We propose that Hook Ridge sediments are an important source of Fe and Mn to the deep waters of the Central Basin in the Bransfield Strait, where concentrations are sustained by the benthic flux, and Fe is stabilised in the water column as either colloidal phases or ligand-bound dissolved species. Entrainment of this water mass into the Drake Passage and thereby the Antarctic Circumpolar Current could provide a significant metal source to this HNLC region of the Southern Ocean if mixing and upwelling occurs before removal of this metal pool to underlying sediments. Sediment-covered volcanic ridges are common within rifted margins and may play a previously overlooked role in the global Fe cycle.
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Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.
2017-01-01
Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.
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NASA Astrophysics Data System (ADS)
Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.
2017-01-01
Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation-reduction reaction.
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NASA Astrophysics Data System (ADS)
Zhong, Weicheng; Mouche, Peter A.; Han, Xiaochun; Heuser, Brent J.; Mandapaka, Kiran K.; Was, Gary S.
2016-03-01
Iron-chromium-aluminum (FeCrAl) coatings deposited on Zircaloy 2 (Zy2) and yttria-stabilized zirconia (YSZ) by magnetron sputtering have been tested with respect to oxidation weight gain in high-temperature steam. In addition, autoclave testing of FeCrAl-coated Zy2 coupons under pressure-temperature-dissolved oxygen coolant conditions representative of a boiling water reactor (BWR) environment has been performed. Four different FeCrAl compositions have been tested in 700 °C steam; compositions that promote alumina formation inhibited oxidation of the underlying Zy2. Parabolic growth kinetics of alumina on FeCrAl-coated Zy2 is quantified via elemental depth profiling. Autoclave testing under normal BWR operating conditions (288 °C, 9.5 MPa with normal water chemistry) up to 20 days demonstrates observable weight gain over uncoated Zy2 simultaneously exposed to the same environment. However, no FeCrAl film degradation was observed. The 900 °C eutectic in binary Fe-Zr is addressed with the FeCrAl-YSZ system.
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Evaluation of In Harmony: Year 1. Interim Report
ERIC Educational Resources Information Center
Lord, Pippa; Sharp, Caroline; Dawson, Anneka; Mehta, Palak; White, Richard; Jeffes, Jennifer
2013-01-01
Arts Council England (ACE) commissioned NFER to undertake the national evaluation of the In Harmony social and music education programme 2012-2015. In Harmony is funded by the Department for Education (DfE) and ACE, and is currently being piloted in six areas. The evaluation is investigating the range and extent of impacts on children, families,…
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Code of Federal Regulations, 2014 CFR
2014-07-01
... producers and importers of denatured fuel ethanol and other oxygenates for use by oxygenate blenders. 80... requirements for producers and importers of denatured fuel ethanol and other oxygenates for use by oxygenate blenders. Beginning January 1, 2017, producers and importers of denatured fuel ethanol (DFE) and other...
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Code of Federal Regulations, 2014 CFR
2014-07-01
... producers and importers of denatured fuel ethanol and other oxygenates designated for use in transportation... requirements for producers and importers of denatured fuel ethanol and other oxygenates designated for use in transportation fuel. Beginning January 1, 2017, producers and importers of denatured fuel ethanol (DFE) or other...
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Earth Science: It's All about the Processes
ERIC Educational Resources Information Center
King, Chris
2013-01-01
Readers of the draft new English primary science curriculum (DfE, 2012) might be concerned to see that there is much more detail on the Earth science content than previously in the United Kingdom. In this article, Chris King, a professor of Earth Science Education at Keele University and Director of the Earth Science Education Unit (ESEU),…
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Cereal Box Design: An Interdisciplinary Graphics Activity
ERIC Educational Resources Information Center
Fitzgerald, Mike; Tsosie, Teri
2012-01-01
The cereal box design activity is intriguing both for its simplicity and the resourcefulness that it can generate in young people. Also, it lends itself to a variety of curriculums. It covers both consumerism and Design for the Environment (DfE) concepts broadly and in depth. The activity introduces a wide range of topics. They include graphic…
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Federal Register 2010, 2011, 2012, 2013, 2014
2013-06-25
... Submitted to OMB for Review and Approval; Comment Request; EPA's Design for the Environment Formulator... Environment Formulator Product Recognition Program'' (EPA ICR No. 2302.02, OMB Control No. 2070-0178), to the..., visit http://www.epa.gov/dockets . Abstract: EPA's Design for the Environment (DfE) Formulator Product...
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Release of dissolved cadmium and sulfur nanoparticles from oxidizing sulfide minerals
Cadmium enrichment (relative to Fe and Zn) in paddy rice grain occurs during the pre-harvest drainage of flooded soil, which causes oxidative dissolution of sulfide minerals present in reduced soil. We investigated this process over a range of environmentally realistic Cdcontain...
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NASA Astrophysics Data System (ADS)
Xie, Kaiyu; Shi, Zhongning; Xu, Junli; Hu, Xianwei; Gao, Bingliang; Wang, Zhaowen
2017-10-01
Aluminothermic reduction-electrolysis using an inert anode process is proposed to extract oxygen and metals from Minnesota Lunar Simulant-1 (MLS-1). Effective aluminothermic reduction between dissolved MLS-1 and dissolved metal aluminum was achieved in cryolite salt media. The product phases obtained by aluminothermic reduction at 980°C for 4 h were Al, Si, and Al5FeSi, while the chemical components were 79.71 mass% aluminum, 12.03 mass% silicon, 5.91 mass% iron, and 2.35 mass% titanium. The cryolite salt containing Al2O3 was subsequently electrolyzed with Fe0.58-Ni0.42 inert anode at 960°C for 4 h. Oxygen was evolved at the anode with an anodic current efficiency of 78.28%. The results demonstrate that this two-step process is remarkably feasible for the extraterrestrial extraction of oxygen and metals. This process will help expand the existing in situ resource utilization methods.
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Seagrass-Mediated Phosphorus and Iron Solubilization in Tropical Sediments
2017-01-01
Tropical seagrasses are nutrient-limited owing to the strong phosphorus fixation capacity of carbonate-rich sediments, yet they form densely vegetated, multispecies meadows in oligotrophic tropical waters. Using a novel combination of high-resolution, two-dimensional chemical imaging of O2, pH, iron, sulfide, calcium, and phosphorus, we found that tropical seagrasses are able to mobilize the essential nutrients iron and phosphorus in their rhizosphere via multiple biogeochemical pathways. We show that tropical seagrasses mobilize phosphorus and iron within their rhizosphere via plant-induced local acidification, leading to dissolution of carbonates and release of phosphate, and via local stimulation of microbial sulfide production, causing reduction of insoluble Fe(III) oxyhydroxides to dissolved Fe(II) with concomitant phosphate release into the rhizosphere porewater. These nutrient mobilization mechanisms have a direct link to seagrass-derived radial O2 loss and secretion of dissolved organic carbon from the below-ground tissue into the rhizosphere. Our demonstration of seagrass-derived rhizospheric phosphorus and iron mobilization explains why seagrasses are widely distributed in oligotrophic tropical waters. PMID:29149570
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NASA Astrophysics Data System (ADS)
Vazquez, A.; Hernández, S.; Rasmussen, C.; Chorover, J.
2010-12-01
Al and Fe oxy-hydroxide minerals have been implicated in dissolved organic matter (DOM) stabilization. DOM solutions from a Pinus ponderosa forest floor (PPDOM) were used to irrigate polypropylene columns, 3.2 cm long by 0.9 cm diameter (total volume 2.0 cm3), that were packed with quartz sand (QS), gibbsite-quartz sand (Al-QS), and goethite-quartz sand (Fe-QS) mixtures. To investigate the mobilization and fractionation of DOM during reactive transport, effluent solutions were characterized by UV-Vis absorbance and excitation-emission matrix (EEM) fluorescence spectroscopies. Magnitude of PPDOM sorption followed the trend Al-QS > Fe-QS > QS during the initial transport. Effluent pH values suggest that ligand exchange is a primary mechanism for PPDOM sorption onto oxy-hydroxide minerals. Low molar absorptivity values were observed in effluent solutions of early pore volumes, indicating preferential mobilization of compounds with low aromatic character. Compounds traditionally characterized by EEM spectroscopy as being more highly humified were favorably absorbed onto the gibbsite and goethite surfaces. Humification index values (HIX) were also correlated with DOM aromaticity. HIX results suggest that the presence of low mass fractions of oxy-hydroxide minerals affect the preferential uptake of high molar mass constituents of PPDOM during reactive transport.
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NASA Astrophysics Data System (ADS)
Soto-Varela, Fátima; Rodríguez-Blanco, M. Luz; Mercedes Taboada-Castro, M.; Taboada-Castro, M. Teresa
2017-12-01
Evaluation of levels and spatial variations of metals in surface waters within a catchment are critical to understanding the extent of land-use impact on the river system. The aims of this study were to investigate the spatial and temporal variations of five dissolved metals (Al, Fe, Mn, Cu and Zn) in surface waters of a small agroforestry catchment (16 km2) in NW Spain. The land uses include mainly forests (65%) and agriculture (pastures: 26%, cultivation: 4%). Stream water samples were collected at four sampling sites distributed along the main course of the Corbeira stream (Galicia, NW Spain) between the headwaters and the catchment outlet. The headwater point can be considered as pristine environment with natural metal concentrations in waters because of the absence of any agricultural activity and limited accessibility. Metal concentrations were determined by ICP-MS. The results showed that metal concentrations were relatively low (Fe > Al > Mn > Zn > Cu), suggesting little influence from agricultural activities in the area. Mn and Zn did not show significant differences between sampling points along main stream, while for Fe and Cu significant differences were found between the headwaters and all other points. Al tended to decrease from the headwaters to the catchment outlet.
