Sample records for organic carbon iron

  1. Iron-sulfur-carbon relationships in organic-carbon-rich sequences I: Cretaceous Western Interior seaway

    USGS Publications Warehouse

    Dean, W.E.; Arthur, M.A.

    1989-01-01

    Cretaceous marine strata deposited in shallow to intermediate depths in the Western Interior seaway of North America show considerable variation in organic-carbon enrichment and degree of pyrite formation. The extreme range of paleoceanographic and depositional conditions that occurred in this seaway provide a unique opportunity to examine the effects of iron-, carbon-, and sulfur-limitation on pyrite formation in one region over about 30 my. Ternary diagrams of the system Fe-S-OC, together with some measure of the reactivity of organic matter (pyrolysis hydrogen index), provide a rapid means of recognizing iron-, carbon-, and sulfur-limitation on pyrite formation in a series of samples from a single lithologic unit. Iron limitation is indicated by a concentration of data along a line of constant S/Fe ratio on a Fe-S-OC ternary diagram. Carbon limitation is indicated by a concentration of data along a line of constant S/OC ratio. Sulfur-limitation is suggested by the lack of a systematic Fe-S-OC relationship and residual organic matter that is high in abundance and reactivity. -from Authors

  2. The Role of Reactive Iron in Organic Carbon Burial of the Wax Lake Delta, Louisiana

    NASA Astrophysics Data System (ADS)

    Bianchi, T. S.; Shields, M. R.; Gelinas, Y.; Allison, M. A.; Twilley, R.

    2016-02-01

    Deltaic systems are responsible for 41% of the total organic carbon buried on continental shelves (Smith et al., 2015). Furthermore, 21.5 ± 8.6% of the organic carbon in marine sediments is reported to be associated to reactive iron phases (Lalonde et al., 2012). Here, we examine the role of reactive iron in preserving organic carbon across a chronosequence in deltaic soils/sediments of the Wax Lake Delta, Louisiana. This prograding delta is part of the youngest subdelta of the Mississippi River Delta and serves as a model for deltas in an active progradational stage. We report the proportion, δ13C, lignin phenol content, and fatty acid content of organic carbon associated to iron in three unique environments along the delta topset. We found that over 15 % of the organic carbon in the top 0.5 meters was associated to reactive iron phases at our sampling locations. However, this amount varied between the mudflat, meadow, and canopy dominated sites. Moreover, the type of binding shifts from 1:1 sorption in the sediment dominated (mudflat) region to chelation/co-precipitation in the more soil-dominated regions. Acidic lignin phenols are preferentially sorbed in the mudflat region, which likely occurs pre-depositionally. These results add to our knowledge of the carbon burial processes in young deltas and present new questions about the selective preservation of organic compounds in deltaic sediments.

  3. Effects of iron-aluminium oxides and organic carbon on aggregate stability of bauxite residues.

    PubMed

    Zhu, Feng; Li, Yubing; Xue, Shengguo; Hartley, William; Wu, Hao

    2016-05-01

    In order to successfully establish vegetation on bauxite residue, properties such as aggregate structure and stability require improvement. Spontaneous plant colonization on the deposits in Central China over the last 20 years has revealed that natural processes may improve the physical condition of bauxite residues. Samples from three different stacking ages were selected to determine aggregate formation and stability and its relationship with iron-aluminium oxides and organic carbon. The residue aggregate particles became coarser in both dry and wet sieving processes. The mean weight diameter (MWD) and geometry mean diameter (GMD) increased significantly, and the proportion of aggregate destruction (PAD) decreased. Natural stacking processes could increase aggregate stability and erosion resistant of bauxite residues. Free iron oxides and amorphous aluminium oxides were the major forms in bauxite residues, but there was no significant correlation between the iron-aluminium oxides and aggregate stability. Aromatic-C, alkanes-C, aliphatic-C and alkenes-C were the major functional groups present in the residues. With increasing stacking age, total organic carbon content and aggregate-associated organic carbon both increased. Alkanes-C, aliphatic-C and alkenes-C increased and were mainly distributed in macro-aggregates, whereas aromatic-C was mainly distributed in <0.05-mm aggregates. Organic carbon stability in micro-aggregates was higher than that in macro-aggregates and became more stable. Organic carbon contents in total residues, and within different aggregate sizes, were all negatively correlated with PAD. It indicated that organic materials had a more significant effect on macro-aggregate stability and the effects of iron-aluminium oxides maybe more important for stability of micro-aggregates.

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

    NASA Astrophysics Data System (ADS)

    Balind, K.; Barber, A.; Gélinas, Y.

    2017-12-01

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

  5. Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

    NASA Astrophysics Data System (ADS)

    Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

    2017-12-01

    The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular

  6. Iron, phytoplankton growth, and the carbon cycle.

    PubMed

    Street, Joseph H; Paytan, Adina

    2005-01-01

    Iron is an essential nutrient for all living organisms. Iron is required for the synthesis of chlorophyll and of several photosynthetic electron transport proteins and for the reduction of CO2, SO4(2-), and NO3(-) during the photosynthetic production of organic compounds. Iron concentrations in vast areas of the ocean are very low (<1 nM) due to the low solubility of iron in oxic seawater. Low iron concentrations have been shown to limit primary production rates, biomass accumulation, and ecosystem structure in a variety of open-ocean environments, including the equatorial Pacific, the subarctic Pacific and the Southern Ocean and even in some coastal areas. Oceanic primary production, the transfer of carbon dioxide into organic carbon by photosynthetic plankton (phytoplankton), is one process by which atmospheric CO2 can be transferred to the deep ocean and sequestered for long periods of time. Accordingly, iron limitation of primary producers likely plays a major role in the global carbon cycle. It has been suggested that variations in oceanic primary productivity, spurred by changes in the deposition of iron in atmospheric dust, control atmospheric CO2 concentrations, and hence global climate, over glacial-interglacial timescales. A contemporary application of this "iron hypothesis" promotes the large-scale iron fertilization of ocean regions as a means of enhancing the ability of the ocean to store anthropogenic CO2 and mitigate 21st century climate change. Recent in situ iron enrichment experiments in the HNLC regions, however, cast doubt on the efficacy and advisability of iron fertilization schemes. The experiments have confirmed the role of iron in regulating primary productivity, but resulted in only small carbon export fluxes to the depths necessary for long-term sequestration. Above all, these experiments and other studies of iron biogeochemistry over the last two decades have begun to illustrate the great complexity of the ocean system. Attempts to

  7. Soil organic carbon stabilization by iron in permafrost regions of the Qinghai-Tibet Plateau

    NASA Astrophysics Data System (ADS)

    Mu, C. C.; Zhang, T. J.; Zhao, Q.; Guo, H.; Zhong, W.; Su, H.; Wu, Q. B.

    2016-10-01

    A close relationship exists between soil organic carbon (SOC) and reactive iron; however, little is known about the role of iron in SOC preservation in permafrost regions. We determined the amount of SOC associated with reactive iron phases (OC-Fe) in the permafrost regions of the Qinghai-Tibetan Plateau (QTP). The results showed that the percentage of OC-Fe ranged between 0.9% and 59.5% in the upper 30 cm of soil and that the OC-Fe represented 19.5 ± 12.3% of the total SOC pool. No clear vertical distribution pattern in OC-Fe was present in the upper 1 m of soil. Throughout the year, the OC-Fe accounted for relatively stable proportions of the total SOC pool. This study suggests that approximately 20% of SOC is a potential rusty OC pool in the permafrost regions of the QTP. Biogeochemical processes related to the reaction of iron may play important roles in soil carbon cycles in permafrost regions.

  8. Tropical forest soil microbial communities couple iron and carbon biogeochemistry

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

    Dubinsky, E.A.; Silver, W.L.; Firestone, M.K.

    2009-10-15

    We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500 - 5000 mm yr-1) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally dynamic redox conditions make iron-transforming microbial communities central to the belowground carbon cycle in these wet tropical forests. The exceedingly high abundance of iron-reducing bacteria (up to 1.2 x 10{sup 9} cells per gram soil) indicated that they possess extensive metabolic capacity to catalyze the reduction ofmore » iron minerals. In soils from the higher rainfall sites, measured rates of ferric iron reduction could account for up to 44 % of organic carbon oxidation. Iron reducers appeared to compete with methanogens when labile carbon availability was limited. We found large numbers of bacteria that oxidize reduced iron at sites with high rates of iron reduction and large numbers of iron-reducers. the coexistence of large populations of ironreducing and iron-oxidizing bacteria is evidence for rapid iron cycling between its reduced and oxidized states, and suggests that mutualistic interactions among these bacteria ultimately fuel organic carbon oxidation and inhibit CH4 production in these upland tropical forests.« less

  9. Carbonate counter pump stimulated by natural iron fertilization in the Polar Frontal Zone

    NASA Astrophysics Data System (ADS)

    Salter, Ian; Schiebel, Ralf; Ziveri, Patrizia; Movellan, Aurore; Lampitt, Richard; Wolff, George A.

    2014-12-01

    The production of organic carbon in the ocean's surface and its subsequent downward export transfers carbon dioxide to the deep ocean. This CO2 drawdown is countered by the biological precipitation of carbonate, followed by sinking of particulate inorganic carbon, which is a source of carbon dioxide to the surface ocean, and hence the atmosphere over 100-1,000 year timescales. The net transfer of CO2 to the deep ocean is therefore dependent on the relative amount of organic and inorganic carbon in sinking particles. In the Southern Ocean, iron fertilization has been shown to increase the export of organic carbon, but it is unclear to what degree this effect is compensated by the export of inorganic carbon. Here we assess the composition of sinking particles collected from sediment traps located in the Polar Frontal Zone of the Southern Ocean. We find that in high-nutrient, low-chlorophyll regions that are characterized by naturally high iron concentrations, fluxes of both organic and inorganic carbon are higher than in regions with no iron fertilization. However, the excess flux of inorganic carbon is greater than that of organic carbon. We estimate that the production and flux of carbonate in naturally iron-fertilized waters reduces the overall amount of CO2 transferred to the deep ocean by 6-32%, compared to 1-4% at the non-fertilized site. We suggest that an increased export of organic carbon, stimulated by iron availability in the glacial sub-Antarctic oceans, may have been accompanied by a strengthened carbonate counter pump.

  10. Hydrologically mediated iron reduction/oxidation fluctuations and dissolved organic carbon exports in tidal wetlands

    NASA Astrophysics Data System (ADS)

    Guimond, J. A.; Seyfferth, A.; Michael, H. A.

    2017-12-01

    Salt marshes are biogeochemical hotspots where large quantities of carbon are processed and stored. High primary productivity and deposition of carbon-laden sediment enable salt marsh soils to accumulate and store organic carbon. Conversely, salt marshes can laterally export carbon from the marsh platform to the tidal channel and eventually the ocean via tidal pumping. However, carbon export studies largely focus on tidal channels, missing key physical and biogeochemical mechanisms driving the mobilization of dissolved organic carbon (DOC) within the marsh platform and limiting our understanding of and ability to predict coastal carbon dynamics. We hypothesize that iron redox dynamics mediate the mobilization/immobilization of DOC in the top 30 cm of salt marsh sediment near tidal channels. The mobilized DOC can then diffuse into the flooded surface water or be advected to tidal channels. To elucidate DOC dynamics driven by iron redox cycles, we measured porewater DOC, Fe(II), total iron, total sulfate, pH, redox potential, and electrical conductivity (EC) beside the creek, at the marsh levee, and in the marsh interior in a mid-latitude tidal salt marsh in Dover, Delaware. Samples were collected at multiple tide stages during a spring and neap tide at depths of 5-75cm. Samples were also collected from the tidal channel. Continuous Eh measurements were made using in-situ electrodes. A prior study shows that DOC and Fe(II) concentrations vary spatially across the marsh. Redox conditions near the creek are affected by tidal oscillations. High tides saturate the soil and decrease redox potential, whereas at low tide, oxygen enters the sediment and increases the Eh. This pattern is always seen in the top 7-10cm of sediment, with more constant low Eh at depth. However, during neap tides, this signal penetrates deeper. Thus, between the creek and marsh levee, hydrology mediates redox conditions. Based on porewater chemistry, if DOC mobilization can be linked to redox

  11. Carbonate-sensitive phytotransferrin controls high-affinity iron uptake in diatoms

    NASA Astrophysics Data System (ADS)

    McQuaid, Jeffrey B.; Kustka, Adam B.; Oborník, Miroslav; Horák, Aleš; McCrow, John P.; Karas, Bogumil J.; Zheng, Hong; Kindeberg, Theodor; Andersson, Andreas J.; Barbeau, Katherine A.; Allen, Andrew E.

    2018-03-01

    In vast areas of the ocean, the scarcity of iron controls the growth and productivity of phytoplankton. Although most dissolved iron in the marine environment is complexed with organic molecules, picomolar amounts of labile inorganic iron species (labile iron) are maintained within the euphotic zone and serve as an important source of iron for eukaryotic phytoplankton and particularly for diatoms. Genome-enabled studies of labile iron utilization by diatoms have previously revealed novel iron-responsive transcripts, including the ferric iron-concentrating protein ISIP2A, but the mechanism behind the acquisition of picomolar labile iron remains unknown. Here we show that ISIP2A is a phytotransferrin that independently and convergently evolved carbonate ion-coordinated ferric iron binding. Deletion of ISIP2A disrupts high-affinity iron uptake in the diatom Phaeodactylum tricornutum, and uptake is restored by complementation with human transferrin. ISIP2A is internalized by endocytosis, and manipulation of the seawater carbonic acid system reveals a second-order dependence on the concentrations of labile iron and carbonate ions. In P. tricornutum, the synergistic interaction of labile iron and carbonate ions occurs at environmentally relevant concentrations, revealing that carbonate availability co-limits iron uptake. Phytotransferrin sequences have a broad taxonomic distribution and are abundant in marine environmental genomic datasets, suggesting that acidification-driven declines in the concentration of seawater carbonate ions will have a negative effect on this globally important eukaryotic iron acquisition mechanism.

  12. Iron traps terrestrially derived dissolved organic matter at redox interfaces

    PubMed Central

    Riedel, Thomas; Zak, Dominik; Biester, Harald; Dittmar, Thorsten

    2013-01-01

    Reactive iron and organic carbon are intimately associated in soils and sediments. However, to date, the organic compounds involved are uncharacterized on the molecular level. At redox interfaces in peatlands, where the biogeochemical cycles of iron and dissolved organic matter (DOM) are coupled, this issue can readily be studied. We found that precipitation of iron hydroxides at the oxic surface layer of two rewetted fens removed a large fraction of DOM via coagulation. On aeration of anoxic fen pore waters, >90% of dissolved iron and 27 ± 7% (mean ± SD) of dissolved organic carbon were rapidly (within 24 h) removed. Using ultra-high-resolution MS, we show that vascular plant-derived aromatic and pyrogenic compounds were preferentially retained, whereas the majority of carboxyl-rich aliphatic acids remained in solution. We propose that redox interfaces, which are ubiquitous in marine and terrestrial settings, are selective yet intermediate barriers that limit the flux of land-derived DOM to oceanic waters. PMID:23733946

  13. The influence of iron oxide nanoparticles upon the adsorption of organic matter on magnetic powdered activated carbon.