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The role of iron and reactive oxygen species in the production of CO2 in arctic soil waters
NASA Astrophysics Data System (ADS)
Trusiak, Adrianna; Treibergs, Lija A.; Kling, George W.; Cory, Rose M.
2018-03-01
Hydroxyl radical (radOH) is a highly reactive oxidant of dissolved organic carbon (DOC) in the environment. radOH production in the dark was observed through iron and DOC mediated Fenton reactions in natural environments. Specifically, when dissolved oxygen (O2) was added to low oxygen and anoxic soil waters in arctic Alaska, radOH was produced in proportion to the concentrations of reduced iron (Fe(II)) and DOC. Here we demonstrate that Fe(II) was the main electron donor to O2 to produce radOH. In addition to quantifying radOH production, hydrogen peroxide (H2O2) was detected in soil waters as a likely intermediate in radOH production from oxidation of Fe(II). For the first time in natural systems we detected carbon dioxide (CO2) production from radOH oxidation of DOC. More than half of the arctic soil waters tested showed production of CO2 under conditions conducive for production of radOH. Findings from this study strongly suggest that DOC is the main sink for radOH, and that radOH can oxidize DOC to yield CO2. Thus, this iron-mediated, dark chemical oxidation of DOC may be an important component of the arctic carbon cycle.
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Gabka, Grzegorz; Bujak, Piotr; Ostrowski, Andrzej; Tomaszewski, Waldemar; Lisowski, Wojciech; Sobczak, Janusz W; Pron, Adam
2016-07-05
Cu-Fe-S nanocrystals exhibiting a strong localized surface plasmon resonance (LSPR) effect were synthesized for the first time. The elaborated reproducible preparation procedure involved copper(II) oleate, iron(III) stearate, and sulfur powder dissolved in oleylamine (OLA) as precursors. The wavelength of the plasmonic resonance maximum could be tuned by changing the Cu/Fe ratio in the resulting nanocrystals, being the most energetic for the 1:1 ratio (486 nm) and undergoing a bathochromic shift to ca. 1200 nm with an increase to 6:1. LSPR could also be observed in nanocrystals prepared from the same metal precursors and sulfur powder dissolved in 1-octadecene (ODE), provided that the sulfur precursor was taken in excess. Detailed analysis of the reaction mixture by chromatographic techniques, supplemented by mass spectrometry and (1)H NMR spectroscopy enabled the identification of the true chemical nature of the sulfur precursor in S/OLA, namely, (C18H35NH3(+))(C18H35NH-S8(-)), a reactive product of the reduction of elemental sulfur by the amine groups of OLA. In the case of the S/ODE precursor, the true precursors are much less reactive primary or secondary thioethers and dialkyl polysulfides.
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Balistrieri, L.S.; Seal, R.R.; Piatak, N.M.; Paul, B.
2007-01-01
The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 ??g/L in the dynamic mixing and reaction zone that is downstream of the river's confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO4 concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates. The uptake of dissolved metals by aquatic organisms is dependent on the aqueous speciation of the metals and kinetics of complexation reactions between metals, ligands and solid surfaces. Dissolved speciation of Cd, Cu, Ni and Zn in the mixing and reaction zone is assessed using the diffusive gradients in thin films (DGT) technique and results of speciation calculations using the Biotic Ligand Model (BLM). Data from open and restricted pore DGT units indicate that almost all dissolved metal species are inorganic and that aqueous labile or DGT available metal concentrations are generally equal to total dissolved concentrations in the mixing zone. Exceptions occur when labile metal concentrations are underestimated due to competition between H+ and metal ions for Chelex-100 binding sites in the DGT units at low pH values. Calculations using the BLM indicate that dissolved Cd and Zn species in the mixing and reaction zone are predominantly inorganic, which is consistent with the DGT results. Although the DGT method indicates that the majority of aqueous Cu species are inorganic, BLM calculations indicate that dissolved Cu is inorganic at pH 5.5. Integrated dissolved labile concentrations of Cd, Cu and Zn in the mixing and reaction zone are compared to calculated acute toxicity concentrations (LC50 values) for fathead minnows (Pimephales promelas) (Cd, Cu and Zn) and water fleas (Ceriodaphnia dubia) (Cd and Cu) using the BLM, and to national recommended water quality criteria [i.e., criteria maximum concentration (CMC) and criterion continuous concentration (CCC)]. Observed labile concentrations of Cd and Zn are below LC50 values and CMC for Cd, but above CCC and CMC for Zn at sites <30 m downstream of the confluence. In contrast, labile Cu concentrations exceed LC50 values for the organisms as well as CCC and CMC at sites <30 m downstream of the confluence. These results suggest that environmental conditions at sites closest to the confluence of the river and acid-mine drainage should not support healthy aquatic organisms. ?? 2007 Elsevier Ltd. All rights reserved.
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Shaheen, Sabry M; Frohne, Tina; White, John R; DeLaune, Ron D; Rinklebe, Jörg
2017-01-15
Studies about the mobilization of potentially toxic elements (PTEs) in deltaic soils can be challenging, provide critical information on assessing the potential risk and fate of these elements and for sustainable management of these soils. The impact of redox potential (E H ), pH, iron (Fe), manganese (Mn), sulfate (SO 4 2- ), chloride (Cl - ), aliphatic dissolved organic carbon (DOC), and aromatic dissolved organic carbon (DAC) on the mobilization of copper (Cu), selenium (Se), and zinc (Zn) was studied in two soils collected from the Nile and Mississippi Rivers deltaic plains focused on increasing our understanding of the fate of these toxic elements. Soils were exposed to a range of redox conditions stepwise from reducing to oxidizing soil conditions using an automated biogeochemical microcosm apparatus. Concentrations of DOC and Fe were high under reducing conditions as compared to oxidizing conditions in both soils. The proportion of DAC in relation to DOC in solution (aromaticity) was high in the Nile Delta soil (NDS) and low in the Mississippi Delta soil (MDS) under oxidizing conditions. Mobilization of Cu was low under reducing conditions in both soils which was likely caused by sulfide precipitation and as a result of reduction of Cu 2+ to Cu 1+ . Mobilization of Se was high under low E H in both soils. Release of Se was positively correlated with DOC, Fe, Mn, and SO 4 2- in the NDS, and with Fe in the MDS. Mobilization of Zn showed negative correlations with E H and pH in the NDS while these correlations were non-significant in the MDS. The release dynamics of dissolved Zn could be governed mainly by the chemistry of Fe and Mn in the NDS and by the chemistry of Mn in the MDS. Our findings suggest that a release of Se and Zn occurs under anaerobic conditions, while aerobic conditions favor the release of Cu in both soils. In conclusion, the release of Cu, Se, and Zn under different reducing and oxidizing conditions in deltaic wetland soils should be taken into account due to increased mobilization and the potential environmental risks associated with food security in utilizing these soils for flooded agricultural and fisheries systems. Copyright © 2016 Elsevier Ltd. All rights reserved.
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O'Reilly, S Erin; Watkins, Janet; Furukawa, Yoko
2005-01-01
Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III) respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred regardless of the extent of microbial Fe(III) reduction in all of our experimental systems, including those that contained heat-killed bacteria and those in which O2, rather than Fe(III), was the primary terminal electron acceptor. The solid alteration products observed under transmission electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III) species even in the systems in which Fe(III) was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial respiration of Fe(III) in our laboratory systems proceeded through the following: (1) alteration of NAu-1 and concurrent release of Fe(III) from the octahedral sheets of NAu-1; and (2) subsequent microbial respiration of Fe(III).
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Influence of Magnetite Stoichiometry on the Binding of Emerging Organic Contaminants.
Cheng, Wei; Marsac, Rémi; Hanna, Khalil
2018-01-16
While the magnetite stoichiometry (i.e., Fe(II)/Fe(III) ratio) has been extensively studied for the reductive transformation of chlorinated or nitroaromatic compounds, no work exists examining the influence of stoichiometry of magnetite on its binding properties. This study, for the first time, demonstrates that the stoichiometry strongly affects the capacity of magnetite to bind not only quinolone antibiotics such as nalidixic acid (NA) and flumequine (FLU), but also salicylic acid (SA), natural organic matter (humic acid, HA), and dissolved silicates. Fe(II)-amendment of nonstoichiometric magnetite (Fe(II)/Fe(III) = 0.40) led to similar sorbed amounts of NA, FLU, SA, silicates or HA as compared to the stoichiometric magnetite (i.e., Fe(II)/Fe(III) = 0.50). At any pH between 6 and 10, all magnetites exhibiting similar Fe(II)/Fe(III) ratio in the solid phase showed similar adsorption properties for NA or FLU. This enhancement in binding capability of magnetite for NA is still observed in the presence of environmentally relevant ligands (e.g., 10 mg L -1 of HA or 100 μM of silicates). Using surface complexation modeling, it was shown that the NA-magnetite complexation constant does not vary with Fe(II)/Fe(III) between 0.24 and 0.40, but increases by 8 orders of magnitude when Fe(II)/Fe(III) increases from 0.40 to 0.50.
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Xiong, Zhaokun; Lai, Bo; Yang, Ping; Zhou, Yuexi; Wang, Juling; Fang, Shuping
2015-10-30
In order to further compare the degradation capacity of Fe(0) and Fe/Cu bimetallic system under different aeration conditions, the mineralization of PNP under different aeration conditions has been investigated thoroughly. The results show that the removal of PNP by Fe(0) or Fe/Cu system followed the pseudo-first-order reaction kinetics. Under the optimal conditions, the COD removal efficiencies obtained through Fe(0) or Fe/Cu system under different aeration conditions followed the trend that Fe/Cu (air)>Fe/Cu (N2: 0-30 min, air: 30-120 min)>control-Fe (air)>Fe/Cu (without aeration)>Fe/Cu (N2)>control-Fe (N2). It revealed that dissolved oxygen (DO) could improve the mineralization of PNP, and Cu could enhance the reactivity of Fe(0). In addition, the degradation of PNP was further analyzed by using UV-vis, FTIR and GC/MS, and the results suggest that Fe/Cu bimetallic system with air aeration could completely break the benzene ring and NO2 structure of PNP and could generate the nontoxic and biodegradable intermediate products. Meanwhile, most of these intermediate products were further mineralized into CO2 and H2O, which brought about a high COD removal efficiency (83.8%). Therefore, Fe/Cu bimetallic system with air aeration would be a promising process for toxic refractory industry wastewater. Copyright © 2015 Elsevier B.V. All rights reserved.