    PubMed

    Lompe, Kim Maren; Menard, David; Barbeau, Benoit

    2017-10-15

    Combining powdered activated carbon (PAC) with magnetic iron oxides has been proposed in the past to produce adsorbents for natural organic matter (NOM) removal that can be easily separated using a magnetic field. However, the trade-off between the iron oxides' benefits and the reduced carbon content, porosity, and surface area has not yet been investigated systematically. We produced 3 magnetic powdered activated carbons (MPAC) with mass fractions of 10%, 38% and 54% maghemite nanoparticles and compared them to bare PAC and pure nanoparticles with respect to NOM adsorption kinetics and isotherms. While adsorption kinetics were not influenced by the presence of the iron oxide nanoparticles (IONP), as shown by calculated diffusion coefficients from the homogeneous surface diffusion model, nanoparticles reduced the adsorption capacity of NOM due to their lower adsorption capacity. Although the nanoparticles added mesoporosity to the composite materials they blocked intrinsic PAC mesopores at mass fractions >38% as measured by N 2 -adsorption isotherms. Below this mass fraction, the adsorption capacity was mainly dependent on the carbon content in MPAC and mesopore blocking was negligible. If NOM adsorption with MPAC is desired, a highly mesoporous PAC and a low IONP mass fraction should be chosen during MPAC synthesis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Soil Iron Content as a Predictor of Carbon and Nutrient Mobilization in Rewetted Fens

    PubMed Central

    Emsens, Willem-Jan; Aggenbach, Camiel J. S.; Schoutens, Ken; Smolders, Alfons J. P.; Zak, Dominik; van Diggelen, Rudy

    2016-01-01

    Rewetted, previously drained fens often remain sources rather than sinks for carbon and nutrients. To date, it is poorly understood which soil characteristics stimulate carbon and nutrient mobilization upon rewetting. Here, we assess the hypothesis that a large pool of iron in the soil negatively affects fen restoration success, as flooding-induced iron reduction (Fe3+ to Fe2+) causes a disproportionate breakdown of organic matter that is coupled with a release of inorganic compounds. We collected intact soil cores in two iron-poor and two iron-rich drained fens, half of which were subjected to a rewetting treatment while the other half was kept drained. Prolonged drainage led to the mobilization of nitrate (NO3-, > 1 mmol L-1) in all cores, regardless of soil iron content. In the rewetted iron-rich cores, a sharp increase in pore water iron (Fe) concentrations correlated with concentrations of inorganic carbon (TIC, > 13 mmol L-1) and dissolved organic carbon (DOC, > 16 mmol L-1). Additionally, ammonium (NH4+) accumulated up to phytotoxic concentrations of 1 mmol L-1 in the pore water of the rewetted iron-rich cores. Disproportionate mobilization of Fe, TIC, DOC and NH4+ was absent in the rewetted iron-poor cores, indicating a strong interaction between waterlogging and iron-mediated breakdown of organic matter. Concentrations of dissolved phosphorus (P) rose slightly in all cores upon rewetting, but remained low throughout the experiment. Our results suggest that large pools of iron in the top soil of drained fens can hamper the restoration of the fen’s sink-service for ammonium and carbon upon rewetting. We argue that negative effects of iron should be most apparent in fens with fluctuating water levels, as temporary oxygenation allows frequent regeneration of Fe3+. We conclude that rewetting of iron-poor fens may be more feasible for restoration. PMID:27050837

  15. Study of adsorption process of iron colloid substances on activated carbon by ultrasound

    NASA Astrophysics Data System (ADS)

    Machekhina, K. I.; Shiyan, L. N.; Yurmazova, T. A.; Voyno, D. A.

    2015-04-01

    The paper reports on the adsorption of iron colloid substances on activated carbon (PAC) Norit SA UF with using ultrasound. It is found that time of adsorption is equal to three hours. High-frequency electrical oscillation is 35 kHz. The adsorption capacity of activated carbon was determined and it is equal to about 0.25 mg iron colloid substances /mg PAC. The iron colloid substances size ranging from 30 to 360 nm was determined. The zeta potential of iron colloid substances which consists of iron (III) hydroxide, silicon compounds and natural organic substances is about (-38mV). The process of destruction iron colloid substances occurs with subsequent formation of a precipitate in the form of Fe(OH)3 as a result of the removal of organic substances from the model solution.

  16. Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

    NASA Technical Reports Server (NTRS)

    Beukes, N. J.; Klein, C.; Kaufman, A. J.; Hayes, J. M.

    1990-01-01

    The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

  17. Tracing iron-carbon redox from surface to core

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

  18. Iron-mediated stabilization of soil carbon amplifies the benefits of ecological restoration in degraded lands.

    PubMed

    Silva, Lucas C R; Doane, Timothy A; Corrêa, Rodrigo S; Valverde, Vinicius; Pereira, Engil I P; Horwath, William R

    2015-07-01

    Recent observations across a 14-year restoration chronosequence have shown an unexpected accumulation of soil organic carbon in strip-mined areas of central Brazil. This was attributed to the rapid plant colonization that followed the incorporation of biosolids into exposed regoliths, but the specific mechanisms involved in the stabilization of carbon inputs from the vegetation remained unclear. Using isotopic and elemental analyses, we tested the hypothesis that plant-derived carbon accumulation was triggered by the formation of iron-coordinated complexes, stabilized into physically protected (occluded) soil fractions. Confirming this hypothesis, we identified a fast formation of microaggregates shortly after the application of iron-rich biosolids, which was characterized by a strong association between pyrophosphate-extractable iron and plant-derived organic matter. The formation of microaggregates preceded the development of macroaggregates, which drastically increased soil carbon content (-140 Mg C/ha) a few years after restoration. Consistent with previous theoretical work, iron-coordinated organic complexes served as nuclei for aggregate formation, reflecting the synergistic effect of biological, chemical, and physical mechanisms of carbon stabilization in developing soils. Nevertheless, iron was not the only factor affecting soil carbon content. The highest carbon accumulation was observed during the period of highest plant diversity (> 30 species; years 3-6), declining significantly with the exclusion of native species by invasive grasses (years 9-14). Furthermore, the increasing dominance of invasive grasses was associated with a steady decline in the concentration of soil nitrogen and phosphorus per unit of accumulated carbon. These results demonstrate the importance of interdependent ecological and biogeochemical processes, and the role of soil-plant interactions in determining the success of restoration efforts. In contrast with previous but

  19. Carbon in iron phases under high pressure

    NASA Astrophysics Data System (ADS)

    Huang, L.; Skorodumova, N. V.; Belonoshko, A. B.; Johansson, B.; Ahuja, R.

    2005-11-01

    The influence of carbon impurities on the properties of iron phases (bcc, hcp, dhcp, fcc) has been studied using the first-principles projector augmented-wave (PAW) method for a wide pressure range. It is shown that the presence of ~6 at. % of interstitial carbon has a little effect on the calculated structural sequence of the iron phases under high pressure. The bcc -> hcp transition both for pure iron and iron containing carbon takes place around 9 GPa. According to the enthalpies comparison, the solubility of carbon into the iron solid is decreased by high pressure. The coexistence of iron carbide (Fe3C) + pure hcp Fe is most stable phase at high pressure compared with other phases. Based on the analysis of the pressure-density dependences for Fe3C and hcp Fe, we suggest that there might be some fraction of iron carbide present in the core.

  20. Binding of dinitrogen to an iron-sulfur-carbon site

    NASA Astrophysics Data System (ADS)

    Čorić, Ilija; Mercado, Brandon Q.; Bill, Eckhard; Vinyard, David J.; Holland, Patrick L.

    2015-10-01

    Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2-bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site.

  1. Iron Reduction and Carbonate Precipitation by Shewanella oneidensis

    NASA Astrophysics Data System (ADS)

    Zeng, Z.; Tice, M. M.

    2011-12-01

    This study is to contribute to better understanding of how Archean microbes induced carbonate diagenesis in mats and stromatolites. Previous studies showed sulfate reduction, a common promoter of carbonate precipitation in modern mats[1], is likely to have been less effective in Archean mats in marine fluids lower in sulfate[2]. Alternatively, iron reduction produces far more alkalinity per unit carbon respired than sulfate reduction. Therefore, we hypothesize iron reduction can promote much more carbonate precipitation than sulfate reduction. Our study might also have some relevance to banded iron formation on which microbial iron reduction played a potential role[3]. To test our hypothesis, Shewanella oneidensis MR-1, a dissimilatory iron reducing bacterium will be cultured anaerobically (79%N2, 20%CO2 and 1%H2) in basal medium to trigger iron reduction. Lactate will be used as electron donor, and the electron acceptor will be fresh ferrihydrite. Culture medium will be added with various metal ions, such as Ca2+ and Mg2+, to obtain potential carbonate precipitate. Escherichia coli (with fumarate added as an electron acceptor) will be used to provide a comparison to live but non-iron- reduction cells. After 20 days incubation, precipitate will be collected, washed and identified by X-ray diffraction (XRD). Besides, iron reduction rate (ferrozine assay)[4], PH and amount of precipitate (carbonate and oxidize fractions)[5] will be measured over time to well understand how S. oneidensis drives carbonate precipitation.

  2. Fabrication of Iron-Containing Carbon Materials From Graphite Fluoride

    NASA Technical Reports Server (NTRS)

    Hung, Ching-cheh

    1996-01-01

    Carbon materials containing iron alloy, iron metal, iron oxide or iron halide were fabricated. Typical samples of these metals were estimated to contain 1 iron atom per 3.5 to 5 carbon atoms. Those carbon materials containing iron alloy, iron metal, and/or Fe3O4 were magnetic. The kinetics of the fabrication process were studied by exposing graphite fluoride (CF(0.68)) to FeCl3 over a 280 to 420 C temperature range. Between 280 and 295 C, FeCl3 quickly entered the structure of CF(0.68), broke the carbon-fluorine bonds, and within 10 to 30 min, completely converted it to carbon made up of graphite planes between which particles of crystalline FeF3 and noncrystalline FeCl3 were located. Longer reaction times (e.g., 28 hr) or higher reaction temperatures (e.g., 420 C) produced materials containing graphite, a FeCl3-graphite intercalation compound, FeCl2(center dot)4H2O, and FeCl2(center dot)2H2O. These products were further heat treated to produce iron-containing carbon materials. When the heating temperature was kept in the 750 to 850 C range, and the oxygen supply was kept at the optimum level, the iron halides in the carbon structure were converted to iron oxides. Raising the heat to temperatures higher than 900 C reduced such iron oxides to iron metal. The kinetics of these reactions were used to suggest processes for fabricating carbon materials containing iron alloy. Such processes were then tested experimentally. In one of the successful trial runs, commercially purchased CF(0.7) powder was used as the reactant, and NiO was added during the final heating to 1200 C as a source of both nickel and oxygen. The product thus obtained was magnetic and was confirmed to be a nickel-iron alloy in carbon.

  3. In-Situ Regeneration of Saturated Granular Activated Carbon by an Iron Oxide Nanocatalyst

    EPA Science Inventory

    Granular activated carbon (GAC) can remove trace organic pollutants and natural organic matter (NOM) from industrial and municipal waters. This paper evaluates an iron nanocatalyst approach, based on Fenton-like oxidation reactions, to regenerate spent GAC within a packed bed con...

  4. Iron-carbonate interaction at Earth's core-mantle boundary

    NASA Astrophysics Data System (ADS)

    Dorfman, S. M.; Badro, J.; Nabiei, F.; Prakapenka, V.; Gillet, P.

    2015-12-01

    Carbon storage and flux in the deep Earth are moderated by oxygen fugacity and interactions with iron-bearing phases. The amount of carbon stored in Earth's mantle versus the core depends on carbon-iron chemistry at the core-mantle boundary. Oxidized carbonates subducted from Earth's surface to the lowermost mantle may encounter reduced Fe0 metal from disproportionation of Fe2+ in lower mantle silicates or mixing with the core. To understand the fate of carbonates in the lowermost mantle, we have performed experiments on sandwiches of single-crystal (Ca0.6Mg0.4)CO3 dolomite and Fe foil in the laser-heated diamond anvil cell at lower mantle conditions of 49-110 GPa and 1800-2500 K. Syntheses were conducted with in situ synchrotron X-ray diffraction to identify phase assemblages. After quench to ambient conditions, samples were sectioned with a focused Ga+ ion beam for composition analysis with transmission electron microscopy. At the centers of the heated spots, iron melted and reacted completely with the carbonate to form magnesiowüstite, iron carbide, diamond, magnesium-rich carbonate and calcium carbonate. In samples heated at 49 and 64 GPa, the two carbonates exhibit a eutectoid texture. In the sample heated at 110 GPa, the carbonates form rounded ~150-nm-diameter grains with a higher modal proportion of interspersed diamonds. The presence of reduced iron in the deep lower mantle and core-mantle boundary region will promote the formation of diamonds in carbonate-bearing subducted slabs. The complete reaction of metallic iron to oxides and carbides in the presence of mantle carbonate supports the formation of these phases at the Earth's core-mantle boundary and in ultra-low velocity zones.

  5. Iron encapsulated in 3D N-doped carbon nanotube/porous carbon hybrid from waste biomass for enhanced oxidative activity.

    PubMed

    Yao, Yunjin; Zhang, Jie; Wu, Guodong; Wang, Shaobin; Hu, Yi; Su, Cong; Xu, Tongwen

    2017-03-01

    Novel iron encapsulated in nitrogen-doped carbon nanotubes (CNTs) supported on porous carbon (Fe@N-C) 3D structured materials for degrading organic pollutants were fabricated from a renewable, low-cost biomass, melamine, and iron salt as the precursors. SEM and TEM micrographs show that iron encapsulated bamboo shaped CNTs are vertically standing on carbon sheets, and thus, a 3D hybrid was formed. The catalytic activities of the prepared samples were thoroughly evaluated by activation of peroxymonosulfate for catalytic oxidation of Orange II solutions. The influences of some reaction conditions (pH, temperature, and concentrations of reactants, peroxymonosulfate, and dye) were extensively evaluated. It was revealed that the adsorption could enrich the pollutant which was then rapidly degraded by the catalytically generated radicals, accelerating the continuous adsorption of residual pollutant. Remarkable carbon structure, introduction of CNTs, and N/Fe doping result in promoted adsorption capability and catalytic performances. Due to the simple synthetic process and cheap carbon precursor, Fe@N-C 3D hybrid can be easily scaled up and promote the development of Fenton-like catalysts.

  6. Preparation of iron oxide-impregnated spherical granular activated carbon-carbon composite and its photocatalytic removal of methylene blue in the presence of oxalic acid.

    PubMed

    Kadirova, Zukhra C; Hojamberdiev, Mirabbos; Katsumata, Ken-Ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Sharipov, Khasan; Okada, Kiyoshi

    2014-01-01

    The spherical granular activated carbon-carbon composites (GAC-Fe) with different iron oxide contents (Fe mass% = 0.6-10) were prepared by a pore volume impregnation method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2-adsorption results confirm the presence of amorphous iron oxide, pyrolytic carbon, and graphitized globular carbon nanoparticles covered with amorphous carbon in the CAG-Fe. The rate of photodegradation of methylene blue (MB) in aqueous solution under UV light in the presence of oxalic acid correlates with porosity of the prepared materials. The total MB removal includes the combination of adsorption and photodegradation without the addition of H2O2. The results of total organic carbon (TOC) analysis reveal that the decolorization of MB in aqueous solution containing oxalic acid corresponds to the decomposition of organic compounds to CO2 and H2O.

  7. State-Space Estimation of Soil Organic Carbon Stock

    NASA Astrophysics Data System (ADS)

    Ogunwole, Joshua O.; Timm, Luis C.; Obidike-Ugwu, Evelyn O.; Gabriels, Donald M.