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Ferrous and ferric ion generation during iron electrocoagulation.
Lakshmanan, Divagar; Clifford, Dennis A; Samanta, Gautam
2009-05-15
Our research on arsenate removal by iron electrocoagulation (EC) produced highly variable results, which appeared to be due to Fe2+ generation without subsequent oxidation to Fe3+. Because the environmental technology literature is contradictory with regard to the generation of ferric or ferrous ions during EC, the objective of this research was to establish the iron species generated during EC with iron anodes. Experimental results demonstrated that Fe2+, not Fe3+, was produced at the iron anode. Theoretical current efficiency was attained based on Fe2+ production with a clean iron rod, regardless of current, dissolved-oxygen (DO) level, or pH (6.5-8.5). The Fe2+ remaining after generation and mixing decreased with increasing pH and DO concentration due to rapid oxidation to Fe3+. At pH 8.5, Fe2+ was completely oxidized, which resulted in the desired Fe(OH)3(s)/ FeOOH(s), whereas, at pH 6.5 and 7.5, incomplete oxidation was observed, resulting in a mixture of soluble Fe2+ and insoluble Fe(OH)3(s)/FeOOH(s). When compared with Fe2+ chemical coagulation, a transient pH increase during EC led to faster Fe2+ oxidation. In summary, for EC in the pH 6.5-7.5 range and at low DO conditions, there is a likelihood of soluble Fe2+ species passing through a subsequentfiltration process resulting in secondary contamination and inefficient contaminant removals.
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Omanović, Dario; Pižeta, Ivanka; Vukosav, Petra; Kovács, Elza; Frančišković-Bilinski, Stanislav; Tamás, János
2015-04-01
The distribution and speciation of elements along a stream subjected to neutralised acid mine drainage (NAMD) effluent waters (Mátra Mountain, Hungary; Toka stream) were studied by a multi-methodological approach: dissolved and particulate fractions of elements were determined by HR-ICPMS, whereas speciation was carried out by DGT, supported by speciation modelling performed by Visual MINTEQ. Before the NAMD discharge, the Toka is considered as a pristine stream, with averages of dissolved concentrations of elements lower than world averages. A considerable increase of element concentrations caused by effluent water inflow is followed by a sharp or gradual concentration decrease. A large difference between total and dissolved concentrations was found for Fe, Al, Pb, Cu, Zn and As in effluent water and at the first downstream site, with high correlation factors between elements in particulate fraction, indicating their common behaviour, governed by the formation of ferri(hydr)oxides (co)precipitates. In-situ speciation by the DGT technique revealed that Zn, Cd, Ni, Co, Mn and U were predominantly present as a labile, potentially bioavailable fraction (>90%). The formation of strong complexes with dissolved organic matter (DOM) resulted in a relatively low DGT-labile concentration of Cu (42%), while low DGT-labile concentrations of Fe (5%) and Pb (12%) were presumably caused by their existence in colloidal (particulate) fraction which is not accessible to DGT. Except for Fe and Pb, a very good agreement between DGT-labile concentrations and those predicted by the applied speciation model was obtained, with an average correlation factor of 0.96. This study showed that the in-situ DGT technique in combination with model-predicted speciation and classical analysis of samples could provide a reasonable set of data for the assessment of the water quality status (WQS), as well as for the more general study of overall behaviour of the elements in natural waters subjected to high element loads. Copyright © 2014 Elsevier B.V. All rights reserved.
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Cr(VI) Sorption by Nanosized FeS-Coated Sand
NASA Astrophysics Data System (ADS)
Park, M.; Jeong, H. Y.; Lee, S.; Kang, N.; Kim, K. H.; Choi, H. J.
2015-12-01
Cr(VI) sorption experiments were conducted as a function of pH (4.7, 7.0 and 9.7) using nanosized FeS-coated sand under anoxic environments. Under the experimental conditions, the sand used, with the FeS content of 0.068 mmol per 1 g sand, completely reduced the initially added Cr(VI) to Cr(III) over the pH range examined. The sorption of the once-reduced Cr(III) varied greatly with the solution pH. By the solution-phase analysis, significant amounts of Cr(III) remained as dissolved species at pH 4.7. On the other hands, dissolved Cr was below the detection limit (0.2 μM) at pH 7.0 and 9.7, indicating the greater sorption of Cr(III) at neutral to basic pH than acidic pH. From Cr-K edge X-ray absorption spectroscopy (XAS) analysis of the solid products, the sorbed Cr was shown to be present predominantly as trivalent state in all samples. Regardless of pH, the second coordination shell around Cr (i.e., the Cr-Cr(Fe) shell) was shown to be located at ~2.6 Å, which was far shorter than those in Cr(III)-bearing model compounds such as Cr(OH)3(s) and [Cr, Fe](OH)3(s). Furthermore, the coordination numbers of the second and third shells in the sorption samples (N = 0.7-1.8) were much lower than those in Cr(OH)3(s) and [Cr, Fe](OH)3(s). Taken together, the sorption of the once-reduced Cr(III) was likely to occur via surface-mediated processes (e.g., surface complexation and/or surface precipitation) rather than the bulk-phase precipitation. Financial support was provided by the "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).
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NASA Astrophysics Data System (ADS)
Hettiarachchi, E.; Rubasinghege, G. R. S.; Reynolds, R. L.; Goldstein, H. L.; Moskowitz, B. M.
2017-12-01
Iron is one of the important trace elements for the life. Though it is the fourth most abundant element in the terrestrial crust, given higher pH ( 8.5) in the ocean, the direct dissolution of iron from the Earth crust is limited. Despite this limitation, ocean contains about 2 nM of dissolved iron that is 20-fold greater. Therefore, it is hypothesized most iron comes to the ocean via atmosphere, and dissolution occurs in the acidic atmospheric environments. The current work focuses on the effect of minerology on atmospheric processing of Fe-containing mineral dust using four authentic dust samples, collected from different parts of the world, along with three model systems, hematite (α-Fe2O3), magnetite (Fe3O4) and ilmenite (FeTiO3). Here, spectroscopic methods are combined with batch reactor studies to investigate total iron dissolution and speciation, with a specific focus on source material i.e. particle size, mineralogy, and environmental conditions, i.e. pH, temperature and solar flux. Our data suggests that the presence of Ti metal enhances the dissolution of iron regardless the total %Fe in the mineral. The surface area normalized total iron dissolution in ilmenite, under the dark conditions, in the presence of nitric acid (HNO3) is 3-fold higher than that of hematite. In authentic samples, similar effects were observed for samples containing %Ti. Further, 74% of the dissolved iron in ilmenite remained as Fe(II), bioavailable iron, whereas it was only 60% for magnetite and 8% for hematite. In this study, these results were used to interpret similar trends observed for authentic dust samples with high magnetite content. Thus, the findings of the current study highlight important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.
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Nanocompounds of iron and zinc: their potential in nutrition
NASA Astrophysics Data System (ADS)
Zimmermann, Michael B.; Hilty, Florentine M.
2011-06-01
Recent studies suggest nanostructured oxides and phosphates of Fe and atomically mixed Fe/Zn may be useful for nutritional applications. These compounds may have several advantages over existing fortificants, such as ferrous sulfate (FeSO4), NaFeEDTA and electrolytic iron. Because of their very low solubility and formation of soft agglomerates of micron size at neutral pH as well as their light native color, they tend to be less reactive in difficult-to-fortify foods and thus have superior sensory performance. At gastric pH the soft agglomerates break up and the Fe compounds rapidly and completely dissolve due to their very high surface area. This results in in vitro solubility and in vivo bioavailability comparable to FeSO4. Doping with Mg and/or Ca may increase solubility and improve sensory characteristics by lightening color. Feeding the nanostructured compounds at 150-400 µg Fe day-1 for 15 days to weanling rats in two studies did not induce measurable histological or biochemical adverse effects. No significant Fe was detected in the submucosa of the gastrointestinal tract or lymphatic tissues, suggesting that the nanosized Fe is absorbed through usual non-heme Fe absorption pathways. Thus, these novel compounds show promise as food fortificants or supplements.
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Iron-sulfur mineralogy of Mars - Magmatic evolution and chemical weathering products
NASA Technical Reports Server (NTRS)
Burns, Roger G.; Fisher, Duncan S.
1990-01-01
Models are developed for the magmatic evolution and the oxidative weathering of sulfide minerals on Mars, based on petrogenetic associations among komatiitic rock types, Viking geochemical data, SNC meteorites, and terrestrial Fi-Ni deposits. The weathering model was tested by exposing komatiitic pyrrhotites and olivines to sulfuric acid solutions, with or without dissolved ferric iron, and identifying the reaction products by Moessbauer spectroscopy. The results suggest that, on Mars, acidic groundwater has induced oxidative weathering of pyrrhotite, yielding FeS2 and then FeOOH.