    2014-04-01

    Understanding soil spatial variability and identifying soil parameters most determinant to soil organic carbon stock is pivotal to precision in ecological modelling, prediction, estimation and management of soil within a landscape. This study investigates and describes field soil variability and its structural pattern for agricultural management decisions. The main aim was to relate variation in soil organic carbon stock to soil properties and to estimate soil organic carbon stock from the soil properties. A transect sampling of 100 points at 3 m intervals was carried out. Soils were sampled and analyzed for soil organic carbon and other selected soil properties along with determination of dry aggregate and water-stable aggregate fractions. Principal component analysis, geostatistics, and state-space analysis were conducted on the analyzed soil properties. The first three principal components explained 53.2% of the total variation; Principal Component 1 was dominated by soil exchange complex and dry sieved macroaggregates clusters. Exponential semivariogram model described the structure of soil organic carbon stock with a strong dependence indicating that soil organic carbon values were correlated up to 10.8m.Neighbouring values of soil organic carbon stock, all waterstable aggregate fractions, and dithionite and pyrophosphate iron gave reliable estimate of soil organic carbon stock by state-space.

  8. Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon.

    PubMed

    Genovese, Chiara; Schuster, Manfred E; Gibson, Emma K; Gianolio, Diego; Posligua, Victor; Grau-Crespo, Ricardo; Cibin, Giannantonio; Wells, Peter P; Garai, Debi; Solokha, Vladyslav; Krick Calderon, Sandra; Velasco-Velez, Juan J; Ampelli, Claudio; Perathoner, Siglinda; Held, Georg; Centi, Gabriele; Arrigo, Rosa

    2018-03-05

    The carbon-carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (-0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials.

  9. 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).

  10. Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst

    NASA Astrophysics Data System (ADS)

    Li, Wenhui; Wu, Xiaofeng; Li, Shuangde; Tang, Wenxiang; Chen, Yunfa

    2018-04-01

    The synthesis of effective and recyclable Fenton-like catalyst is still a key factor for advanced oxidation processes. Herein, magnetic porous Fe3O4/carbon octahedra were constructed by a two-step controlled calcination of iron-based metal organic framework. The porous octahedra were assembled by interpenetrated Fe3O4 nanoparticles coated with graphitic carbon layer, offering abundant mesoporous channels for the solid-liquid contact. Moreover, the oxygen-containing functional groups on the surface of graphitic carbon endow the catalysts with hydrophilic nature and well-dispersion into water. The porous Fe3O4/carbon octahedra show efficiently heterogeneous Fenton-like reactions for decomposing the organic dye methylene blue (MB) with the help of H2O2, and nearly 100% removal efficiency within 60 min. Furthermore, the magnetic catalyst retains the activity after ten cycles and can be easily separated by external magnetic field, indicating the long-term catalytic durability and recyclability. The good Fenton-like catalytic performance of the as-synthesized Fe3O4/carbon octahedra is ascribed to the unique mesoporous structure derived from MOF-framework, as well as the sacrificial role and stabilizing effect of graphitic carbon layer. This work provides a facile strategy for the controllable synthesis of integrated porous octahedral structure with graphitic carbon layer, and thereby the catalyst holds significant potential for wastewater treatment.

  11. Iron [Fe(0)]-rich substrate based on iron-carbon micro-electrolysis for phosphorus adsorption in aqueous solutions.

    PubMed

    Deng, Shihai; Li, Desheng; Yang, Xue; Xing, Wei; Li, Jinlong; Zhang, Qi

    2017-02-01

    The phosphorus (P) adsorption properties of an iron [Fe(0)]-rich substrate (IRS) composed of iron scraps and activated carbon were investigated based on iron-carbon micro-electrolysis (IC-ME) and compared to the substrates commonly used in constructed wetlands (CWs) to provide an initial characterization of the [Fe(0)]-rich substrate. The results showed that P was precipitated by Fe(III) dissolved from the galvanic cell reactions in the IRS and the reaction was suppressed by the pH and stopped when the pH exceeded 8.90 ± 0.09. The adsorption capacity of the IRS decreased by only 4.6% in the second round of adsorption due to Fe(0) consumption in the first round. Substrates with high Ca- and Mg-oxide contents and high Fe- and Al-oxide contents had higher P adsorption capacities at high and low pH values, respectively. Substrates containing high Fe and Al concentrations and low Ca concentrations were more resistant to decreases in the P adsorption capacity resulting from organic matter (OM) accumulation. The IRS with an iron scrap to activated carbon volume ratio of 3:2 resulted in the highest P adsorption capacity (9.34 ± 0.14 g P kg -1 ), with minimal pH change and strong adaptability to OM accumulation. The Fe(0)-rich substrate has the considerable potential for being used as a CW substrate. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Effect of carbon content on friction and wear of cast irons

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1977-01-01

    Friction and wear experiments were conducted with cast irons and wrought steels containing various amounts of carbon in the alloy structure in contact with 52100 steel. Gray cast irons were found to exhibit lower friction and wear characteristics than white cast irons. Further, gray cast iron wear was more sensitive to carbon content than was white. Wear with gray cast iron was linearly related to load, and friction was found to be sensitive to relative humidity and carbon content. The form, in which the carbon is present in the alloy, is more important, as the carbon content and no strong relationship seems to exist between hardness of these ferrous alloys and wear.

  13. 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.

  14. Iron-bound organic carbon in forest soils: quantification and characterization

    DOE PAGES

    Zhao, Qian; Poulson, Simon R.; Obrist, Daniel; ...

    2016-08-24

    Iron oxide minerals play an important role in stabilizing organic carbon (OC) and regulating the biogeochemical cycles of OC on the earth surface. To predict the fate of OC, it is essential to understand the amount, spatial variability, and characteristics of Fe-bound OC in natural soils. In this study, we investigated the concentrations and characteristics of Fe-bound OC in soils collected from 14 forests in the United States and determined the impact of ecogeographical variables and soil physicochemical properties on the association of OC and Fe minerals. On average, Fe-bound OC contributed 37.8 % of total OC (TOC) in forestmore » soils. Atomic ratios of OC : Fe ranged from 0.56 to 17.7, with values of 1–10 for most samples, and the ratios indicate the importance of both sorptive and incorporative interactions. The fraction of Fe-bound OC in TOC (fFe-OC) was not related to the concentration of reactive Fe, which suggests that the importance of association with Fe in OC accumulation was not governed by the concentration of reactive Fe. Concentrations of Fe-bound OC and fFe-OC increased with latitude and reached peak values at a site with a mean annual temperature of 6.6 °C. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) and near-edge X-ray absorption fine structure (NEXAFS) analyses revealed that Fe-bound OC was less aliphatic than non-Fe-bound OC. Fe-bound OC also was more enriched in 13C compared to the non-Fe-bound OC, but C/N ratios did not differ substantially. In summary, 13C-enriched OC with less aliphatic carbon and more carboxylic carbon was associated with Fe minerals in the soils, with values of fFe-OC being controlled by both sorptive and incorporative associations between Fe and OC. Overall, this study demonstrates that Fe oxides play an important role in regulating the biogeochemical cycles of C in forest soils and uncovers the governing factors for the spatial variability and characteristics of Fe-bound OC.« less

  15. Iron-carbon composites for the remediation of chlorinated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Sunkara, Bhanu Kiran

    This research is focused on engineering submicron spherical carbon particles as effective carriers/supports for nanoscale zerovalent iron (NZVI) particles to address the in situ remediation of soil and groundwater chlorinated contaminants. Chlorinated hydrocarbons such as trichloroethylene (TCE) and tetrachloroethylene (PCE) form a class of dense non-aqueous phase liquid (DNAPL) toxic contaminants in soil and groundwater. The in situ injection of NZVI particles to reduce DNAPLs is a potentially simple, cost-effective, and environmentally benign technology that has become a preferred method in the remediation of these compounds. However, unsupported NZVI particles exhibit ferromagnetism leading to particle aggregation and loss in mobility through the subsurface. This work demonstrates two approaches to prepare carbon supported NZVI (iron-carbon composites) particles. The objective is to establish these iron-carbon composites as extremely useful materials for the environmental remediation of chlorinated hydrocarbons and suitable materials for the in situ injection technology. This research also demonstrates that it is possible to vary the placement of iron nanoparticles either on the external surface or within the interior of carbon microspheres using a one-step aerosol-based process. The simple process of modifying iron placement has significant potential applications in heterogeneous catalysis as both the iron and carbon are widely used catalysts and catalyst supports. Furthermore, the aerosol-based process is applied to prepare new class of supported catalytic materials such as carbon-supported palladium nanoparticles for ex situ remediation of contaminated water. The iron-carbon composites developed in this research have multiple functionalities (a) they are reactive and function effectively in reductive dehalogenation (b) they are highly adsorptive thereby bringing the chlorinated compound to the proximity of the reactive sites and also serving as adsorption

  16. Reactive-transport modeling of iron diagenesis and associated organic carbon remineralization in a Florida (USA) subterranean estuary

    USGS Publications Warehouse

    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.

  17. Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

    USGS Publications Warehouse

    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

  18. Iron-carbon compacts and process for making them

    DOEpatents

    Sheinberg, Haskell

    2000-01-01

    The present invention includes iron-carbon compacts and a process for making them. The process includes preparing a slurry comprising iron powder, furfuryl alcohol, and a polymerization catalyst for initiating the polymerization of the furfuryl alcohol into a resin, and heating the slurry to convert the alcohol into the resin. The resulting mixture is pressed into a green body and heated to form the iron-carbon compact. The compact can be used as, or machined into, a magnetic flux concentrator for an induction heating apparatus.

  19. Iron-Doped Carbon Aerogels: Novel Porous Substrates for Direct Growth of Carbon Nanotubes

    DOE R&D Accomplishments Database

    Steiner, S. A.; Baumann, T. F.; Kong, J.; Satcher, J. H.; Dresselhaus, M. S.

    2007-02-20

    We present the synthesis and characterization of Fe-doped carbon aerogels (CAs) and demonstrate the ability to grow carbon nanotubes directly on monoliths of these materials to afford novel carbon aerogel-carbon nanotube composites. Preparation of the Fe-doped CAs begins with the sol-gel polymerization of the potassium salt of 2,4-dihydroxybenzoic acid with formaldehyde, affording K{sup +}-doped gels that can then be converted to Fe{sup 2+}- or Fe{sup 3+}-doped gels through an ion exchange process, dried with supercritical CO{sub 2} and subsequently carbonized under an inert atmosphere. Analysis of the Fe-doped CAs by TEM, XRD and XPS revealed that the doped iron species are reduced during carbonization to form metallic iron and iron carbide nanoparticles. The sizes and chemical composition of the reduced Fe species were related to pyrolysis temperature as well as the type of iron salt used in the ion exchange process. Raman spectroscopy and XRD analysis further reveal that, despite the presence of the Fe species, the CA framework is not significantly graphitized during pyrolysis. The Fe-doped CAs were subsequently placed in a thermal CVD reactor and exposed to a mixture of CH{sub 4} (1000 sccm), H{sub 2} (500 sccm), and C{sub 2}H{sub 4} (20 sccm) at temperatures ranging from 600 to 800 C for 10 minutes, resulting in direct growth of carbon nanotubes on the aerogel monoliths. Carbon nanotubes grown by this method appear to be multiwalled ({approx}25 nm in diameter and up to 4 mm long) and grow through a tip-growth mechanism that pushes catalytic iron particles out of the aerogel framework. The highest yield of CNTs were grown on Fe-doped CAs pyrolyzed at 800 C treated at CVD temperatures of 700 C.

  20. 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.

  1. Preservation of organic matter in marine sediments by inner-sphere interactions with reactive iron

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

    Barber, Andrew; Brandes, Jay; Leri, Alessandra

    Interactions between organic matter and mineral matrices are critical to the preservation of soil and sediment organic matter. In addition to clay minerals, Fe(III) oxides particles have recently been shown to be responsible for the protection and burial of a large fraction of sedimentary organic carbon (OC). Through a combination of synchrotron X-ray techniques and high-resolution images of intact sediment particles, we assessed the mechanism of interaction between OC and iron, as well as the composition of organic matter co-localized with ferric iron. We present scanning transmission x-ray microscopy images at the Fe L 3 and C K1 edges showingmore » that the organic matter co-localized with Fe(III) consists primarily of C=C, C=O and C-OH functional groups. Coupling the co-localization results to iron K-edge X-ray absorption spectroscopy fitting results allowed to quantify the relative contribution of OC-complexed Fe to the total sediment iron and reactive iron pools, showing that 25–62% of total reactive iron is directly associated to OC through inner-sphere complexation in coastal sediments, as much as four times more than in low OC deep sea sediments. Direct inner-sphere complexation between OC and iron oxides (Fe-O-C) is responsible for transferring a large quantity of reduced OC to the sedimentary sink, which could otherwise be oxidized back to CO 2.« less

  2. Linkage of iron elution and dissolved oxygen consumption with removal of organic pollutants by nanoscale zero-valent iron: Effects of pH on iron dissolution and formation of iron oxide/hydroxide layer.

    PubMed

    Fujioka, Nanae; Suzuki, Moe; Kurosu, Shunji; Kawase, Yoshinori

    2016-02-01

    The iron elution and dissolved oxygen (DO) consumption in organic pollutant removal by nanoscale zero-valent iron (nZVI) was examined in the range of solution pH from 3.0 to 9.0. Their behaviors were linked with the removal of organic pollutant through the dissolution of iron and the formation of iron oxide/hydroxide layer affected strongly by solution pH and DO. As an example of organic pollutants, azo-dye Orange II was chosen in this study. The chemical composition analyses before and after reaction confirmed the corrosion of nZVI into ions, the formation of iron oxide/hydroxide layer on nZVI surface and the adsorption of the pollutant and its intermediates. The complete decolorization of Orange II with nZVI was accomplished very quickly. On the other hand, the total organic carbon (TOC) removal was considerably slow and the maximum TOC removal was around 40% obtained at pH 9.0. The reductive cleavage of azo-bond by emitted electrons more readily took place as compared with the cleavage of aromatic rings of Orange II leading to the degradation to smaller molecules and subsequently the mineralization. A reaction kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach was developed to elucidate mechanisms for organic pollutant removal controlled by the formation of iron oxide/hydroxide layer, the progress of which could be characterized by considering the dynamic concentration changes in Fe(2+) and DO. The dynamic profiles of Orange II removal linked with Fe(2+) and DO could be reasonably simulated in the range of pH from 3.0 to 9.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Thick-shelled, grazer-protected diatoms decouple ocean carbon and silicon cycles in the iron-limited Antarctic Circumpolar Current

    PubMed Central

    Assmy, Philipp; Smetacek, Victor; Montresor, Marina; Klaas, Christine; Henjes, Joachim; Strass, Volker H.; Arrieta, Jesús M.; Bathmann, Ulrich; Berg, Gry M.; Breitbarth, Eike; Cisewski, Boris; Friedrichs, Lars; Fuchs, Nike; Herndl, Gerhard J.; Jansen, Sandra; Krägefsky, Sören; Latasa, Mikel; Peeken, Ilka; Röttgers, Rüdiger; Scharek, Renate; Schüller, Susanne E.; Steigenberger, Sebastian; Webb, Adrian; Wolf-Gladrow, Dieter

    2013-01-01

    Diatoms of the iron-replete continental margins and North Atlantic are key exporters of organic carbon. In contrast, diatoms of the iron-limited Antarctic Circumpolar Current sequester silicon, but comparatively little carbon, in the underlying deep ocean and sediments. Because the Southern Ocean is the major hub of oceanic nutrient distribution, selective silicon sequestration there limits diatom blooms elsewhere and consequently the biotic carbon sequestration potential of the entire ocean. We investigated this paradox in an in situ iron fertilization experiment by comparing accumulation and sinking of diatom populations inside and outside the iron-fertilized patch over 5 wk. A bloom comprising various thin- and thick-shelled diatom species developed inside the patch despite the presence of large grazer populations. After the third week, most of the thinner-shelled diatom species underwent mass mortality, formed large, mucous aggregates, and sank out en masse (carbon sinkers). In contrast, thicker-shelled species, in particular Fragilariopsis kerguelensis, persisted in the surface layers, sank mainly empty shells continuously, and reduced silicate concentrations to similar levels both inside and outside the patch (silica sinkers). These patterns imply that thick-shelled, hence grazer-protected, diatom species evolved in response to heavy copepod grazing pressure in the presence of an abundant silicate supply. The ecology of these silica-sinking species decouples silicon and carbon cycles in the iron-limited Southern Ocean, whereas carbon-sinking species, when stimulated by iron fertilization, export more carbon per silicon. Our results suggest that large-scale iron fertilization of the silicate-rich Southern Ocean will not change silicon sequestration but will add carbon to the sinking silica flux. PMID:24248337

  4. Iron-mediated soil carbon response to water-table decline in an alpine wetland

    PubMed Central

    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

  5. 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.

  6. Linking carbon and iron cycles by investigating transport, fate and mineralogy of iron-bearing colloids from peat-draining rivers - Scotland as model for high-latitude rivers

    NASA Astrophysics Data System (ADS)

    Wood, Deborah; Crocket, Kirsty; Brand, Tim; Stutter, Marc; Wilson, Clare; Schröder, Christian

    2016-04-01

    Linking carbon and iron cycles by investigating transport, fate and mineralogy of iron-bearing colloids from peat-draining rivers - Scotland as model for high-latitude rivers Wood, D.A¹, Crocket, K², Brand, T², Stutter, M³, Wilson, C¹ & Schröder, C¹ ¹Biological and Environmental Sciences, University of Stirling, Stirling, FK9 4LA ²Scottish Association for Marine Science, University of the Highlands and Islands, Dunbeg, Oban, PA37 1QA ³James Hutton Institute, Craigiebuckler, Aberdeen, AB15 8QH The biogeochemical iron cycle exerts significant control on the carbon cycle¹. Iron is a limiting nutrient in large areas of the world's oceans and its bioavailability controls CO2 uptake by marine photosynthesizing microorganisms. While atmospheric iron inputs to the open ocean have been extensively measured, global river inputs have likely been underestimated because most major world rivers exhibit extensive iron removal by flocculation and sedimentation during seawater mixing. Iron minerals and organic matter mutually stabilise each other², which results in a 'rusty carbon sink' in sediments³ on the one hand but may also enhance transport beyond the salinity gradient on the other. Humic-rich, high latitude rivers have a higher iron-carrying capacity⁴-⁶ but are underrepresented in iron flux calculations. The West Coast sea lochs in Scotland are fed by predominantly peatland drainage catchments, and the rivers entering the sea lochs carry a high load of organic matter. The short distance between many of these catchments and the coastal ocean facilitates source-to-sea research investigating transport, fate and mineralogy of iron-bearing colloids providing a good analogue for similar high latitude fjordic systems. We use SeaFAST+ICP-MS and Mössbauer spectroscopy to survey trace metal concentrations, with emphasis on iron concentrations, speciation and mineralogy, across salinity gradients. In combination with ultra-filtration techniques, this allows

  7. Investigation of the mechanisms of membrane fouling by intracellular organic matter under different iron treatments during ultrafiltration.

    PubMed

    Huang, Weiwei; Qin, Xiao; Dong, Bingzhi; Zhou, Wenzong; Lv, Weiguang

    2018-05-30

    Iron is an important trace element in algal growth and water eutrophication. This study focused on the ultrafiltration (UF) membrane fouling mechanism by the intracellular organic matter (IOM) of Microcystis aeruginosa under different iron treatments. The results indicated that the membranes experienced faster flux decline and worse fouling reversibility when the IOM formed under low iron concentrations. In contrast, less IOM membrane fouling was found under normal and high iron concentrations. The mass balances of the dissolved organic carbon (DOC) content implied that the IOM in the low-iron treatment was associated with higher IOM retention and a higher capacity of reversibly deposited organics, whereas more IOM in the high-iron treatment passed through the UF membrane. The IOM in the low-iron treatment was composed of more biopolymer macromolecules, whereas the IOM in the high-iron treatment contained more UV-absorbing hydrophobic organics. The fluorescence excitation-emission matrix (EEM) spectra coupled with peak-fitting analysis implied that the fouling associated with protein-like components was more irreversible in the low-iron treatment than those in the normal- and high-iron treatments. Cake formation combined with intermediate blocking was identified as the main membrane fouling mechanism responsible for the flux decline caused by IOM solutions in the three iron treatments in this study. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Evidence for iron-sulfate coupling in salt marsh sediments

    NASA Astrophysics Data System (ADS)

    Mills, Jennifer; Antler, Gilad; Turchyn, Alexandra

    2014-05-01

    Organic carbon burial in shallow marine sediments represents an important net sink in the global carbon cycle. Microbially mediated oxidation of organic matter in oxic, suboxic, and anoxic sediments however, prevents the ultimate burial of organic carbon and its removal from the surface of the planet. Although the subsurface transformations of organic carbon have been studied extensively, an enigmatic question remains: when organic matter is deposited, what determines whether it will be buried, reoxidized, or undergo methanogenesis? One hypothesis is that the sulfur cycle, due to the abundance of sulfate in many surface environments, dominates the subsurface oxidation or other fate of organic carbon. However, it has also been suggested that iron may in turn play a key role in determining the behavior of the sulfur cycle. To better understand the controls on these processes, we are using stable isotope and geochemical techniques to explore the microbially mediated oxidation of organic carbon in salt marsh sediments in North Norfolk, UK. In these sediments there is a high supply of organic carbon, iron, and sulfate (from diurnal tidal cycles). Thus these environments may provide insight into the nature of interactions between the carbon, iron, and sulfur cycles. A series of sampling missions was undertaken in the autumn and winter of 2013-2014. In subsurface fluid samples we observe very high ferrous iron concentrations (>1mM), indicative of extended regions of iron reduction (to over 30cm depth). Within these zones of iron reduction we would predict no sulfate reduction, and as expected δ34Ssulfate remains unchanged with depth. However, δ18Osulfate exhibits significant enrichments of up to 5 permil. This decoupling in the sulfur and oxygen isotopes of sulfate is suggestive of a sulfate recycling process in which sulfate is reduced to an intermediate sulfur species and subsequently reoxidized to sulfate. Taken together, these data suggest that microbial assemblages

  9. Characterization of bacterial community and iron corrosion in drinking water distribution systems with O3-biological activated carbon treatment.

    PubMed

    Xing, Xueci; Wang, Haibo; Hu, Chun; Liu, Lizhong

    2018-07-01

    Bacterial community structure and iron corrosion were investigated for simulated drinking water distribution systems (DWDSs) composed of annular reactors incorporating three different treatments: ozone, biologically activated carbon and chlorination (O 3 -BAC-Cl 2 ); ozone and chlorination (O 3 -Cl 2 ); or chlorination alone (Cl 2 ). The lowest corrosion rate and iron release, along with more Fe 3 O 4 formation, occurred in DWDSs with O 3 -BAC-Cl 2 compared to those without a BAC filter. It was verified that O 3 -BAC influenced the bacterial community greatly to promote the relative advantage of nitrate-reducing bacteria (NRB) in DWDSs. Moreover, the advantaged NRB induced active Fe(III) reduction coupled to Fe(II) oxidation, enhancing Fe 3 O 4 formation and inhibiting corrosion. In addition, O 3 -BAC pretreatment could reduce high-molecular-weight fractions of dissolved organic carbon effectively to promote iron particle aggregation and inhibit further iron release. Our findings indicated that the O 3 -BAC treatment, besides removing organic pollutants in water, was also a good approach for controlling cast iron corrosion and iron release in DWDSs. Copyright © 2017. Published by Elsevier B.V.

  10. Synthetic effect between iron oxide and sulfate mineral on the anaerobic transformation of organic substance.

    PubMed

    Chen, Tian-Hu; Wang, Jin; Zhou, Yue-Fei; Yue, Zheng-Bo; Xie, Qiao-Qin; Pan, Min

    2014-01-01

    Synthetic effect between sulfate minerals (gypsum) and iron oxide (hematite) on the anaerobic transformation of organic substance was investigated in the current study. The results showed that gypsum was completely decomposed while hematite was partially reduced. The mineral phase analysis results showed that FeS and CaCO3 was the major mineralization product. Methane generation process was inhibited and inorganic carbon contents in the precipitates were enhanced compared to the control without hematite and gypsum. The inorganic carbon content increased with the increasing of hematite dosages. Co-addition of sulfate minerals and iron oxide would have a potential application prospect in the carbon sequestration area and reduction of the greenhouse gas release. The results would also reveal the role of inorganic mineral in the global carbon cycle. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    DOEpatents

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  12. Attrition and carbon formation on iron catalysts

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

    Kohler, S.D.; Harrington, M.S.; Jackson, N.B.

    1994-08-01

    A serious engineering problem that needs to be addressed in the scale-up of slurry-phase, Fischer-Tropsch reactors is attrition of the precipitated iron catalyst. Attrition, which can break down the catalyst into particles too small to filter, results from both mechanical and chemical forces. This study examines the chemical causes of attrition in iron catalysts. A bench-scale, slurry-phase CSTR is used to simulate operating conditions that lead to attrition of the catalyst. The average particle size and size distribution of the catalyst samples are used to determine the effect of slurry temperature, reducing gas, gas flow rate and time upon attritionmore » of the catalyst. Carbon deposition, a possible contributing factor to attrition, has been examined using gravimetric analysis and TEM. Conditions affecting the rate of carbon deposition have been compared to those leading to attrition of the precipitated iron catalyst.« less

  13. Carbonates of the Gunflint Banded Iron Formation as Analogs of Martian Carbonates

    NASA Technical Reports Server (NTRS)

    Pun, A.; Papike, J. J.; Shearer, C. K.

    2001-01-01

    Terrestrial iron formations preserve remnants of life on Earth and may serve as analogs for identifying evidence of biologic activity in martian rocks. We report on the petrography, mineralogy and trace-element abundances of carbonates of the Gunflint banded iron formation. Additional information is contained in the original extended abstract.

  14. Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism

    NASA Technical Reports Server (NTRS)

    Kaufman, A. J.; Hayes, J. M.; Knoll, A. H.; Germs, G. J.

    1991-01-01

    Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

  15. Coupling of iron and organic matter under fluctuation redox conditions: implications for carbon turnover, mineral formation, and contaminant transport

    NASA Astrophysics Data System (ADS)

    Nico, P. S.

    2015-12-01

    Interactions between naturally occurring organic matter and minerals surfaces play a determining role on the transport, chemical composition, and bio-availability of reduced carbon. These processes are controlled on the molecular scale by mineral dissolution and precipitation dynamics which are in turn controlled by both changing solution chemistry and redox regime. The presentation will highlight recent work by our group and others on elucidating some of these mechanisms with particular emphasis on the impacts of redox cycling and Fe mineral transformation. We are particular interested in how the form of organic matter impacts the formation and transformation of iron minerals and vis-a-versa under fluctuating redox conditions, and how that in turn impacts the transport of other elements controlled by Fe surfaces, e.g. uranium. In two different field conditions, in a ground water well and at a ground water-surface water interface, Fe(II) was oxidized in an organic rich environment leading to different types of Fe-organic matter co-precipitates. We followed the evolution of those participates under a return to reduced conditions in order to understand the transformations, or lack thereof, of the Fe minerals and the fate of the associated organic matter.

  16. Removal of trichloroethylene by zerovalent iron/activated carbon derived from agricultural wastes.

    PubMed

    Su, Yuh-fan; Cheng, Yu-ling; Shih, Yang-hsin

    2013-11-15

    Activated carbon (AC) and zerovalent iron (ZVI) have been widely used in the adsorption and dehalogenation process, respectively, for the removal of organic compounds in environmental treatments. This study aims to prepare ZVI/AC derived from an agricultural waste, coir pith, through simple one-step pyrolysis. The effect of activation temperature and time on the surface area, iron content, and zerovalent iron ratio of ZVI/AC was systemically investigated. The results indicated that the activation of AC by FeSO4 significantly increased surface area of AC and distributed elemental iron over the AC. The X-ray diffraction (XRD), electron spectroscopy for chemical analysis (ESCA), and X-ray absorption near edge structure (XANES) spectra of ZVI/AC revealed that zerovalent iron was present. As compared to AC without FeSO4 activation, ZVI/AC increased the trichloroethylene removal rate constant by 7 times. The dechlorination ability of ZVI/AC was dominated by the zerovalent iron content. We have shown that lab-made ZVI/AC from coir pith can effectively adsorb and dehalogenate the chlorinated compounds in water. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. The role of heterotrophic bacteria in iron-limited ocean ecosystems

    NASA Astrophysics Data System (ADS)

    Tortell, Philippe D.; Maldonado, Maria T.; Price, Nell M.

    1996-09-01

    IRON availability limits phytoplankton growth in large areas of the world's oceans1-3 and may influence the strength of the biological carbon pump4,5. Very little is known of the iron requirements of oceanic heterotrophic bacteria, which constitute up to 50% of the total particulate organic carbon in open ocean waters6,7 and are important in carbon cycling as remineralizers of dissolved organic matter and hence producers of CO2 (ref. 8). Here we report that oceanic bacteria contain more iron per biomass than phytoplankton. In the subarctic Pacific, they constitute a large fraction of biogenic iron and account for 20-45% of biological iron uptake. Bacterial iron quotas in the field are similar to those of iron-deficient laboratory cultures, which exhibit reduced elec-tron transport, slow growth, and low carbon growth efficiency. Heterotrophic bacteria therefore play a major role in the biogeo-chemical cycling of iron. In situ iron limitation of heterotrophic metabolism may have profound effects on carbon flux in the ocean.

  18. Closed system Fischer-Tropsch synthesis over meteoritic iron, iron ore and nickel-iron alloy. [deuterium-carbon monoxide reaction catalysis

    NASA Technical Reports Server (NTRS)

    Nooner, D. W.; Gibert, J. M.; Gelpi, E.; Oro, J.

    1976-01-01

    Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.