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NASA Astrophysics Data System (ADS)
Sodano, Marcella; Lerda, Cristina; Martin, Maria; Celi, Luisella; Said-Pullicino, Daniel
2016-04-01
The dissimilatory reduction of Fe oxides is the main organic C-consuming process in paddy soils under anoxic conditions. The contribution of Fe(III) reduction to anaerobic C mineralization depends on many factors, but most importantly on the bioavailability of labile organic matter and a reducible Fe pool as electron donors and acceptors, respectively. On the other hand, the strong affinity of these minerals for organic matter and their capability of protecting it against microbial decomposition is well known. Natural Fe oxides in these soils may therefore play a key role in determining the C source/sink functions of these agro-ecosystems. Apart from contributing to C stabilization, the interaction between Fe oxides and dissolved organic C (DOC) may influence the structure and reactivity of these natural oxides, and selectively influence the chemical properties of DOC. Indeed, Fe-DOC associations may not only reduce the availability of DOC, but may also limit the microbial reduction of Fe oxides under anoxic conditions. In fact, the accessibility of these minerals to microorganisms, extracellular enzymes, redox active shuttling compound or reducing agents may be impeded by the presence of sorbed organic matter. In soils that are regularly subjected to fluctuations in redox conditions the interaction between DOC and Fe oxides may not only involve organic coatings on mineral surfaces, but also Fe-DOC coprecipitates that form during the rapid oxidation of soil solutions containing important amounts of DOC and Fe(II). However, little is known on how these processes influence DOC retention, and the structure and subsequent reducibility of these Fe-DOC associations. We hypothesized that the nature and extent of the interaction between DOC and Fe oxides may influence the accessibility of the bioavailable Fe pool and consequently its reducibility. We tested this hypothesis by synthesizing a series of Fe-DOC systems with increasing C:Fe ratios prepared by either surface adsorption or coprecipitation, DOC was obtained by incubating a suspension of rice straw in water (straw-solution ratio of 1:30) under oxic conditions at 25° C for 30 days to simulate the decomposition of rice straw in the field. Increasing amounts of DOC were equilibrated (pH = 6) with a known mass of ferrihydrite (initial molar C:Fe ratios of 1, 5 and 10) to obtain surface coated Fe-DOC systems with increasing C loading. On the other hand, coprecipitates with similar initial C:Fe ratios were obtained by oxidation of a Fe(II) solution in the presence of increasing amounts of DOC at pH = 6. A natural Fe-DOC coprecipitate was also obtained by in situ sampling of a paddy soil solution from the topsoil during a cropping season, and subsequent oxidation in the laboratory. The surface and chemical properties of all substrates were subsequently evaluated and compared. We hereby present the first results of the influence of adsorption vs coprecipitation on the selective retention of DOC, structure and surface charge, as well as their susceptibility to chemical reduction with ascorbic acid.
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NASA Astrophysics Data System (ADS)
Poigner, H.; Monien, D.; Monien, P.; Kriews, M.; Brumsack, H.-J.; Wilhelms-Dick, D.; Abele, D.
2012-04-01
Trace metals in bivalve carbonate shells are frequently used as environmental or paleoclimate proxies. Carbonate mineralogy and animals' physiology affect the incorporation of elements from different environmental sources into bivalve shells. Generally, metals from particulate matter are assimilated via the digestive tract; whereas dissolved metals are absorbed via gills. Therefore, measurements of element concentrations deposited in the shell matrix do not necessarily allow inference with respect to the assimilation pathways. In this study, we used element ratios between digestive gland (DG) and gills (cDG/cGill) of the Circum-Antarctic clam Laternula elliptica to identify predominating assimilation pathways and potential sources of bio-available metals. This normalization between tissues of each individual eliminates the effects of individual age and physiological condition (e.g. accumulation over lifetime, metabolic activity) on metal assimilation. These effects also minimize the reproducibility, when absolute element concentrations are compared between individuals from different locations. Therefore, an additional normalization is required. We favored "ellipsoid shell volume" over shell length or soft tissue weight as more conservative approximation for intra- and intersite comparisons. Metal concentrations in DG, gills, and hemolymph of the bivalve L. elliptica, collected at Potter Cove (King George Island, Antarctic Peninsula), were analyzed by means of inductively coupled plasma - optical emission spectroscopy and mass spectrometry after total acid digestion. The element ratios (cDG/cGill) indicate a predominant assimilation of Al, Ca, Fe, K, Mn, and Mg from the dissolved phase. These high Al and Fe concentrations in gill tissues and hemolymph are in contrast to the low solubility of Al and Fe in seawater. But high dissolved Fe concentrations in pore waters (up to 1400 μg L-1 due to suboxic sediment conditions) and glacial melt waters enriched in dissolved Al (of approx. 54 μg L-1 due to weathering processes) with respect to seawater concentrations (5.4-13.5 μg L-1) are likely bio-available sources at Potter Cove. In contrast, Cd, Cu, and Sr are mainly assimilated via the digestion of particulates. Since most studies on metal incorporation into bivalve shells have provided mathematical correlations to environmental data, this proxy-based approach provides a more causal relationship between sources and assimilation pathways. It improves the interpretation of element variations (if independent from shell mineralogy) in bivalve shells, especially, where a full characterization of the biogeochemical environment of the bivalves is lacking.
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Low temperature hydrogen production during experimental hydration of partially-serpentinized dunite
NASA Astrophysics Data System (ADS)
Miller, Hannah M.; Mayhew, Lisa E.; Ellison, Eric T.; Kelemen, Peter; Kubo, Mike; Templeton, Alexis S.
2017-07-01
Dissolved hydrogen is common in mafic and ultramafic aquifers; however, the water/rock reactions that give rise to hydrogen production at near-surface temperatures are enigmatic. Similarly, mineral hydration experiments have not yet unequivocally demonstrated whether H2 can be produced at low-temperatures at significant rates from reaction of aqueous fluids with basalts and peridotites for prolonged amounts of time. We conducted laboratory-based water/rock reactions between partially serpentinized Oman dunite and a simulated Oman rainwater (RW) media, as well as a simulated seawater (SW) media, to quantify H2 generation rates at 100 °C. Throughout more than 9 months of water/rock reaction, extensive hydrogen production and consumption were observed in RW and SW media. In the first 24 h of reaction in anoxic fluids containing only dissolved N2 and CO2, the room-temperature pH in both RW and SW media increased from 6.5 to ∼9, and the average pH then remained relatively constant at pH 8.5 (±0.5 pH) for the duration of the experiments. We also measured some of the highest hydrogen concentrations observed in experimental low-temperature serpentinization reactions. The maximum measured H2 concentrations in SW media were 470 nmol H2 per g mineral after ∼3 months, while RW media H2 concentrations reached 280 nmol/g H2 after ∼3 months. After reaching micromolar dissolved H2(aq), the H2 concentrations notably declined, and CO2 was almost fully consumed. We measured the formation of formate (up to 98 μM) and acetate (up to 91 μM) associated with a drawdown of H2 and CO2 in the experiments. No CH4 or carbonate formation was observed. To identify reactions giving rise to low-temperature hydrogen production, the mineralogy and oxidation state of the Fe-bearing species in the dunite were extensively characterized before and after reaction using Raman spectroscopy, Quantitative Evaluation of Minerals by SCANing electron microscopy (QEMSCAN), powder X-ray diffraction (XRD), magnetic susceptibility, scanning electron microscopy (SEM), and Fe K-edge X-ray absorption near edge structure (XANES) spectroscopic techniques. The mineralogy of the solid starting material was dominated by olivine and serpentine with minor brucite, pyroxene and spinel. After reaction, additional serpentine and magnetite could be detected as reaction products, and pre-existing brucite was consumed. No changes were observed in the abundance or grain sizes of olivine or pyroxene. Thus, we propose that the destabilization of Fe(II)-bearing brucite and the subsequent oxidation of the aqueous Fe(II) to form magnetite and Fe(III)-rich serpentine give rise to H2 production at 100 °C. This work demonstrates that dissolved hydrogen and low molecular weight organic acids can be produced by the reaction of labile Fe(II)-bearing minerals generated during a prior stage of water/rock reactions. In particular, progressive alteration of partially-serpentinized peridotites containing brucite may generate sufficient electron donors to fuel in-situ subsurface microbial activity.
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Complexation of Arsenite with Humic Acid in the Presence of Ferric Iron
Liu, Guangliang; Fernandez, Aymara; Cai, Yong
2011-01-01
In the presence of iron (Fe), dissolved organic matter (DOM) may bind considerable amounts of arsenic (As), through formation of Fe-bridged As-Fe-DOM complexes and surface complexation of As on DOM-stabilized Fe-colloids (collectively referred to as As-Fe-DOM complexation). However, direct (e.g., chromatographic and spectroscopic) evidence and fundamental kinetic and stability constants have been rarely reported for this As-Fe-DOM complexation. Using a size exclusion chromatography (SEC)-UV-inductively coupled plasma mass spectrometry (ICP-MS) technique, arsenite (AsIII)-Fe-DOM complexation was investigated after adding AsIII into the priorly prepared Fe-DOM. A series of evidence, including coelution of As, Fe, and DOM from the SEC column and coretention of As, Fe, and DOM by 3 kDa MWCO centrifugal filtration membrane, demonstrated the occurrence of AsIII-Fe-DOM complexation. The kinetic data of AsIII-Fe-DOM complexation were well described by a pseudo-first order rate equation (R2 = 0.95), with the rate constant (k′) being 0.17±0.04 1/h. Stability of AsIII-Fe-DOM complexation was characterized by apparent stability constant (Ks) derived from two-site ligand binding model, with log Ks ranging from 4.4±0.2 to 5.6±0.4. Considering the kinetics (within hours) and stability (similar to typical metal-humates) of AsIII-Fe-DOM complexation, this complexation needs to be included when evaluating As mobility in Fe and DOM rich environments. PMID:21322632
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Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas
NASA Astrophysics Data System (ADS)
Lange, R. A.; Waters, L.
2014-12-01
The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels in these 14 rhyolitic magmas, no effect is detected. Therefore, it can be robustly concluded that degassing of substantial amounts of the H2O component (≤ 6.5 wt%), by itself, does not induce oxidation in erupted magmas, particularly those more iron-rich than rhyolites (e.g., arc basalts).