  19. Diatom resting spore ecology drives enhanced carbon export from a naturally iron-fertilized bloom in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Salter, Ian; Kemp, Alan E. S.; Moore, C. Mark; Lampitt, Richard S.; Wolff, George A.; Holtvoeth, Jens

    2012-03-01

    Southern Ocean Island systems sustain phytoplankton blooms induced by natural iron fertilization that are important for the uptake of atmospheric carbon dioxide and serve as analogues for past and future climate change. We present data on diatom flux assemblages and the biogeochemical properties of sinking particles to explain the enhanced particulate organic carbon (POC) export fluxes observed in response to natural iron supply in the Crozet Islands region (CROZeX). Moored deep-ocean sediment traps (>2000 m) were located beneath a naturally fertilized island bloom and beneath an adjacent High Nutrient Low Chlorophyll (HNLC) control site. Deep-ocean carbon flux from the naturally-fertilized bloom area was tightly correlated (R = 0.83, n = 12, P < 0.0006) with the resting spore flux of a single island-associated diatom species,Eucampia antarctica var. antarctica. The unusually well preserved state of the Eucampia-associated carbon flux, determined by amino acid studies of organic matter degradation, was likely influenced by their ecology, since diatom resting spores are adapted to settle rapidly out of the surface ocean preserving viable cells. The naturally fertilized bloom enhanced carbon flux and the resulting Si/C and Si/N ratios were 2.0-3.4-fold and 2.2-3.5-fold lower than those measured in the adjacent HNLC control area. The enhanced carbon export and distinctive stoichiometry observed in naturally fertilized systems is therefore largely not attributable to iron relief of open ocean diatoms, but rather to the advection and growth of diatom species characteristic of island systems and the subsequent flux of resting spores. Carbon export estimates from current natural iron fertilization studies therefore represent a highly specific response of the island systems chosen as natural laboratories and may not be appropriate analogues for the larger Southern Ocean response. The broader implications of our results emphasize the role of phytoplankton diversity and

  20. Sorption of Groundwater Dissolved Organic Carbon onto Minerals

    NASA Astrophysics Data System (ADS)

    Rutlidge, H.; Oudone, P.; McDonough, L.; Meredith, K.; Andersen, M. S.; O'Carrol, D. M.; Baker, A.

    2017-12-01

    Our understanding of groundwater organic matter (OM) as a carbon source or sink in the environmental carbon cycle is limited. The dynamics of groundwater OM is mainly governed by biological processing and its sorption to minerals. In saturated groundwaters, dissolved OM (DOM) represents one part of the groundwater organic carbon pool. Without consideration of the DOM sorption, it is not possible to quantify governing groundwater OM processes. This research explores the rate and extent of DOM sorption on different minerals. Groundwater DOM samples, and International Humic Substances Society (IHSS) standard solutions, were analysed. Each was mixed with a range of masses of iron coated quartz, clean quartz, and calcium carbonate, and shaken for 2 hours to reach equilibrium before being filtered through 0.2 μm for total dissolved organic carbon (DOC) and composition analysis by size-exclusion chromatography-organic carbon detection (LC-OCD). Sorption isotherms were constructed and groundwater DOM sorption were compared to the sorption of IHSS standards. Initial results suggest that for the IHSS standards, the operationally-defined humic substances fraction had the strongest sorption compared to the other LC-OCD fractions and total DOC. Some samples exhibited a small increase in the low molecular weight neutral (LMW-N) aqueous concentration with increasing humic substances sorption. This gradual increase observed could be the result of humic substances desorbing or their breakdown during the experiment. Further results comparing these IHSS standards with groundwater samples will be presented. In conjunction with complementary studies, these results can help provide more accurate prediction of whether groundwater OM is a carbon source or sink, which will enable the management of the groundwater resources as part of the carbon economy.

  1. In-situ regeneration of saturated granular activated carbon by an iron oxide nanocatalyst.

    PubMed

    Chiu, Chao-An; Hristovski, Kiril; Huling, Scott; Westerhoff, Paul

    2013-03-15

    Granular activated carbon (GAC) can remove trace organic pollutants and natural organic matter (NOM) from industrial and municipal waters. This paper evaluates an iron nanocatalyst approach, based on Fenton-like oxidation reactions, to regenerate spent GAC within a packed bed configuration after saturation by organic compounds. Specifically, we focus on regenerating GAC packed beds equilibrated with varying influent concentrations of phenol, a model organic compound. Iron nanocatalysts were synthesized using ferric chloride, a chemical already used as a coagulant at municipal WTPs, and reacted with hydrogen peroxide (H(2)O(2)) for the purpose of in-situ regeneration. Up to 95% of phenol adsorption capacity was regenerated for GAC equilibrated with 1000 mg/L of phenol. Using this technique, at least four adsorption-regeneration cycles can be performed sequentially for the same batch of GAC with fresh iron nanocatalysts while achieving a regeneration efficiency of 90 ± 5% between each loading. Moreover, the iron nanocatalyst can be recovered and reused multiple times. Lower initial adsorbate concentrations (10-500 mg/L) resulted in a slightly lower saturated adsorbent-phase concentration of phenol and lower regeneration efficiencies (72 ± 5%). Additionally, this catalytic in-situ regeneration was applied to GAC saturated by NOM. A slightly lower regeneration efficiency (60%) was observed for the Suwannee River NOM adsorption capacity of GAC. The next step is validation in a pilot-scale test that applies this regeneration technique to a GAC adsorber employed in NOM removal. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Effect of atmospheric organic complexation on iron-bearing dust solubility

    NASA Astrophysics Data System (ADS)

    Paris, R.; Desboeufs, K. V.

    2013-02-01

    Recent studies reported that the effect of organic complexation may be a potentially important process to be considered in models to estimate atmospheric iron flux to the ocean. In this study, we investigated this effect by a series of dissolution experiments on iron-bearing dust in presence or absence of various organic compounds typically found in the atmospheric waters (acetate, formate, oxalate, malonate, succinate, glutarate, glycolate, lactate, tartrate and humic acid as an analogue of humic like substances (HULIS)). Only 4 of tested organic ligands (oxalate, malonate, tartrate and humic acid) caused an enhancement of iron solubility which was associated with an increase of dissolved Fe(II) concentrations. For all of these organic ligands, a positive linear dependence of iron solubility to organic concentrations was observed and showed that the extent of organic complexation on iron solubility decreased in order oxalate > malonate = tartrate > humic acid. This was attributed to the ability of electron donors of organic ligands and implied a reductive ligand-promoted dissolution. This study confirmed that oxalate is the most effective ligand playing on dust iron solubility and showed, for the first time, the potential effect of HULIS on iron dissolution in atmospheric conditions.

  3. Tropical forest soil microbial communities couple iron and carbon biogeochemistry

    Treesearch

    Eric A. Dubinsky; Whendee L. Silver; Mary K. Firestone

    2010-01-01

    We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500–5000 mm/yr) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally...

  4. Iron defecation by sperm whales stimulates carbon export in the Southern Ocean

    PubMed Central

    Lavery, Trish J.; Roudnew, Ben; Gill, Peter; Seymour, Justin; Seuront, Laurent; Johnson, Genevieve; Mitchell, James G.; Smetacek, Victor

    2010-01-01

    The iron-limited Southern Ocean plays an important role in regulating atmospheric CO2 levels. Marine mammal respiration has been proposed to decrease the efficiency of the Southern Ocean biological pump by returning photosynthetically fixed carbon to the atmosphere. Here, we show that by consuming prey at depth and defecating iron-rich liquid faeces into the photic zone, sperm whales (Physeter macrocephalus) instead stimulate new primary production and carbon export to the deep ocean. We estimate that Southern Ocean sperm whales defecate 50 tonnes of iron into the photic zone each year. Molar ratios of Cexport ∶Feadded determined during natural ocean fertilization events are used to estimate the amount of carbon exported to the deep ocean in response to the iron defecated by sperm whales. We find that Southern Ocean sperm whales stimulate the export of 4 × 105 tonnes of carbon per year to the deep ocean and respire only 2 × 105 tonnes of carbon per year. By enhancing new primary production, the populations of 12 000 sperm whales in the Southern Ocean act as a carbon sink, removing 2 × 105 tonnes more carbon from the atmosphere than they add during respiration. The ability of the Southern Ocean to act as a carbon sink may have been diminished by large-scale removal of sperm whales during industrial whaling. PMID:20554546

  5. Intracellular degradation of functionalized carbon nanotube/iron oxide hybrids is modulated by iron via Nrf2 pathway

    PubMed Central

    Elgrabli, Dan; Dachraoui, Walid; Marmier, Hélène de; Ménard-Moyon, Cécilia; Bégin, Dominique; Bégin-Colin, Sylvie; Bianco, Alberto; Alloyeau, Damien; Gazeau, Florence

    2017-01-01

    The in vivo fate and biodegradability of carbon nanotubes is still a matter of debate despite tremendous applications. In this paper we describe a molecular pathway by which macrophages degrade functionalized multi-walled carbon nanotubes (CNTs) designed for biomedical applications and containing, or not, iron oxide nanoparticles in their inner cavity. Electron microscopy and Raman spectroscopy show that intracellularly-induced structural damages appear more rapidly for iron-free CNTs in comparison to iron-loaded ones, suggesting a role of iron in the degradation mechanism. By comparing the molecular responses of macrophages derived from THP1 monocytes to both types of CNTs, we highlight a molecular mechanism regulated by Nrf2/Bach1 signaling pathways to induce CNT degradation via NOX2 complex activation and O2•−, H2O2 and OH• production. CNT exposure activates an oxidative stress-dependent production of iron via Nrf2 nuclear translocation, Ferritin H and Heme oxygenase 1 translation. Conversely, Bach1 was translocated to the nucleus of cells exposed to iron-loaded CNTs to recycle embedded iron. Our results provide new information on the role of oxidative stress, iron metabolism and Nrf2-mediated host defence for regulating CNT fate in macrophages. PMID:28120861

  6. Carbon diffusion in solid iron as function of pressure and temperature

    NASA Astrophysics Data System (ADS)

    Stagno, V.; Crispin, K. L.; Fei, Y.

    2012-12-01

    The knowledge of carbon diffusion in metallic iron is of importance for both industrial and geological applications. In industry the diffusion properties of carbon apply to the massive production of steel through carburizing and galvanization processes at high temperature with the aim to improve the hardness and rust resistance of such materials. In geoscience the diffusion of carbon in metallic phases at high pressure and temperature is important for determining the rate of reactions and crystal growth of carbide phases likely coexisting with mantle silicates. Due to a small atomic radius, carbon is expected to dissolve by interstitial diffusion in solid metals. However, to date there are no experimental data available to understand the role that pressure plays on the mobilization of carbon through solid iron. Further, for light elements such as carbon or sulfur the activation energy is assumed to be lower than in case of lattice diffusion. However, with increasing pressure the activation volume must be taken into account to better understand diffusion processes at the atomic scale. We performed experiments using multianvil and piston cylinder devices at pressures between 1.5 and 6 GPa and temperature of 700-1200°C. Experiments were carried out using cylindrical glassy carbon sandwiched between layers of pure iron rods of known thickness enclosed in MgO capsule. Analytical techniques included FE-SEM for textural observation and accurate analyses of the interface between layers, while concentration profiles were measured using the electron microprobe with an optimized standardization procedure. Concentration profiles of carbon in iron were computed to determine the diffusion coefficients based on Fick's second law formulation assuming isotropic one dimension diffusion. Preliminary results confirm the positive temperature dependence of the diffusion coefficient for carbon widely discussed in literature. However, our results also show that a significant increase in

  7. Effect of atmospheric organic complexation on iron-bearing dust solubility

    NASA Astrophysics Data System (ADS)

    Paris, R.; Desboeufs, K. V.

    2013-05-01

    Recent studies reported that the effect of organic complexation may be a potentially important process to be considered by models estimating atmospheric iron flux to the ocean. In this study, we investigated this process effect by a series of dissolution experiments on iron-bearing dust in the presence or the absence of various organic compounds (acetate, formate, oxalate, malonate, succinate, glutarate, glycolate, lactate, tartrate and humic acid as an analogue of humic like substances, HULIS) typically found in atmospheric waters. Only 4 of tested organic ligands (oxalate, malonate, tartrate and humic acid) caused an enhancement of iron solubility which was associated with an increase of dissolved Fe(II) concentrations. For all of these organic ligands, a positive linear dependence of iron solubility to organic concentrations was observed and showed that the extent of organic complexation on iron solubility decreased in the following order: oxalate >malonate = tartrate > humic acid. This was attributed to the ability of electron donors of organic ligands and implies a reductive ligand-promoted dissolution. This study confirms that among the known atmospheric organic binding ligands of Fe, oxalate is the most effective ligand promoting dust iron solubility and showed, for the first time, the potential effect of HULIS on iron dissolution under atmospheric conditions.

  8. CARBON MONOXIDE REVERSIBLY DISRUPTS IRON HOMEOSTATIS AND RESPIRATORY EPITHELIAL CELLS FUNCTION

    EPA Science Inventory

    Iron dissociation from heme is a major factor in iron metabolism and cellular concentrations of the metal correlate inversely with the expression of heme oxygenase (HO). We tested the hypothesis that 1) exposure to a product of HO, carbon monoxide (CO), disturbs iron homeostas...

  9. Microwave-assisted combustion synthesis of nano iron oxide/iron-coated activated carbon, anthracite, cellulose fiber, and silica, with arsenic adsorption studies

    EPA Science Inventory

    Combustion synthesis of iron oxide/iron coated carbons such as activated carbon, anthracite, cellulose fiber and silica is described. The reactions were carried out in alumina crucibles using a Panasonic kitchen microwave with inverter technology, and the reaction process was com...

  10. Voronoi analysis of the short–range atomic structure in iron and iron–carbon melts

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

    Sobolev, Andrey; Mirzoev, Alexander

    2015-08-17

    In this work, we simulated the atomic structure of liquid iron and iron–carbon alloys by means of ab initio molecular dynamics. Voronoi analysis was used to highlight changes in the close environments of Fe atoms as carbon concentration in the melt increases. We have found, that even high concentrations of carbon do not affect short–range atomic order of iron atoms — it remains effectively the same as in pure iron melts.

  11. Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

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

    Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli

    The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe

  12. Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

    DOE PAGES

    Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli; ...

    2017-10-31

    The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe

  13. Microstructure and properties of pure iron/copper composite cladding layers on carbon steel

    NASA Astrophysics Data System (ADS)

    Wan, Long; Huang, Yong-xian; Lü, Shi-xiong; Huang, Ti-fang; Lü, Zong-liang

    2016-08-01

    In the present study, pure iron/copper composite metal cladding was deposited onto carbon steel by tungsten inert gas welding. The study focused on interfacial morphological, microstructural, and mechanical analyses of the composite cladding layers. Iron liquid-solid-phase zones were formed at copper/steel and iron interfaces because of the melting of the steel substrate and iron. Iron concentrated in the copper cladding layer was observed to exhibit belt, globule, and dendrite morphologies. The appearance of iron-rich globules indicated the occurrence of liquid phase separation (LPS) prior to solidification, and iron-rich dendrites crystallized without the occurrence of LPS. The maximum microhardness of the iron/steel interface was lower than that of the copper/steel interface because of the diffusion of elemental carbon. All samples fractured in the cladding layers. Because of a relatively lower strength of the copper layer, a short plateau region appeared when shear movement was from copper to iron.

  14. Association with pedogenic iron and aluminum: effects on soil organic carbon storage and stability in four temperate forest soils

    DOE PAGES

    Porras, Rachel C.; Hicks Pries, Caitlin E.; McFarlane, Karis J.; ...