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Organic Exudates Enhance Iron Bioavailability to Trichodesmium (IMS101) by Modifying Fe Speciation
NASA Astrophysics Data System (ADS)
Tohidi Farid, H.; Rose, A.; Schulz, K.
2016-02-01
Although ferrous iron (Fe (II)) is believed to be the most readily absorbed form of Fe by cells, under alkaline and oxygenated conditions typical of marine environments, the thermodynamically stable Fe(III) state dominates. In marine environments, this Fe(III) is primarily presents as organic Fe(III)L complexes whose bioavailability is highly variable. However, it has been demonstrated that some eukaryotic marine algae are able to release organic ligands into their surrounding environments that change Fe bioavailability through complexation and/or redox reactions. Nevertheless, it is unclear how Fe(II) oxidation and Fe(III) reduction rates might be modified by these exudates and how this might increase or decrease iron bioavailability to microorganisms. Here, the role of natural organic ligands excreted by the cyanobacterium Trichodesmium erythraeum on the oxidation kinetics of Fe(II) was studied using the luminol chemiluminescence technique. The oxidation kinetics of Fe(II) were examined at nanomolar Fe concentrations in presence of different concentrations of EDTA and dissolved organic carbon exuded by Trichodesmium cells. The results indicated that an increase in the concentration of exuded organic matter, and consequently L:Fe(II) ratio, resulted in decreasing rates of Fe(II) oxidation by oxygen, primarily due to formation of Fe(II) complexes. Moreover, the results demonstrated that the exudates from Trichodesmium may be able to reduce Fe(III) to the more bioavailable Fe(II) state under some circumstances. This study therefore supports the ability of microorganisms to manipulate Fe bioavailability by releasing organic compounds into the extracellular environment that retard Fe(II) oxidation rates or reducing Fe(III) species to Fe(II). It also provides new insight into the potential mechanism(s) by which Trichdesmium may acquire Fe under conditions where Fe bioavailability is otherwise limited.
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Taylor, Howard E.; Antweiler, Ronald C.; Brinton, Terry I.; Roth, David A.; Moody, John A.
1994-01-01
Extensive flooding in the upper Mississippi River Basin during summer 1993 had a significant effect on the water quality of the Mississippi River. To evaluate the change in temporal distribution and transport of dissolved constituents in the Mississippi River, six water samples were collected by a discharge-weighted method from July through September 1993 near Thebes, Illinois. Sampling at this location provided water-quality information from the upper Mississippi, the Missouri, and the Illinois River Basins. Dissolved major constituents that were analyzed in each of the samples included bicarbonate, calcium (Ca), carbonate (C03), chloride (Cl), dissolved organic carbon, magnesium (Mg), potassium (K), silica NOD, sodium (Na), and sulfate (S04). Dissolved nutrients included ammonium ion (NH4), nitrate (N03), nitrite (N02), and orthophosphate (P04) . Dissolved trace elements included aluminum (Al), arsenic (As), barium (Ba), boron (B), beryllium (Be), bromide (Br), cadmium (Cd), chromium (Cr), cobalt, (Co), copper (Cu), fluoride (F), iron (Fe), lead, lithium (Li), manganese (Mn), mercury (Hg), molybdenum (Mo), nickel (Ni), strontium (Sr), thallium, uranium (U), vanadium (V), and zinc (Zn). Other physical properties of water that were measured included specific conductance, pH and suspended-sediment concentration (particle size, less than 63 micrometers). Results of this study indicated that large quantities of dissolved constituents were transported through the river system. Generally, pH, alkalinity, and specific conductance and the concentrations of B, Br, Ca, Cl, Cr, K, Li, Mg, Mo, Na, S04, Sr, U, and V increased as water discharge decreased, while concentrations of F, Hg, and suspended sediment sharply decreased as water discharge decreased after the crest of the flood. Concentrations of other constituents, such as Al, As, Ba, Be, Co, Cu, Ni, N03, N02, NH4, P04, and Si02, varied with time as discharge decreased after the crest of the flood. For most constituents, the load transported during floods generally is much greater than that transported during low-flow conditions. How ever, for Cd, Cr, Fe, Mn, V, and Zn, loads increased substantially as water discharge decreased after the crest of the flood.
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Diaz, X.; Johnson, W.P.; Fernandez, D.; Naftz, D.L.
2009-01-01
The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.
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Usher, Courtney R; Cleveland, Curtis A; Strongin, Daniel R; Schoonen, Martin A
2004-11-01
FeS2 (pyrite) is known to react with water and dissolved molecular oxygen to form sulfate and iron oxyhydroxides. This process plays a large role in the environmentally damaging phenomenon known as acid mine drainage. An outstanding scientific issue has been whether the oxygen in the sulfate and oxyhydroxide product was derived from water and/or dissolved oxygen. By monitoring the reaction in situ with horizontal attenuated total reflectance infrared spectroscopy, it was found that when using 18O isotopically substituted water, the majority of the infrared absorbance due to sulfate product red-shifted approximately 70 cm(-1) relative to the absorbance of sulfate using H(2)16O as a reactant. Bands corresponding to the iron oxyhydroxide product did not shift. These results indicate water as the primary source of oxygen in the sulfate product, while the oxygen atoms in the iron oxyhydroxide product are obtained from dissolved molecular oxygen.
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Sekaran, G; Karthikeyan, S; Boopathy, R; Maharaja, P; Gupta, V K; Anandan, C
2014-01-01
The rice-husk-based mesoporous activated carbon (MAC) used in this study was precarbonized and activated using phosphoric acid. N2 adsorption/desorption isotherm, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy and scanning electron microscopy, transmission electron microscopy, (29)Si-NMR spectroscopy, and diffuse reflectance spectroscopy were used to characterize the MAC. The tannery wastewater carrying high total dissolved solids (TDS) discharged from leather industry lacks biodegradability despite the presence of dissolved protein. This paper demonstrates the application of free electron-rich MAC as heterogeneous catalyst along with Fenton reagent for the oxidation of persistence organic compounds in high TDS wastewater. The heterogeneous Fenton oxidation of the pretreated wastewater at optimum pH (3.5), H2O2 (4 mmol/L), FeSO4[Symbol: see text]7H2O (0.2 mmol/L), and time (4 h) removed chemical oxygen demand, biochemical oxygen demand, total organic carbon and dissolved protein by 86, 91, 83, and 90%, respectively.
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Simmler, Michael; Bommer, Jérôme; Frischknecht, Sarah; Christl, Iso; Kotsev, Tsvetan; Kretzschmar, Ruben
2017-12-01
Mining activities have contaminated many riverine floodplains with arsenic (As). When floodplain soils become anoxic under water-saturated conditions, As can be released from the solid phase. Several microbially-driven As solubilization processes and numerous influential factors were recognized in the past. However, the interplay and relative importance of soil properties and the influence of environmental factors such as temperature remain poorly understood, especially considering the (co)variation of soil properties in a floodplain. We conducted anoxic microcosm experiments at 10, 17.5, and 25 °C using 65 representative soils from the mining-impacted Ogosta River floodplain in Bulgaria. To investigate the processes of As solubilization and its quantitative variation we followed the As and Fe redox dynamics in the solid and the dissolved phase and monitored a range of other solution parameters including pH, Eh, dissolved organic C, and dissolved Mn. We related soil properties to dissolved As observed after 20 days of microcosm incubation to identify key soil properties for As solubilization. Our results evidenced reductive dissolution of As-bearing Fe(III)-oxyhydroxides as the main cause for high solubilization. The availability of nutrients, most likely organic C as the source of energy for microorganisms, was found to limit this process. Following the vertical nutrient gradient common in vegetated soil, we observed several hundred μM dissolved As after 1-2 weeks for some topsoils (0-20 cm), while for subsoils (20-40 cm) with comparable total As levels only minor solubilization was observed. While high Mn contents were found to inhibit As solubilization, the opposite applied for higher temperature (Q 10 2.3-6.1 for range 10-25 °C). Our results suggest that flooding of nutrient-rich surface layers might be more problematic than water-saturation of nutrient-poor subsoil layers, especially in summer floodings when soil temperature is higher than in winter or spring. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Stewart, B.D.; Amos, R.T.; Nico, P.S.
2010-03-15
Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate themore » impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.« less
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NASA Astrophysics Data System (ADS)
Kaiser, M.; Kleber, M.; Berhe, A. A.
2010-12-01
Aggregates play important roles in soil carbon storage and stabilization. Identification of scale-dependent mechanisms of soil aggregate formation and stability is necessary to predict and eventually manage the flow of carbon through terrestrial ecosystems. Application of ultrasonic energy is a common tool to disperse soil aggregates. In this study, we used ultra sonic energy (100 to 2000 J cm-3) to determine the amount of polyvalent cations and organic matter involved in aggregation processes in three arable and three forest soils that varied in soil mineral composition. To determine the amount of organic matter and cations released after application of different amount of ultrasonic energy, we removed the coarse fraction (>250 µm). The remaining residue (<250 µm) was mixed with water and ultrasonically dispersed by application of 100, 200, 400, 500, 1000, 1500 and 2000 J cm-3 energy. After centrifugation the supernatant was filtered and the solid residue freeze dried before we analyzed the amounts of water-extracted organic carbon (OC), Fe, Al, Ca, Mn, and Mg in the filtrates. The extracted OM and solid residues were further characterized by Fourier Transformed Infra Red spectroscopy and Scanning Electron Microscopy. Our results show a linear increase in amount of dissolved OC with increasing amounts of ultra sonic energy up to 1500 J cm-3 indicating maximum dispersion of soil aggregates at this energy level independent from soil type or land use. In contrast to Mn, and Mg, the amounts of dissolved Ca, Fe, and Al increase with increasing ultra sonic energy up to 1500 J cm-3. At 1500 J cm-3, the absolute amounts of OC, Ca, Fe, and Al released were specific for each soil type, likely indicating differences in type of OM-mineral interactions involved in micro-scaled aggregation processes. The amounts of dissolved Fe, and Al released after an application of 1500 J cm-3 are not related to oxalate- and dithionite- extractable, or total Al content indicating less disintegration of pedogenic oxides or clay minerals due to high levels of ultrasonic energy.