    2017-05-13

    Soil organic carbon (SOC) can be stabilized via association with iron (Fe) and aluminum (Al) minerals. Fe and Al can be strong predictors of SOC storage and turnover in soils with relatively high extractable metals content and moderately acidic to circumneutral pH. Here we test whether pedogenic Fe and Al influence SOC content and turnover in soils with low Fe and Al content and acidic pH. In soils from four sites spanning three soil orders, we quantified the amount of Fe and Al in operationally-defined poorly crystalline and organically-complexed phases using selective chemical dissolution applied to the soil fraction containingmore » mineral-associated carbon. We evaluated the correlations of Fe and Al concentrations, mean annual precipitation (MAP), mean annual temperature (MAT), and pH with SOC content and 14C-based turnover times. We found that poorly crystalline Fe and Al content predicted SOC turnover times (p < 0.0001) consistent with findings of previous studies, while organically-complexed Fe and Al content was a better predictor of SOC concentration (p < 0.0001). Greater site-level MAP (p < 0.0001) and colder site-level MAT (p < 0.0001) were correlated with longer SOC turnover times but were not correlated with SOC content. Our results suggest that poorly crystalline Fe and Al effectively slow the turnover of SOC in these acidic soils, even when their combined content in the soil is less than 2% by mass. However, in the strongly acidic Spodosol, organo-metal complexes tended to be less stable resulting in a more actively cycling mineral-associated SOC pool.« less

  15. Association with pedogenic iron and aluminum: effects on soil organic carbon storage and stability in four temperate forest soils

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

    Porras, Rachel C.; Hicks Pries, Caitlin E.; McFarlane, Karis J.

    Soil organic carbon (SOC) can be stabilized via association with iron (Fe) and aluminum (Al) minerals. Fe and Al can be strong predictors of SOC storage and turnover in soils with relatively high extractable metals content and moderately acidic to circumneutral pH. Here we test whether pedogenic Fe and Al influence SOC content and turnover in soils with low Fe and Al content and acidic pH. In soils from four sites spanning three soil orders, we quantified the amount of Fe and Al in operationally-defined poorly crystalline and organically-complexed phases using selective chemical dissolution applied to the soil fraction containingmore » mineral-associated carbon. We evaluated the correlations of Fe and Al concentrations, mean annual precipitation (MAP), mean annual temperature (MAT), and pH with SOC content and 14C-based turnover times. We found that poorly crystalline Fe and Al content predicted SOC turnover times (p < 0.0001) consistent with findings of previous studies, while organically-complexed Fe and Al content was a better predictor of SOC concentration (p < 0.0001). Greater site-level MAP (p < 0.0001) and colder site-level MAT (p < 0.0001) were correlated with longer SOC turnover times but were not correlated with SOC content. Our results suggest that poorly crystalline Fe and Al effectively slow the turnover of SOC in these acidic soils, even when their combined content in the soil is less than 2% by mass. However, in the strongly acidic Spodosol, organo-metal complexes tended to be less stable resulting in a more actively cycling mineral-associated SOC pool.« less

  16. Influence of iron redox cycling on organo-mineral associations in Arctic tundra soil

    DOE PAGES

    Herndon, Elizabeth; Oak Ridge National Lab.; AlBashaireh, Amineh; ...

    2017-03-25

    Arctic tundra stores large quantities of soil organic matter under varying redox conditions. As the climate warms, these carbon reservoirs are susceptible to increased rates of decomposition and release to the atmosphere as the greenhouse gases carbon dioxide (CO 2) and methane (CH 4). Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in Arctic tundra systems and are not considered in decomposition models. The accumulation of iron (Fe) oxyhydroxides and organo- iron precipitates at redox interfaces may be particularly important for carbon cycling given that ferric iron [Fe(III)] species can enhancemore » decomposition by serving as terminal electron acceptors in anoxic soils or inhibit microbial decomposition by binding organic molecules. Here in this paper, we examine chemical properties of solid-phase Fe and organic matter in organic and mineral horizons within the seasonally thawed active layer of Arctic tundra on the North Slope of Alaska. Spectroscopic techniques, including micro-X-ray fluorescence ( XRF) mapping, micro-X-ray absorption near-edge structure ( XANES) spectroscopy, and Fourier transform infrared spectroscopy (FTIR), were coupled with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in soils. Organic horizons were enriched in poorly crystalline and crystalline iron oxides, and approximately 60% of total Fe stored in organic horizons was calculated to derive from upward translocation from anoxic mineral horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris, and in aggregates with clays and particulate organic matter. Minor amounts of ferrous iron [Fe(II)] were present in iron sulfides (i.e., pyrite and greigite) in mineral horizon soils and iron phosphates (vivianite) in organic horizons

  17. Influence of iron redox cycling on organo-mineral associations in Arctic tundra soil

    NASA Astrophysics Data System (ADS)

    Herndon, Elizabeth; AlBashaireh, Amineh; Singer, David; Roy Chowdhury, Taniya; Gu, Baohua; Graham, David

    2017-06-01

    Arctic tundra stores large quantities of soil organic matter under varying redox conditions. As the climate warms, these carbon reservoirs are susceptible to increased rates of decomposition and release to the atmosphere as the greenhouse gases carbon dioxide (CO2) and methane (CH4). Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in Arctic tundra systems and are not considered in decomposition models. The accumulation of iron (Fe) oxyhydroxides and organo-iron precipitates at redox interfaces may be particularly important for carbon cycling given that ferric iron [Fe(III)] species can enhance decomposition by serving as terminal electron acceptors in anoxic soils or inhibit microbial decomposition by binding organic molecules. Here, we examine chemical properties of solid-phase Fe and organic matter in organic and mineral horizons within the seasonally thawed active layer of Arctic tundra on the North Slope of Alaska. Spectroscopic techniques, including micro-X-ray fluorescence (μXRF) mapping, micro-X-ray absorption near-edge structure (μXANES) spectroscopy, and Fourier transform infrared spectroscopy (FTIR), were coupled with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in soils. Organic horizons were enriched in poorly crystalline and crystalline iron oxides, and approximately 60% of total Fe stored in organic horizons was calculated to derive from upward translocation from anoxic mineral horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris, and in aggregates with clays and particulate organic matter. Minor amounts of ferrous iron [Fe(II)] were present in iron sulfides (i.e., pyrite and greigite) in mineral horizon soils and iron phosphates (vivianite) in organic horizons. Concentrations of organic

  18. Influence of iron redox cycling on organo-mineral associations in Arctic tundra soil

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

    Herndon, Elizabeth; Oak Ridge National Lab.; AlBashaireh, Amineh

    Arctic tundra stores large quantities of soil organic matter under varying redox conditions. As the climate warms, these carbon reservoirs are susceptible to increased rates of decomposition and release to the atmosphere as the greenhouse gases carbon dioxide (CO 2) and methane (CH 4). Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in Arctic tundra systems and are not considered in decomposition models. The accumulation of iron (Fe) oxyhydroxides and organo- iron precipitates at redox interfaces may be particularly important for carbon cycling given that ferric iron [Fe(III)] species can enhancemore » decomposition by serving as terminal electron acceptors in anoxic soils or inhibit microbial decomposition by binding organic molecules. Here in this paper, we examine chemical properties of solid-phase Fe and organic matter in organic and mineral horizons within the seasonally thawed active layer of Arctic tundra on the North Slope of Alaska. Spectroscopic techniques, including micro-X-ray fluorescence ( XRF) mapping, micro-X-ray absorption near-edge structure ( XANES) spectroscopy, and Fourier transform infrared spectroscopy (FTIR), were coupled with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in soils. Organic horizons were enriched in poorly crystalline and crystalline iron oxides, and approximately 60% of total Fe stored in organic horizons was calculated to derive from upward translocation from anoxic mineral horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris, and in aggregates with clays and particulate organic matter. Minor amounts of ferrous iron [Fe(II)] were present in iron sulfides (i.e., pyrite and greigite) in mineral horizon soils and iron phosphates (vivianite) in organic horizons

  19. Preparation, Characterization and Adsorption Study of Granular Activated Carbon/Iron oxide composite for the Removal of Boron and Organics from Wastewater

    NASA Astrophysics Data System (ADS)

    Chioma Affam, Augustine; Chung Wong, Chee; Seyam, Mohammed A. B.; Matt, Chelsea Ann Anak Frederick; Lantan Anak Sumbai, Josephine; Evuti, Abdullahi Mohammed

    2018-03-01

    Boron and organics maybe in high concentration during production of oil and gas, fertilizers, glass, and detergents. In addition, boron added to these industrial processes may require to be removed by the wastewater treatment plant. The preparation, characterization and application of iron oxide-activated carbon composite for removal of boron and COD was studied. The one variable at a time (OVAT) method was implemented to obtain desirable operating conditions (adsorbent dosage 5 g/L, reaction time 2 h, agitation speed 100 rpm, pH 5 for COD removal and pH 9 for boron removal). It was found that boron and organics present in a sample wastewater may require to be treated separately to remove the contaminants. The study achieved 97 and 70% for boron and COD removal, respectively. Adsorption as an alternative cheap source of treatment and its practicability for small communities is recommended as effective in removal of contaminants from river water.

  20. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    PubMed

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Pore- and micro-structural characterization of a novel structural binder based on iron carbonation

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

    Das, Sumanta, E-mail: Sumanta.Das@asu.edu; Stone, David, E-mail: dajstone@gmail.com; Convey, Diana, E-mail: Diana.Convey@asu.edu

    2014-12-15

    The pore- and micro-structural features of a novel binding material based on the carbonation of waste metallic iron powder are reported in this paper. The binder contains metallic iron powder as the major ingredient, followed by additives containing silica and alumina to facilitate favorable reaction product formation. Compressive strengths sufficient for a majority of concrete applications are attained. The material pore structure is investigated primarily through mercury intrusion porosimetry whereas electron microscopy is used for microstructural characterization. Reduction in the overall porosity and the average pore size with an increase in carbonation duration from 1 day to 4 days ismore » noticed. The pore structure features are used in predictive models for gas and moisture transport (water vapor diffusivity and moisture permeability) through the porous medium which dictates its long-term durability when used in structural applications. Comparisons of the pore structure with those of a Portland cement paste are also provided. The morphology of the reaction products in the iron-based binder, and the distribution of constituent elements in the microstructure are also reported. - Highlights: • Carbonation of iron produces a dense microstructure. • Pore volume in iron carbonate lower, critical size higher than those in OPC pastes • Reaction product contains iron, carbon, silicon, aluminum and calcium. • Power-law for porosity-moisture permeability relationship was established.« less

  2. The Modification of Carbon with Iron Oxide Synthesized in Electrolysis Using the Arc Discharge Method

    NASA Astrophysics Data System (ADS)

    Endah Saraswati, Teguh; Dewi Indah Prasiwi, Oktaviana; Masykur, Abu; Handayani, Nestri; Anwar, Miftahul

    2017-02-01

    The modification of carbon-based nanomaterials with metals is widely studied due to its unique properties. Here, the modification of carbon nanomaterial with iron oxide has been successfully carried out. This modification was achieved using arc discharge in 50% ethanol liquid media. The anode used in the arc discharge was prepared from a mixture of carbon and iron oxide that was synthesized in electrolysis and was then calcined at 250°C with silicon binder with a mass ratio of 3:1:1, and the cathode used was graphite rod. Both electrodes were set in the nearest gap that could provide an arc during arc-discharging, leading to carbon-based nanoparticle formation. The diffractogram pattern of the X-ray diffraction of the fabricated nanoparticles confirmed the typical peak of carbon, iron oxide and iron. The magnetization value of the result analysis of the vibrating sample magnetometer was 9.9 emu/g. The bandgap energy measurement using diffuse reflectance ultra violet was estimated to be 2.18 eV. Using the transmission electron microscopy, the structure of the nanomaterial produced was observed as carbon-encapsulated iron compound nanoparticles.

  3. Effects of iron and calcium carbonate on the variation and cycling of carbon source in integrated wastewater treatments.

    PubMed

    Zhimiao, Zhao; Xinshan, Song; Yufeng, Zhao; Yanping, Xiao; Yuhui, Wang; Junfeng, Wang; Denghua, Yan

    2017-02-01

    Iron and calcium carbonate were added in wastewater treatments as the adjusting agents to improve the contaminant removal performance and regulate the variation of carbon source in integrated treatments. At different temperatures, the addition of the adjusting agents obviously improved the nitrogen and phosphorous removals. TN and TP removals were respectively increased by 29.41% and 23.83% in AC-100 treatment under 1-day HRT. Carbon source from dead algae was supplied as green microbial carbon source and Fe 2+ was supplied as carbon source surrogate. COD concentration was increased to 30mg/L and above, so the problem of the shortage of carbon source was solved. Dead algae and Fe 2+ as carbon source supplement or surrogate played significant role, which was proved by microbial community analysis. According to the denitrification performance in the treatments, dead algae as green microbial carbon source combined with iron and calcium carbonate was the optimal supplement carbon source in wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Export fluxes in a naturally iron-fertilized area of the Southern Ocean - Part 1: Seasonal dynamics of particulate organic carbon export from a moored sediment trap

    NASA Astrophysics Data System (ADS)

    Rembauville, M.; Salter, I.; Leblond, N.; Gueneugues, A.; Blain, S.

    2015-06-01

    A sediment trap moored in the naturally iron-fertilized Kerguelen Plateau in the Southern Ocean provided an annual record of particulate organic carbon and nitrogen fluxes at 289 m. At the trap deployment depth, current speeds were typically low (~ 10 cm s-1) and primarily tidal-driven (M2 tidal component). Although advection was weak, the sediment trap may have been subject to hydrodynamical and biological (swimmer feeding on trap funnel) biases. Particulate organic carbon (POC) flux was generally low (< 0.5 mmol m-2 d-1), although two episodic export events (< 14 days) of 1.5 mmol m-2 d-1 were recorded. These increases in flux occurred with a 1-month time lag from peaks in surface chlorophyll and together accounted for approximately 40% of the annual flux budget. The annual POC flux of 98.2 ± 4.4 mmol m-2 yr-1 was low considering the shallow deployment depth but comparable to independent estimates made at similar depths (~ 300 m) over the plateau, and to deep-ocean (> 2 km) fluxes measured from similarly productive iron-fertilized blooms. Although undertrapping cannot be excluded in shallow moored sediment trap deployment, we hypothesize that grazing pressure, including mesozooplankton and mesopelagic fishes, may be responsible for the low POC flux beneath the base of the winter mixed layer. The importance of plankton community structure in controlling the temporal variability of export fluxes is addressed in a companion paper.

  5. Iron cycling at corroding carbon steel surfaces.

    PubMed

    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.

  6. Iron cycling at corroding carbon steel surfaces

    PubMed Central

    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 three 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. PMID:24093730

  7. Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water.

    PubMed

    Nieto-Delgado, Cesar; Rangel-Mendez, Jose Rene

    2012-06-01

    The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl(3) concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Enhanced terrestrial carbon preservation promoted by reactive iron in deltaic sediments

    NASA Astrophysics Data System (ADS)

    Shields, Michael R.; Bianchi, Thomas S.; Gélinas, Yves; Allison, Mead A.; Twilley, Robert R.

    2016-02-01

    We examined the role of reactive iron (FeR) in preserving organic carbon (OC) across a subaerial chronosequence of the Wax Lake Delta, a prograding delta within the Mississippi River Delta complex. We found that ~15.0% of the OC was bound to FeR, and the dominant binding mechanisms varied from adsorption in the youngest subaerial region to coprecipitation at the older, vegetated sites. The δ13C of the iron-associated OC was more negative than the total OC (mean = -2.6‰), indicating greater preference for terrestrial material and/or compounds with more negative δ13C values. However, only the adsorbed OC displayed preferential binding of lignin phenols. We estimate that ~8% of the OC initially deposited in deltaic systems is bound to FeR (equivalent to 6 × 1012 gC yr-1), and this percentage increases postdepositionally, as coprecipitation of FeR and OC allows for an even greater amount of OC to be bound to FeR.

  9. Ion probe measurements of carbon and nitrogen in iron meteorites

    NASA Astrophysics Data System (ADS)

    Sugiura, Naoji

    1998-05-01

    Carbon and nitrogen distributions in iron meteorites, their concentrations in various phases, and their isotopic compositions in certain phases were measured by secondary ion mass spectrometry (SIMS). Taenite (and its decomposition products) is the main carrier of carbon except for IAB irons where graphite and/or carbide (cohenite) may be the main carrier. Taenite is also the main carrier of nitrogen in most iron meteorites unless nitrides (carlsbergite CrN or roaldite (Fe,Ni)4N) are present. Carbon and nitrogen distributions in taenite are well correlated, unless carbides and/or nitrides are exsolved. There seem to be three types of C and N distributions within taenite. 1) These elements are enriched at the center of taenite (convex type). 2) They are enriched at the edge of taenite (concave type). 3) They are enriched near but some distance away from the edge of taenite (complex type). The case 1) is explained as equilibrium distribution of C and N in Fe-Ni alloy with M- shape nickel concentration profile. The case 2) seems to be best explained as diffusion controlled C and N distributions. In the case 3), the interior of taenite has been transformed to the a phase (kamacite or martensite). C and N were expelled from the a phase and enriched near the inner border of the remaining g phase. Such differences in the C and N distributions in taenite may reflect different cooling rates of iron meteorites. Nitrogen concentrations in taenite are quite high approaching 1 wt.% in some irons. Nitride (carlsbergite and roaldite) is present in meteorites with high nitrogen concentrations in taenite, suggesting that the nitride was formed due to supersaturation of the metallic phases with nitrogen. The same tendency is generally observed for carbon, i.e. high C concentrations in taenite correlate with the presence of carbide and/or graphite. Concentrations of C and N in kamacite are generally below detection limits. Isotopic compositions of C and N in taenite can be measured

  10. Iron oxidation stimulates organic matter decomposition in humid tropical forest soils.

    PubMed

    Hall, Steven J; Silver, Whendee L

    2013-09-01

    Humid tropical forests have the fastest rates of organic matter decomposition globally, which often coincide with fluctuating oxygen (O2 ) availability in surface soils. Microbial iron (Fe) reduction generates reduced iron [Fe(II)] under anaerobic conditions, which oxidizes to Fe(III) under subsequent aerobic conditions. We demonstrate that Fe (II) oxidation stimulates organic matter decomposition via two mechanisms: (i) organic matter oxidation, likely driven by reactive oxygen species; and (ii) increased dissolved organic carbon (DOC) availability, likely driven by acidification. Phenol oxidative activity increased linearly with Fe(II) concentrations (P < 0.0001, pseudo R(2)  = 0.79) in soils sampled within and among five tropical forest sites. A similar pattern occurred in the absence of soil, suggesting an abiotic driver of this reaction. No phenol oxidative activity occurred in soils under anaerobic conditions, implying the importance of oxidants such as O2 or hydrogen peroxide (H2 O2 ) in addition to Fe(II). Reactions between Fe(II) and H2 O2 generate hydroxyl radical, a strong nonselective oxidant of organic compounds. We found increasing consumption of H2 O2 as soil Fe(II) concentrations increased, suggesting that reactive oxygen species produced by Fe(II) oxidation explained variation in phenol oxidative activity among samples. Amending soils with Fe(II) at field concentrations stimulated short-term C mineralization by up to 270%, likely via a second mechanism. Oxidation of Fe(II) drove a decrease in pH and a monotonic increase in DOC; a decline of two pH units doubled DOC, likely stimulating microbial respiration. We obtained similar results by manipulating soil acidity independently of Fe(II), implying that Fe(II) oxidation affected C substrate availability via pH fluctuations, in addition to producing reactive oxygen species. Iron oxidation coupled to organic matter decomposition contributes to rapid rates of C cycling across humid tropical forests

  11. Macroporous Carbon Supported Zerovalent Iron for Remediation of Trichloroethylene

    DOE PAGES

    Lawrinenko, Michael; Wang, Zhuangji; Horton, Robert; ...

    2016-12-26

    Groundwater contamination with chlorinated hydrocarbons has become a widespread problem that threatens water quality and human health. Permeable reactive barriers (PRBs), which employ zerovalent iron, are effective for remediation; however, a need exists to reduce the economic and environmental costs associated with constructing PRBs. Here, we present a method to produce zerovalent iron supported on macroporous carbon using only lignin and magnetite. Biochar- ZVI (BC-ZVI) produced by this method exhibits a broad pore size distribution with micrometer sized ZVI phases dispersed throughout a carbon matrix. X-ray diffraction revealed that pyrolysis at 900 °C of a 50/50 lignin$-$magnetite mixture resulted inmore » almost complete reduction of magnetite to ZVI and that compression molding promotes iron reduction in pyrolysis due to mixing of starting materials. High temperature pyrolysis of lignin yields some graphite in BC-ZVI due to reduction of carbonaceous gases on iron oxides. TCE was removed from water as it passed through a column packed with BC-ZVI at flow rates representative of average and high groundwater flow. Lastly, one-dimensional convection$-$dispersion modeling revealed that adsorption by biochar influences TCE transport and that BC-ZVI facilitated removal of TCE from contaminated water by both adsorption and degradation.« less

  12. A seasonal carbon budget for a naturally iron-fertilized bloom over the Kerguelen Plateau in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Jouandet, Marie Paule; Blain, Stephane; Metzl, Nicolas; Brunet, Christian; Trull, Thomas W.; Obernosterer, Ingrid

    2008-03-01

    During the Kerguelen Ocean and Plateau compared Study (KEOPS, January-February 2005), a high-resolution distribution of surface fugacity of carbon dioxide ( fCO 2) was obtained from underway measurements. The stations in the core of the naturally iron-fertilized bloom were characterized by low fCO 2 (311±8 μatm) compared to the atmosphere, thus representing a large CO 2 sink. This contrasted with stations typical of high-nutrient low-chlorophyll (HNLC) conditions where the surface water was roughly in equilibrium with the atmosphere ( fCO 2=372±5 μatm). The vertical distribution of dissolved inorganic carbon (DIC) also was obtained at stations within and outside the bloom. Based on this data set, we constructed a carbon budget for the mixed layer that allowed us to determine the seasonal net community production (NCP season) and the seasonal carbon export in two contrasting environments. The robustness of the approach and the errors also were estimated. The NCP season in the core of the bloom was 6.6±2.2 mol m -2, typical of productive areas of the Southern Ocean. At the HNLC station the NCP season was 3 times lower than in the bloom. Our estimate of the daily net community production (NCP daily) within the bloom compares well with shipboard measurements of NCP. The NCP daily obtained above the Kerguelen Plateau was of the same order as the estimates from Southern Ocean artificial iron-fertilization experiments (SOIREE and EisenEx). The seasonal carbon export was derived from NCP season after subtraction of the seasonal accumulation of particulate and dissolved organic carbon. In the bloom, the carbon export (5.4±1.9 mol m -2) was 3-fold higher than at the HNLC station (1.7±0.4 mol m -2). Comparison of our results to artificial iron-fertilization experiments shows that the biological pump is enhanced by natural iron fertilization.

  13. Determining Inorganic and Organic Carbon.

    PubMed

    Koistinen, Jaana; Sjöblom, Mervi; Spilling, Kristian

    2017-11-21

    Carbon is the element which makes up the major fraction of lipids and carbohydrates, which could be used for making biofuel. It is therefore important to provide enough carbon and also follow the flow into particulate organic carbon and potential loss to dissolved organic forms of carbon. Here we present methods for determining dissolved inorganic carbon, dissolved organic carbon, and particulate organic carbon.

  14. Organic carbon sources and controlling processes on aquifer arsenic cycling in the Jianghan Plain, central China.

    PubMed

    Yu, Kai; Gan, Yiqun; Zhou, Aiguo; Liu, Chongxuan; Duan, Yanhua; Han, Li; Zhang, Yanan

    2018-05-30

    Groundwater arsenic contamination is a common environmental problem that threatens the health of over 100 million people globally. Apparent seasonal fluctuations in groundwater arsenic concentrations have been reported in various locations worldwide, including the Jianghan Plain, central China. This phenomenon has been attributed to shifts in redox conditions induced by seasonal incursions of surface water. However, it is not clear what processes during the incursion lead to changes in the redox conditions and what is the source of the organic carbon driving these processes. Therefore, we conducted a long-term investigation of stable carbon isotopic compositions in surface water and groundwater, as well as long-term monitoring of hydraulic gradients and geochemical compositions at the Jianghan Plain. Results indicated that a series of biogeochemical processes occurred during surface water incursion, including aerobic microbial respiration, nitrate and sulfate reduction. Groundwater arsenic was removed by adsorption on iron oxyhydroxides produced during oxidation of ferrous iron, resulting in dramatic decreases in arsenic concentrations during surface water recharge seasons. These processes were likely driven by organic carbon vertically transported from surface water and released from the surficial aquitard above 15 m. Groundwater pumping may accelerate the vertical infiltration of oxidizing recharge water and drive exogenous organic carbon to depth. Findings of this study advance the understandings of the mechanisms that cause temporal variations in groundwater As and the importance of exogenous organic carbon that may influence the temporal behavior of arsenic in groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Rapid bacterial mineralization of organic carbon produced during a phytoplankton bloom induced by natural iron fertilization in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Obernosterer, Ingrid; Christaki, Urania; Lefèvre, Dominique; Catala, Philippe; Van Wambeke, France; Lebaron, Philippe

    2008-03-01

    The response of heterotrophic bacteria ( Bacteria and Archaea) to the spring phytoplankton bloom that occurs annually above the Kerguelen Plateau (Southern Ocean) due to natural iron fertilization was investigated during the KErguelen Ocean and Plateau compared Study (KEOPS) cruise in January-February 2005. In surface waters (upper 100 m) in the core of the phytoplankton bloom, heterotrophic bacteria were, on an average, 3-fold more abundant and revealed rates of production ([ 3H] leucine incorporation) and respiration (<0.8 μm size fraction) that exceeded those in surrounding high-nutrient low-chlorophyll (HNLC) waters by factors of 6 and 5, respectively. These differences in bacterial metabolic activities were attributable to high-nucleic-acid-containing cells that dominated (≈80% of total cell abundance) the heterotrophic bacterial community associated with the phytoplankton bloom. Bacterial growth efficiencies varied between 14% and 20% inside the bloom and were <10% in HNLC waters. Results from bottle-incubation experiments performed at the bloom station indicated that iron had no direct but an indirect effect on heterotrophic bacterial activity, due to the stimulation by phytoplankton-derived dissolved organic matter. Within the Kerguelen bloom, bacterial carbon demand accounted for roughly 45% of gross community production. These results indicate that heterotrophic bacteria processed a significant portion of primary production, with most of it being rapidly respired.

  16. Spatial Associations and Chemical Composition of Organic Carbon Sequestered in Fe, Ca, and Organic Carbon Ternary Systems.

    PubMed

    Sowers, Tyler D; Adhikari, Dinesh; Wang, Jian; Yang, Yu; Sparks, Donald L

    2018-05-25

    Organo-mineral associations of organic carbon (OC) with iron (Fe) oxides play a major role in environmental OC sequestration, a process crucial to mitigating climate change. Calcium has been found to have high coassociation with OC in soils containing high Fe content, increase OC sorption extent to poorly crystalline Fe oxides, and has long been suspected to form bridging complexes with Fe and OC. Due to the growing realization that Ca may be an important component of C cycling, we launched a scanning transmission X-ray microscopy (STXM) investigation, paired with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, in order to spatially resolve Fe, Ca, and OC relationships and probe the effect of Ca on sorbed OC speciation. We performed STXM-NEXAFS analysis on 2-line ferrihydrite reacted with leaf litter-extractable dissolved OC and citric acid in the absence and presence of Ca. Organic carbon was found to highly associate with Ca ( R 2 = 0.91). Carboxylic acid moieties were dominantly sequestered; however, Ca facilitated the additional sequestration of aromatic and phenolic moieties. Also, C NEXAFS revealed polyvalent metal ion complexation. Our results provide evidence for the presence of Fe-Ca-OC ternary complexation, which has the potential to significantly impact how organo-mineral associations are modeled.

  17. Importance of Boreal Rivers in Providing Iron to Marine Waters

    PubMed Central

    Kritzberg, Emma S.; Bedmar Villanueva, Ana; Jung, Marco; Reader, Heather E.

    2014-01-01

    This study reports increasing iron concentrations in rivers draining into the Baltic Sea. Given the decisive role of iron to the structure and biogeochemical function of aquatic ecosystems, this trend is likely one with far reaching consequences to the receiving system. What those consequences may be depends on the fate of the iron in estuarine mixing. We here assess the stability of riverine iron by mixing water from seven boreal rivers with artificial sea salts. The results show a gradual loss of iron from suspension with increasing salinity. However, the capacity of the different river waters to maintain iron in suspension varied greatly, i.e. between 1 and 54% of iron was in suspension at a salinity of 30. The variability was best explained by iron:organic carbon ratios in the riverine waters – the lower the ratio the more iron remained in suspension. Water with an initially low iron:organic carbon ratio could keep even higher than ambient concentrations of Fe in suspension across the salinity gradient, as shown in experiments with iron amendments. Moreover, there was a positive relationship between the molecular size of the riverine organic matter and the amount of iron in suspension. In all, the results point towards a remarkably high transport capacity of iron from boreal rivers, suggesting that increasing concentrations of iron in river mouths may result in higher concentrations of potentially bioavailable iron in the marine system. PMID:25233197

  18. Liquid Plasma Synthesis of Carbon Coated Iron Oxide Particles

    NASA Astrophysics Data System (ADS)

    Uygun, Aysegul; Hershkowitz, Noah; Eren, Esin; Uygun, Emre; Celik Cogal, Gamze; Yurdabak Karaca, Gozde; Manolache, Sorin; Sundaram, Gunasekaran; Sadak, Omer; Oksuz, Lutfi

    2017-10-01

    Recently, magnetic metal or metal oxide nanoparticles encapsulated in carbon are important in biomedical applications. The relevant reason to study toxicity of the magnetic nanoparticles coated by carbon is that they have great potential to contribute to cancer treatment. In this work, the synthesis of iron oxide nano-particles coated by graphitic carbon shells using pulsed plasma in liquid method. Short duration of RF plasma discharge, low electrical energy and fast quenching of the surrounding media can let to synthesize various kinds of pure nanoparticles. Corresponding author: ayseguluygun@sdu.edu.tr, lutfioksuz@sdu.edu.tr.

  19. Computational and experimental studies of iron-bearing carbonates and silicate glasses at lower mantle pressures

    NASA Astrophysics Data System (ADS)

    Solomatova, N. V.; Jackson, J. M.; Asimow, P. D.; Sturhahn, W.; Rossman, G. R.; Roskosz, M.