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Long term in situ monitoring of total dissolved iron concentrations on the MoMAR observatory
NASA Astrophysics Data System (ADS)
Laes-Huon, Agathe; Legrand, Julien; Tanguy, Virginie; Cathalot, Cecile; Blandin, Jérôme; Rolin, Jean-Francois; Sarradin, Pierre-Marie
2015-04-01
Nowadays the scientific community wants relevant monitoring with an increase in spatial and temporal distribution of key chemicals. The hydrothermal ecosystems characterized by strong physico-chemical gradients are also of particular interest as they present an unique fauna, sustained by microbial chemosynthesis. The characterization of the chemical environment in the hydrothermal vent ecosystems implies the use of in situ instrumentation which is a serious challenge in the marine environment (Prien et al. 2007). The CHEMINI (CHEmical MINIaturised analyser), presented here, is a chemical in situ analyser specialized for deep sea uses (Vuillemin et al. 2007). It was first deployed on the autonomous deep sea observatory MoMAR (Monitoring of the Mid-Atlantic Ridge, FIXO3, Fixed point Open Ocean Observatories) in 2010. The first part of the presentation will focus on the description of the CHEMINI, then on the results obtained on the MoMAR observatory during the last 4 years. CHEMINI, implemented on the TEMPO ecological module determined total dissolved iron concentrations associated with an optode and a temperature probe. Several months of total iron concentrations, of T°C and videos were recorded permitting the study of the temporal dynamics of faunal assemblages and their habitat on the Lucky strike vent (-1700m, Cuvelier et al. 2011). Long term in situ analysis of total dissolved iron (31st of August 2013 - 23rd of February 2014, [DFe] = 7.12 +- 2.11 µmol L-1, n = 519) at the Eiffel Tower edifice is presented in details. The daily analyzed in situ standard (25µmol.L-1) showed an excellent reproducibility (1.07%, n=522). CHEMINI was reliable, robust over time for in situ analysis. The averaged total dissolved iron concentrations for the 6 months period remain low but they correlated significantly with temperature showing a spectra frequency with a maximal contribution around 4-5 days for both variables. The analytical results will be commented and the future technical challenges will be discussed in this presentation. References: Cuvelier, D, Sarrazin,J, Colaco A. Copley J.T., Glover A.G. Paul, A. Tyler, Serrao Santos R., Desbruyères D. (2011), Community dynamics over 14 years at the Eiffel Tower hydrothermal edifice on the Mid-Atlantic Ridge, Limnol. Oceanogr., 56(5), 1624-1640 Prien, R. (2007), The future of chemical in situ sensors, Mar. Chem., 107 (3), 422-432. Vuillemin, R., Le Roux, D., Dorval, P., Bucas, K., Sudreau, J.P., Hamon, M., Le Gall, C., Sarradin, P.M., 2009. CHEMINI: A new in situ CHEmical MINIaturized analyzer. Deep Sea Res. Part Oceanogr. Res. Pap. 56, 1391-1399.
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ERIC Educational Resources Information Center
Elton-Chalcraft, Sally; Lander, Vini; Revell, Lynn; Warner, Diane; Whitworth, Linda
2017-01-01
In this article we seek to problematize the presence of the requirement within the teachers' standards (DfE, 2012), that they "should not undermine fundamental British values" in the context of initial teacher education in England. The inclusion of this statement within the teachers' code of conduct has made its way from the…
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ERIC Educational Resources Information Center
Wild, Mary; Silberfeld, Carolyn; Nightingale, Beverley
2015-01-01
This paper considers the overt and covert discourses in two contemporary policy documents in England and Wales, "The Nutbrown Review: Foundations for Quality" ([DfE] Department for Education Department for Education. 2012. "The Nutbrown Review: Foundations for Quality: The Independent Review of Early Education and Childcare…
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ERIC Educational Resources Information Center
Schools Network, 2011
2011-01-01
The Specialist Schools and Academies Trust (SSAT) was commissioned by the Department for Education (DfE) to research ways to improve outcomes for children and young people with the most complex educational needs and disabilities through the development of evidence-based teaching and learning strategies. The programme of research brought together a…
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ERIC Educational Resources Information Center
Hennessy, Sarah
2017-01-01
The National Plan for Music (DfE (Department for Education). 2011. The "Importance of Music: a National Plan for Music Education." https://www.gov.uk/government/publications/the-importance-of-music-a-national-plan-for-music-education.) reflected the need for increasing the numbers of primary class teachers able to teach music and of…
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ERIC Educational Resources Information Center
Pearson, Sue; Mitchell, Rafael; Rapti, Maria
2015-01-01
The Coalition Government's "Green Paper" (DfE 2011) proposes a systemic overhaul of services for pupils with special educational needs in England, with increased parental choice of provision and "sharper accountability" (p. 67) in schools. Deadlines for various stages of this reform have not been met, and its final nature…
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Traditional Tales and Imaginary Contexts in Primary Design and Technology: A Case Study
ERIC Educational Resources Information Center
McLain, Matt; McLain, Mel; Tsai, Jess; Martin, Mike; Bell, Dawne; Wooff, David
2017-01-01
Working with contexts is a key component to design and technology activity and education. The most recent iteration of the national curriculum programme of study for design and technology, in England, sets out that children between the ages of 5 and 7 "should work in a range of relevant contexts" (DfE, 2013, p.193); suggested contexts…
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Recruitment, Retention and the Workload Challenge: A Critique of the Government Response
ERIC Educational Resources Information Center
Quicke, John
2018-01-01
Various surveys have confirmed that there is a crisis of recruitment and retention of teachers in schools. This article examines the government response to this crisis, in particular to what is commonly cited as the main cause--unmanageable workloads. What it describes as the workload challenge has certainly not been ignored by the DfE, which in…
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Okumura, Kazuhiro
2009-05-01
The demand for environmentally preferable products is increasing in the area of Institutional and Industrial (I&I) cleaners. The GreenBlue Institute (GreenBlue) and U.S. Environmental Protection Agency's (U.S. EPA's) Design for Environment (DfE) launched two programs to review surfactant ingredients and final cleaning products, with the National Sanitation Foundation (NSF) conducting third-party reviews. The Local Hazardous Waste Management Program (LHWMP) in King County, Washington, has a strategic goal to reduce the risk of exposure of hazardous chemicals to vulnerable populations such as janitorial workers. This report summarizes the NSF partnership with GreenBlue, CleanGredients, and U.S. EPA's DfE to perform third-party reviews of cleaning product ingredients and its relevance to LHWMP's interest in reducing risks to workers in the janitorial industry. Due to information barriers, workers in the janitorial industry are at risk daily to these hazardous chemicals. The surfactant and formulator review program will make positive contributions towards the reduction of toxic chemical exposure to the employees of the janitorial industry. With proper communication and an increased use of less toxic cleaners, exposures to vulnerable populations can be reduced.
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Preisig, James C
2005-07-01
Equations are derived for analyzing the performance of channel estimate based equalizers. The performance is characterized in terms of the mean squared soft decision error (sigma2(s)) of each equalizer. This error is decomposed into two components. These are the minimum achievable error (sigma2(0)) and the excess error (sigma2(e)). The former is the soft decision error that would be realized by the equalizer if the filter coefficient calculation were based upon perfect knowledge of the channel impulse response and statistics of the interfering noise field. The latter is the additional soft decision error that is realized due to errors in the estimates of these channel parameters. These expressions accurately predict the equalizer errors observed in the processing of experimental data by a channel estimate based decision feedback equalizer (DFE) and a passive time-reversal equalizer. Further expressions are presented that allow equalizer performance to be predicted given the scattering function of the acoustic channel. The analysis using these expressions yields insights into the features of surface scattering that most significantly impact equalizer performance in shallow water environments and motivates the implementation of a DFE that is robust with respect to channel estimation errors.
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Montiel Corona, Virginia; Le Borgne, Sylvie; Revah, Sergio; Morales, Marcia
2017-02-01
A Rhodobacter capsulatus strain and a photoheterotrophic culture (IZT) were cultivated to produce hydrogen under different light-dark cycles. A dark fermentation effluent (DFE) was used as substrate. It was found that IZT culture had an average cumulative hydrogen production (Paccum H 2 ) of 1300±43mLH 2 L -1 under continuous illumination and light-dark cycles of 30 or 60min. In contrast, R. capsulatus reduced its Paccum H 2 by 20% under 30:30min light-dark cycles, but tripled its poly-β-hydroxybutyrate (PHB) content (308±2mgPHB gdw -1 ) compared to continuous illumination. The highest PHB content by IZT culture was 178±10mgPHB gdw -1 under 15:15min light-dark cycles. PCR-DGGE analysis revealed that the IZT culture was mainly composed of Rhodopseudomonas palustris identified with high nucleotide similarity (99%). The evaluated cultures might be used for hydrogen and PHB production. They might provide energy savings by using light-dark cycles and DFE valorization. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Kang, Heerim; Lee, Chang Hyung; Kim, Jong Rhan; Kwon, Jung Yeon; Seo, Sang Gwon; Han, Jae Gab; Kim, Byung Gon; Kim, Jong-Eun; Lee, Ki Won
2015-01-01
Atopic dermatitis (AD) is a chronic and inflammatory skin disease that can place a significant burden on quality of life for patients. AD most frequently appears under the age of six and although its prevalence is increasing worldwide, therapeutic treatment options are limited. Chlorella vulgaris (CV) is a species of the freshwater green algae genus chlorella, and has been reported to modulate allergy-inducible factors when ingested. Here, we examined the effect of CV supplementation on AD-like symptoms in NC/Nga mice. CV was orally administrated for six weeks while AD-like symptoms were induced via topical application of Dermatophagoides farinae extract (DFE). CV treatment reduced dermatitis scores, epidermal thickness, and skin hydration. Histological analysis also revealed that CV treatment reduced DFE-induced eosinophil and mast cell infiltration into the skin, while analysis of serum chemokine levels indicated that CV treatment downregulated thymus- and activation-regulated chemokine (TARC) and macrophage-derived chemokine (MDC) levels. In addition, CV treatment downregulated mRNA expression levels of IL-4 and IFN-γ. Taken together, these results suggest that CV extract may have potential as a nutraceutical ingredient for the prevention of AD. PMID:26404252
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THE EFFECTS OF ELEVATED METALS ON BENTHIC COMMUNITY METABOLISM IN A ROCKY MOUNTAIN STREAM
The effects of elevated metals (dissolved Zn, Mn and/or Fe) in a Rocky Mountain stream were assessed using measures of primary productivity, community respiration and water-column toxicity. Primary productivity was measured as rates of O2 evolution from natural substrates incubat...
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Iron-mediated soil carbon response to water-table decline in an alpine wetland
Wang, Yiyun; Wang, Hao; He, Jin-Sheng; Feng, Xiaojuan
2017-01-01
The tremendous reservoir of soil organic carbon (SOC) in wetlands is being threatened by water-table decline (WTD) globally. However, the SOC response to WTD remains highly uncertain. Here we examine the under-investigated role of iron (Fe) in mediating soil enzyme activity and lignin stabilization in a mesocosm WTD experiment in an alpine wetland. In contrast to the classic ‘enzyme latch’ theory, phenol oxidative activity is mainly controlled by ferrous iron [Fe(II)] and declines with WTD, leading to an accumulation of dissolvable aromatics and a reduced activity of hydrolytic enzyme. Furthermore, using dithionite to remove Fe oxides, we observe a significant increase of Fe-protected lignin phenols in the air-exposed soils. Fe oxidation hence acts as an ‘iron gate’ against the ‘enzyme latch’ in regulating wetland SOC dynamics under oxygen exposure. This newly recognized mechanism may be key to predicting wetland soil carbon storage with intensified WTD in a changing climate. PMID:28649988
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Air pollution–aerosol interactions produce more bioavailable iron for ocean ecosystems
Li, Weijun; Xu, Liang; Liu, Xiaohuan; Zhang, Jianchao; Lin, Yangting; Yao, Xiaohong; Gao, Huiwang; Zhang, Daizhou; Chen, Jianmin; Wang, Wenxing; Harrison, Roy M.; Zhang, Xiaoye; Shao, Longyi; Fu, Pingqing; Nenes, Athanasios; Shi, Zongbo
2017-01-01
It has long been hypothesized that acids formed from anthropogenic pollutants and natural emissions dissolve iron (Fe) in airborne particles, enhancing the supply of bioavailable Fe to the oceans. However, field observations have yet to provide indisputable evidence to confirm this hypothesis. Single-particle chemical analysis for hundreds of individual atmospheric particles collected over the East China Sea shows that Fe-rich particles from coal combustion and steel industries were coated with thick layers of sulfate after 1 to 2 days of atmospheric residence. The Fe in aged particles was present as a “hotspot” of (insoluble) iron oxides and throughout the acidic sulfate coating in the form of (soluble) Fe sulfate, which increases with degree of aging (thickness of coating). This provides the “smoking gun” for acid iron dissolution, because iron sulfate was not detected in the freshly emitted particles and there is no other source or mechanism of iron sulfate formation in the atmosphere. PMID:28275731
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Yang, Jianjun; Zhu, Shenhai; Zheng, Cuiqing; Sun, Lijuan; Liu, Jin; Shi, Jiyan
2015-04-09
Impact of S fertilization on Cu mobility and transformation in contaminated paddy soils has been little reported. In this study, we investigated the dynamics and transformation of dissolved and colloidal Cu in the pore water of a contaminated paddy soil after applying ammonium sulphate (AS) and sulfur coated urea (SCU) with various flooding periods (1, 7 and 60 days). Compared to the control soil, the AS-treated soil released more colloidal and dissolved Cu over the entire flooding period, while the SCU-treated soil had lower colloidal Cu after 7-day flooding but higher colloidal and dissolved Cu after 60-day flooding. Microscopic X-ray fluorescence (μ-XRF) analysis found a close relationship between Fe and Cu distribution on soil colloids after 60-day flooding, implying the formation of colloidal Fe/Cu sulphide coprecipitates. Cu K-edge X-ray absorption near-edge structure (XANES) spectroscopy directly revealed the transformation of outer-sphere complexed Cu(II) species to Cu(II) sulphide and reduced Cu2O in the colloids of S-treated soils after 60-day flooding. These results demonstrated the great influence of S fertilization on pore-water Cu mobility by forming Cu sulphide under flooding conditions, which facilitated our understanding and control of Cu loss in contaminated paddy soils under S fertilization. Copyright © 2015 Elsevier B.V. All rights reserved.
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A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts.
Stolper, Daniel A; Keller, C Brenhin
2018-01-18
The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O 2 ) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe 3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).
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A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts
NASA Astrophysics Data System (ADS)
Stolper, Daniel A.; Keller, C. Brenhin
2018-01-01
The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O2) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).
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Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water.
Sit, Patrick H-L; Car, Roberto; Cohen, Morrel H; Selloni, Annabella
2013-02-05
Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 10(4)/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe](P)/FeS(2), a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe](P)/FeS(2) is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant.
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Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water
Sit, Patrick H.-L.; Car, Roberto; Cohen, Morrel H.; Selloni, Annabella
2013-01-01
Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 104/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe]P/FeS2, a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe]P/FeS2 is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant. PMID:23341607
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Experimental modeling of the interaction of subducted carbonates and sulfur with mantle silicates
NASA Astrophysics Data System (ADS)
Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Sobolev, N. V.
2016-09-01
Experimental studies in the system Fe,Ni-olivine-carbonate-S ( P = 6.3 GPa, T = 1050-1550°C, t = 40-60 h) aimed at modeling of the interaction of subducted carbonates and sulfur with rocks of the silicate mantle and at investigation of the likely mechanism of the formation of mantle sulfides were performed. It is shown that an association of olivine + orthopyroxene + magnesite + pyrite coexisting with a sulfur melt/fluid with dissolved Fe, Ni, and O is formed at T ≤ 1250°C. An association of low-Fe olivine, orthopyroxene, and magnesite and two immiscible melts of the carbonate and S-Fe-Ni-O compositions are formed at T ≥ 1350°C. It is shown that the reduced S-bearing fluids may transform silicates and carbonates, extract metals from the solid-phase matrix, and provide conditions for generation of sulfide melts.
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Mejia, Jacqueline; Roden, Eric E; Ginder-Vogel, Matthew
2016-04-05
Oscillations between reducing and oxidizing conditions are observed at the interface of anaerobic/oxic and anaerobic/anoxic environments, and are often stimulated by an alternating flux of electron donors (e.g., organic carbon) and electron acceptors (e.g., O2 and NO3(-)). In iron (Fe) rich soils and sediments, these oscillations may stimulate the growth of both Fe-reducing bacteria (FeRB) and Fe-oxidizing bacteria (FeOB), and their metabolism may induce cycling between Fe(II) and Fe(III), promoting the transformation of Fe (hydr)oxide minerals. Here, we examine the mineralogical evolution of lepidocrocite and ferrihydrite, and the adaptation of a natural microbial community to alternating Fe-reducing (anaerobic with addition of glucose) and Fe-oxidizing (with addition of nitrate or air) conditions. The growth of FeRB (e.g., Geobacter) is stimulated under anaerobic conditions in the presence of glucose. However, the abundance of these organisms depends on the availability of Fe(III) (hydr)oxides. Redox cycling with nitrate results in decreased Fe(II) oxidation thereby decreasing the availability of Fe(III) for FeRB. Additionally, magnetite is detected as the main product of both lepidocrocite and ferrihydrite reduction. In contrast, introduction of air results in increased Fe(II) oxidation, increasing the availability of Fe(III) and the abundance of Geobacter. In the lepidocrocite reactors, Fe(II) oxidation by dissolved O2 promotes the formation of ferrihydrite and lepidocrocite, whereas in the ferrihydrite reactors we observe a decrease in magnetite stoichiometry (e.g., oxidation). Understanding Fe (hydr)oxide transformation under environmentally relevant redox cycling conditions provides insight into nutrient availability and transport, contaminant mobility, and microbial metabolism in soils and sediments.
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Degens, Bradley P; Krassoi, Rick; Galvin, Lynette; Reynolds, Brad; Micevska, Tina
2018-05-01
Measurements of potential acidity in water are used to manage aquatic toxicity risks of discharge from acid sulfate soils or acid mine drainage. Net acidity calculated from pH, dissolved metals and alkalinity is a common measurement of potential acidity but the relevance of current risk thresholds to aquatic organisms are unclear. Aquatic toxicity testing was carried out using four halophytic organisms with water from four saline sources in southern Western Australia (3 acidic drains and one alkaline river; 39-40 g TDS/L) where acidity was varied by adjusting pH to 4.5-6.5. The test species were brine shrimps (Artemia salina), locally sourced ostracods (Platycypris baueri), microalgae (Dunaliella salina) and amphipods (Allorchestes compressa). Testing found the EC 10 and IC 10 of net acidity ranged from -7.8 to 10.5 mg CaCO 3 /L with no survival or growth of any species at >47 mg CaCO 3 /L. Reduced net acidity indicated reduced whole effluent toxicity more reliably than increased pH alone with organisms tolerating pH up to 1.1 units lower in the absence of dissolved metals. Variation in toxicity indicated by net acidity was mostly attributed to reduced concentrations of dissolved Al and Fe combined with higher pH and alkalinity and some changes in speciation of Al and Fe with pH. These results indicate that rapid in-field assessments of net acidity in acidic, Al dominated waters may be an indicator of potential acute and sub-chronic impacts on aquatic organisms. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.
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Rapid photooxidation of Sb(III) in the presence of different Fe(III) species
NASA Astrophysics Data System (ADS)
Kong, Linghao; He, Mengchang; Hu, Xingyun
2016-05-01
The toxicity and mobility of antimony (Sb) are strongly influenced by the redox processes associated with Sb. Dissolved iron (Fe) is widely distributed in the environment as different species and plays a significant role in Sb speciation. However, the mechanisms of Sb(III) oxidation in the presence of Fe have remained unclear because of the complexity of Fe and Sb speciation. In this study, the mechanisms of Sb(III) photooxidation in the presence of different Fe species were investigated systematically. The photooxidation of Sb(III) occurred over a wide pH range, from 1 to 10. Oxygen was not a predominant or crucial factor in the Sb(III) oxidation process. The mechanism of Sb(III) photooxidation varied depending on the Fe(III) species. In acidic solution (pH 1-3), dichloro radicals (radCl2-) and hydroxyl radicals (radOH) generated by the photocatalysis of FeCl2+ and FeOH2+ were the main oxidants for Sb(III) oxidation. Fe(III) gradually transformed into the colloid ferric hydroxide (CFH) and ferrihydrite in circumneutral and alkaline solutions (pH 4-10). Photooxidation of Sb(III) occurred through electron transfer from Sb(III) to Fe(III) along with the reduction of Fe(III) to Fe(II) through a ligand-to-metal charge-transfer (LMCT) process. The photocatalysis of different Fe(III) species may play an important role in the geochemical cycle of Sb(III) in surface soil and aquatic environments.
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Muehe, E Marie; Adaktylou, Irini J; Obst, Martin; Zeitvogel, Fabian; Behrens, Sebastian; Planer-Friedrich, Britta; Kraemer, Ute; Kappler, Andreas
2013-01-01
Cadmium (Cd) is of environmental relevance as it enters soils via Cd-containing phosphate fertilizers and endangers human health when taken up by crops. Cd is known to associate with Fe(III) (oxyhydr)oxides in pH-neutral to slightly acidic soils, though it is not well understood how the interrelation of Fe and Cd changes under Fe(III)-reducing conditions. Therefore, we investigated how the mobility of Cd changes when a Cd-bearing soil is faced with organic carbon input and reducing conditions. Using fatty acid profiles and quantitative PCR, we found that both fermenting and Fe(III)-reducing bacteria were stimulated by organic carbon-rich conditions, leading to significant Fe(III) reduction. The reduction of Fe(III) minerals was accompanied by increasing soil pH, increasing dissolved inorganic carbon, and decreasing Cd mobility. SEM-EDX mapping of soil particles showed that a minor fraction of Cd was transferred to Ca- and S-bearing minerals, probably carbonates and sulfides. Most of the Cd, however, correlated with a secondary iron mineral phase that was formed during microbial Fe(III) mineral reduction and contained mostly Fe, suggesting an iron oxide mineral such as magnetite (Fe3O4). Our data thus provide evidence that secondary Fe(II) and Fe(II)/Fe(III) mixed minerals could be a sink for Cd in soils under reducing conditions, thus decreasing the mobility of Cd in the soil.
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RECOVERY OF URANIUM FROM LOW GRADE URANIUM BEARING ORES
Rhodes, H.B.; Pesold, W.F.; Hirshon, J.M.
1959-06-01
Recovery of U, Fe, and Al from Chattanooga shale is described. Ground shale (-4 to +325 mesh) is roasted to remove organic and volatile matter. The heated shale is then reacted with a chlorinating agent (CCl/sub 4/, COCl/sub 2/, Cl, and SCl) at 600 to 1000 C. The metal chloride vapor is separated from entrained solids and then contacted with a liquid alkali metal chloride which removes U. The U is reeovered by cooling and dissolving the bath followed by acidification and solvent extraction. A condensed phase of Al, Fe, and K chlorides is treated to separate Al as alumina by passing through a Fe/sub 2/O/ sub 3/ bed. The remaining FeCl/sub 3/ is oxidized by O/sub 2/ at 1000 C to form Fe/sub 2/O/sub 3/ and Cl/sub 2/. Alternatively, vapor from the U separation step may be passed to a liquid KCl bath at 500 to 650 C. The resulting mixture is oxidized to form Cl/sub 2/ and Fe/sub 2/O/sub 3/ + Al/sub 2/O/sub 3/. The Al and Fe are separated by reaction with NaOH at high temperatures and pressures. (T.R.H.)
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Haron, Md Jelas; Jahangirian, Hossein; Silong, Sidik; Yusof, Nor Azah; Kassim, Anuar; Rafiee-Moghaddam, Roshanak; Mahdavi, Behnam; Peyda, Mazyar; Abdollahi, Yadollah; Amin, Jamileh
2012-01-01
Liquid-liquid iron(III) extraction was investigated using benzyl fatty hydroxamic acids (BFHAs) and methyl fatty hydroxamic acids (MFHAs) as chelating agents through the formation of iron(III) methyl fatty hydroxamate (Fe-MFHs) or iron(III) benzyl fatty hydroxamate (Fe-BFHs) in the organic phase. The results obtained under optimized conditions, showed that the chelating agents in hexane extract iron(III) at pH 1.9 were realized effectively with a high percentage of extraction (97.2% and 98.1% for MFHAs and BFHAs, respectively). The presence of a large amount of Mg(II), Ni(II), Al(III), Mn(II) and Co(II) ions did affect the iron(III) extraction. Finally stripping studies for recovering iron(III) from organic phase (Fe-MFHs or Fe-BFHs dissolved in hexane) were carried out at various concentrations of HCl, HNO3 and H2SO4. The results showed that the desired acid for recovery of iron(III) was 5 M HCl and quantitative recovery of iron(III) was achieved from Fe(III)-MFHs and Fe(III)-BFHs solutions in hexane containing 5 mg/L of Fe(III). PMID:22408444
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Biogeochemical stability and reactions of iron-organic carbon complexes
NASA Astrophysics Data System (ADS)
Yang, Y.; Adhikari, D.; Zhao, Q.; Dunham-Cheatham, S.; Das, K.; Mejia, J.; Huang, R.; Wang, X.; Poulson, S.; Tang, Y.; Obrist, D.; Roden, E. E.
2017-12-01
Our core hypothesis is that the degradation rate of soil organic carbon (OC) is governed by the amount of iron (Fe)-bound OC, and the ability of microbial communities to utilize OC as an energy source and electron shuttle for Fe reduction that in turn stimulates reductive release of Fe-bound labile dissolved OC. This hypothesis is being systematically evaluated using model Fe-OC complexes, natural soils, and microcosm system. We found that hematite-bound aliphatic C was more resistant to reduction release, although hematite preferred to sorb more aromatic C. Resistance to reductive release represents a new mechanism that aliphatic soil OC was stabilized by association with Fe oxide. In other studies, pyrogenic OC was found to facilitate the reduction of hematite, by enhancing extracellular electron transport and sorbing Fe(II). For ferrihydrite-OC co-precipitates, the reduction of Fe and release of OC was closely governed by the C/Fe ratio in the system. Based on the XPS, XANES and XAFS analysis, the transformation of Fe speciation was heterogeneous, depending on the conformation and composition of Fe-OC complexes. For natural soils, we investigated the quantity, characteristics, and reactivity of Fe-bound OC in soils collected from 14 forests in the United States. Fe-bound OC contributed up to 57.8% of total OC in the forest soils. Under the anaerobic conditions, the reduction of Fe was positively correlated to the electron accepting capacity of OC. Our findings highlight the closely coupled dynamics of Fe and OC, with broad implications on the turnover of OC and biogeochemical cycles of Fe.
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Iron cycling at corroding carbon steel surfaces.
Lee, Jason S; McBeth, Joyce M; Ray, Richard I; Little, Brenda J; Emerson, David
2013-01-01
Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media.
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Synergistic operation of photocatalytic degradation and Fenton process by magnetic Fe3O4 loaded TiO2
NASA Astrophysics Data System (ADS)
Sun, Qiong; Hong, Yong; Liu, Qiuhong; Dong, Lifeng
2018-02-01
The magnetic Fe3O4 loaded anatase TiO2 photocatalysts with different mass ratios were successfully synthesized by a one-step convenient calcining method. The morphology and structure analysis revealed that Fe3O4 was formed in TiO2 with very fine-grained particles. After a small amount of Fe3O4 loaded onto TiO2, the photocatalytic property enhanced obviously for the degradation of organic dye. Furthermore, the photo-Fenton-like catalysis of the iron-containing samples could also be induced after the addition of hydrogen peroxide. The apparent kinetic constant of the reaction that catalyzed by Fe-TiO2 was about 5.3 and 8.3 times of that catalyzed by TiO2 or Fe3O4 only, respectively, proving an effective synergistic contribution of the photocatalysis and Fenton reaction in the composite. Compared with Fe3O4 or free Fe3+ ions, only 13% of iron in TiO2 dissolved into acidic solution (25% for Fe3O4 and 100% for Fe3+) after the reaction, which confirmed the iron had been well immobilized onto TiO2. In addition, the extremely stable photocatalytic activity in cycling experiments proved the immobilized iron had been tightly attached onto TiO2, indicating the great potential of the catalyst for practical applications.