    2017-12-01

    Decomposition of carbonates may be responsible for creating silicate melts within the lower mantle by lowering the melting temperature of surrounding rock. Identifying and characterizing the stability of carbonates is therefore a necessary step towards understanding the transport of carbon in Earth's interior. Dolomite is one of the major mineral forms in which carbon is subducted into the Earth's mantle. Although iron-free dolomite is expected to break down upon compression, high-pressure polymorphs of iron-bearing dolomite may resist decomposition. Using a genetic algorithm that predicts crystal structures, we found a monoclinic phase with space group C2/c that has a lower energy than all previously reported dolomite structures at pressures above 15 GPa, where the substitution of iron for magnesium stabilizes monoclinic dolomite at certain pressures of the lower mantle. Thus, an iron-bearing dolomite polymorph may be an important carbon carrier in regions of Earth's lower mantle. The depth at which carbonates will decompose is dependent on the age, temperature and density of subducting slabs. Decarbonation reactions may lower the melting temperature of surrounding rocks to produce silicate melts. In regions of the mantle where silicate melts may exist, it is important to understand the physical properties and dynamic behavior of the melts because they affect the chemical and thermal evolution of its interior. Composition, degree of polymerization, and iron's spin state affect such properties. The behavior of iron in silicate melts is poorly understood but, in some cases, may be approximated by iron-bearing glasses. We measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to 120 GPa and 100 GPa, respectively, in a neon pressure medium using time-domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe2+-like sites with distinct quadrupole splittings, reflecting

  20. Origin and fate of particulate and dissolved organic matter in a naturally iron-fertilized region of the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Tremblay, L.; Caparros, J.; Leblanc, K.; Obernosterer, I.

    2015-01-01

    Natural iron fertilization of high-nutrient low-chlorophyll (HNLC) waters induces annually occurring spring phytoplankton blooms off the Kerguelen Islands (Southern Ocean). To examine the origin and fate of particulate and dissolved organic matter (POM and DOM), D- and L-amino acids (AA) were quantified at bloom and HNLC stations. Total hydrolyzable AA accounted for 21-25% of surface particulate organic carbon (%POCAA) at the bloom sites, but for 10% at the HNLC site. A marked decrease in %POCAA with depth was observed at the most productive stations leading to values between 3 and 5% below 300 m depth. AA contributed to only 0.9-4.4% of dissolved organic carbon (%DOCAA) at all stations. The only consistent vertical trend was observed at the most productive station (A3-2) where %DOCAA decreased from ~ 2% in the surface waters to 0.9% near 300 m. These AA yields revealed that POM and DOM were more rapidly altered or mineralized at the bloom sites compared to the HNLC site. Alteration state was also assessed by trends in C / N ratio, %D-AA and degradation index. Different molecular markers indicated that POM mostly originated from diatoms and bacteria. The estimated average proportion of POM from intact phytoplankton cells in surface waters was 45% at the bloom station A3-2, but 14% at the HNLC site. Estimates based on D-AA yields indicated that ~ 15% of POM and ~ 30% of DOM was of bacterial origin (cells and cell fragments) at all stations. Surprisingly, the DOM in HNLC waters appeared less altered than the DOM from the bloom, had slightly higher dissolved AA concentrations, and showed no sign of alteration within the water column. Unfavorable conditions for bacterial degradation in HNLC regions can explain these findings. In contrast, large inputs of labile organic molecules and iron likely stimulate the degradation of organic matter (priming effect) and the production of more recalcitrant DOM (microbial carbon pump) during iron-fertilized blooms.

  1. Origin and fate of particulate and dissolved organic matter in a naturally iron-fertilized region of the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Tremblay, L.; Caparros, J.; Leblanc, K.; Obernosterer, I.

    2014-10-01

    Natural iron fertilization of high-nutrient low-chlorophyll (HNLC) waters induces annually occurring spring phytoplankton blooms off Kerguelen Islands (Southern Ocean). To examine the origin and fate of particulate and dissolved organic matter (POM and DOM), D- and L-amino acids (AA) were quantified at bloom and HNLC stations. Total hydrolysable AA accounted for 21-25% of surface particulate organic carbon (%POCAA) at the bloom sites, but for 10% at the HNLC site. A marked decrease in %POCAA with depth was observed at the most productive stations leading to values between 3 and 5% below 300 m depth. AA contributed to only 0.9-4.4% of dissolved organic carbon (%DOCAA) at all stations. The only consistent vertical trend was observed at the most productive station (A3-2) where %DOCAA decreased from ∼2% in the surface waters to 0.9% near 300 m. These AA yields and other markers revealed that POM and DOM were more rapidly altered or mineralized at the bloom sites compared to the HNLC site. Different molecular markers indicated that POM mostly originated from diatoms and bacteria. The estimated average proportion of POM from intact phytoplankton cells in surface waters was 45% at the bloom station A3-2, but 14% at the HNLC site. Estimates based on D-AA yields indicated that ∼15% of POM and ∼30% of DOM was of bacterial origin (cells and cell fragments) at all stations. Surprisingly, the DOM in HNLC waters appeared less altered than the DOM from the bloom, had slightly higher dissolved AA concentrations, and showed no sign of alteration within the water column. Unfavorable conditions for bacterial degradation in HNLC regions can explain these findings. In contrast, large inputs of labile organic molecules and iron, likely stimulate the degradation of organic matter (priming effect) and the production of more recalcitrant DOM (microbial carbon pump) during iron-fertilized blooms.

  2. Shallow Carbon Export from an Iron fertilised Plankton Bloom in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Sanders, R.; Pollard, R.; Morris, P.; Statham, P.; Moore, C. M. M.; Lucas, M.

    2009-04-01

    Some regions of the global ocean, notably the Southern Ocean, have high levels of macronutrients yet low levels of chlorophyll (the high nutrient, low chlorophyll or HNLC condition). Numerous artificial iron fertilization experiments conducted in the Southern Ocean have resulted in enhanced phytoplankton biomass and macronutrient drawdown. However the subsequent long-term biogeochemical consequences of such iron fertilization are unclear due in part to the limited size and duration of such experiments. An alternative way to assess the affect of iron over the Southern Ocean biological carbon pump is to observe the evolution of plankton production in regions of the Southern Ocean where shallow topography and Ocean currents interact to promote to release terrestrial iron into HNLC waters. During 2004-5 RRS Discovery conduced a complex programme of observations in such a region around the Crozet Islands in the SW Indian Ocean. The results of this programme, focussing on a quantitative estimate of carbon export per unit iron addition, will be presented.

  3. Iron geochemistry and organic carbon preservation by iron (oxyhydr)oxides in surface sediments of the East China Sea and the south Yellow Sea

    NASA Astrophysics Data System (ADS)

    Ma, Wei-Wei; Zhu, Mao-Xu; Yang, Gui-Peng; Li, Tie

    2018-02-01

    In marine sediments factors that influence iron (Fe) geochemistry and its interactions with other elements are diverse and remain poorly understood. Here we comparatively study Fe speciation and reactive Fe-bound organic carbon (Fe-OC) in surface sediments of the East China Sea (ECS) and the south Yellow Sea (SYS). The objectives are to better understand the potential impacts of geochemically distinct sediment sources and depositional/diagenetic settings on Fe geochemistry and OC preservation by Fe (hydr)oxides in sediments of the two extensive shelf seas around the world. Contents of carbonate- and acid-volatile-sulfide (AVS)-associated Fe(II) (FeAVS + carb) and magnetite (Femag) in the ECS sediments are about 5 and 9 times higher, respectively, than in the SYS. This could be ascribed to the ferruginous conditions of the ECS sediments that favor the formation/accumulation of Fecarb and Femag, a unique feature of marine unsteady depositional regimes. Much lower total Fe(II) contents in the SYS than in the ECS suggest that lower availability of highly reactive Fe (FeHR) and/or weak Fe reduction is a factor limiting Fe(II) formation and accumulation in the SYS sediments. The ratio of FeHR to total Fe is, on average, markedly higher (2.4 times) in the ECS sediments than in the SYS, which may be a combined result of several factors relevant to different sediment sources and depositional/diagenetic settings. In comparison with many other marine sediments, the percent fractions (fFe-OC) of Fe-OC to total organic carbon (TOC) in the ECS and the SYS are low, which can be ascribed to surface adsorption of OC rather than coprecipitation or organic complexation as the dominant binding mechanisms. Based on the fFe-OC in this study, total Fe-OC estimated for global continental shelves is equivalent to 38% of the atmospheric CO2 pool, which indicates the important role of sorptive stabilization of Fe-OC in continental shelf sediments for buffering CO2 release to the atmosphere

  4. Influence of iron redox cycling on organo-mineral associations in arctic tundra soils

    NASA Astrophysics Data System (ADS)

    Herndon, E.; AlBashaireh, A.; Duroe, K.; Singer, D. M.

    2016-12-01

    Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in arctic tundra systems. In tundra soils that are periodically to persistently saturated, the accumulation of iron oxyhydroxides and organo-iron precipitates at redox interfaces may inhibit decomposition by binding organic molecules and protecting them from microbial degradation. Here, we couple synchrotron-source spectroscopic techniques with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in organic and mineral horizons of the seasonally thawed active layer in tundra soils from northern Alaska. Mineral-associated organic matter comprised 63 ± 9% of soil organic carbon stored in the active layer of ice wedge polygons. Ferrous iron produced in anoxic mineral horizons diffused upwards and precipitated as poorly-crystalline oxyhydroxides and organic-bound Fe(III) in the organic horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris and in aggregates with clays and particulate organic matter. Organic matter released through acid-dissolution of iron oxides may represent a small pool of readily-degradable organic molecules temporarily stabilized by sorption to iron oxyhydroxide surfaces, while larger quantities of particulate organic carbon and humic-like substances may be physically protected from decomposition by Fe-oxide coatings and aggregation. We conclude that formation of poorly-crystalline and crystalline iron oxides at redox interfaces contributes to mineral protection of organic matter through sorption, aggregation, and co-precipitation reactions. Further study of organo-mineral associations is necessary to determine the net impact of mineral-stabilization on carbon storage in rapidly warming arctic ecosystems.

  5. Iron Hydroxy Carbonate Formation in Zerovalent Iron Permeable Reactive Barriers: Characterization and Evaluation of Phase Stability

    EPA Science Inventory

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently obs...

  6. A general strategy toward graphitized carbon coating on iron oxides as advanced anodes for lithium-ion batteries.

    PubMed

    Ding, Chunyan; Zhou, Weiwei; Wang, Bin; Li, Xin; Wang, Dong; Zhang, Yong; Wen, Guangwu

    2017-08-25

    Integration of carbon materials with benign iron oxides is blazing a trail in constructing high-performance anodes for lithium-ion batteries (LIBs). In this paper, a unique general, simple, and controllable strategy is developed toward in situ uniform coating of iron oxide nanostructures with graphitized carbon (GrC) layers. The basic synthetic procedure only involves a simple dip-coating process for the loading of Ni-containing seeds and a subsequent Ni-catalyzed chemical vapor deposition (CVD) process for the growth of GrC layers. More importantly, the CVD treatment is conducted at a quite low temperature (450 °C) and with extremely facile liquid carbon sources consisting of ethylene glycol (EG) and ethanol (EA). The GrC content of the resulting hybrids can be controllably regulated by altering the amount of carbon sources. The electrochemical results reveal remarkable performance enhancements of iron oxide@GrC hybrids compared with pristine iron oxides in terms of high specific capacity, excellent rate and cycling performance. This can be attributed to the network-like GrC coating, which can improve not only the electronic conductivity but also the structural integrity of iron oxides. Moreover, the lithium storage performance of samples with different GrC contents is measured, manifesting that optimized electrochemical property can be achieved with appropriate carbon content. Additionally, the superiority of GrC coating is demonstrated by the advanced performance of iron oxide@GrC compared with its corresponding counterpart, i.e., iron oxides with amorphous carbon (AmC) coating. All these results indicate the as-proposed protocol of GrC coating may pave the way for iron oxides to be promising anodes for LIBs.

  7. Magnetic graphene-carbon nanotube iron nanocomposites as adsorbents and antibacterial agents for water purification.

    PubMed

    Sharma, Virender K; McDonald, Thomas J; Kim, Hyunook; Garg, Vijayendra K

    2015-11-01

    One of the biggest challenges of the 21st century is to provide clean and affordable water through protecting source and purifying polluted waters. This review presents advances made in the synthesis of carbon- and iron-based nanomaterials, graphene-carbon nanotubes-iron oxides, which can remove pollutants and inactivate virus and bacteria efficiently in water. The three-dimensional graphene and graphene oxide based nanostructures exhibit large surface area and sorption sites that provide higher adsorption capacity to remove pollutants than two-dimensional graphene-based adsorbents and other conventional adsorbents. Examples are presented to demonstrate removal of metals (e.g., Cu, Pb, Cr(VI), and As) and organics (e.g., dyes and oil) by grapheme-based nanostructures. Inactivation of Gram-positive and Gram-negative bacterial species (e.g., Escherichia coli and Staphylococcus aureus) is also shown. A mechanism involving the interaction of adsorbents and pollutants is briefly discussed. Magnetic graphene-based nanomaterials can easily be separated from the treated water using an external magnet; however, there are challenges in implementing the graphene-based nanotechnology in treating real water. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Electron Spin Relaxation Rates for High-Spin Fe(III) in Iron Transferrin Carbonate and Iron Transferrin Oxalate

    PubMed Central

    Gaffney, Betty Jean; Eaton, Gareth R.; Eaton*, Sandra S.

    2005-01-01

    To optimize simulations of CW EPR spectra for high-spin Fe(III) with zero-field splitting comparable to the EPR quantum, information is needed on the factors that contribute to the line shapes and line widths. Continuous wave electron paramagnetic resonance (EPR) spectra obtained for iron transferrin carbonate from 4 to 150 K and for iron transferrin oxalate from 4 to 100 K did not exhibit significant temperature dependence of the line shape, which suggested that the line shapes were not relaxation determined. To obtain direct information concerning the electron spin relaxation rates, electron spin echo and inversion recovery EPR were used to measure T1 and Tm for the high-spin Fe(III) in iron transferrin carbonate and iron transferrin oxalate between 5 and 20–30 K. For comparison with the data for the transferrin complexes, relaxation times were obtained for tris(oxalato)ferrate(III). The relaxation rates are similar for the three complexes and do not exhibit a strong dependence on position in the spectrum. Extrapolation of the observed temperature dependence of the relaxation rates to higher temperatures gives values consistent with the conclusion that the CW line shapes are not relaxation determined up to 150 K. PMID:16429607

  9. Surface carbon influences on the reductive transformation of TCE in the presence of granular iron.

    PubMed

    Firdous, R; Devlin, J F

    2018-04-05

    To gain insight into the processes of transformations in zero-valent iron systems, electrolytic iron (EI) has been used as a surrogate for the commercial products actually used in barriers. This substitution facilitates mechanistic studies, but may not be fully representative of all the relevant processes at work in groundwater remediation. To address this concern, the kinetic iron model (KIM) was used to investigate sorption and reactivity differences between EI and Connelly brand GI, using TCE as a probe compound. It was observed that retardation factors (R app ) for GI varied non-linearly with influent concentrations to the columns (C o ), and declined significantly as GI aged. In contrast, R app values for EI were small and insensitive to C o , and changed minimally with iron aging. Moreover, although declines in the rate constants (k) and increases in the sorption coefficients were observed for both iron types, they were most pronounced in the case of EI. SEM scans of the EI surface before and after aging (90 days) established the appearance of carbon on the older surface. This work provides evidence that iron with a higher surface carbon content outperforms pure iron, suggesting that the carbon is actively involved in promoting TCE reduction. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. 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.

  11. Microbial diversity and iron oxidation at Okuoku-hachikurou Onsen, a Japanese hot spring analog of Precambrian iron formations.

    PubMed

    Ward, L M; Idei, A; Terajima, S; Kakegawa, T; Fischer, W W; McGlynn, S E

    2017-11-01

    Banded iron formations (BIFs) are rock deposits common in the Archean and Paleoproterozoic (and regionally Neoproterozoic) sedimentary successions. Multiple hypotheses for their deposition exist, principally invoking the precipitation of iron via the metabolic activities of oxygenic, photoferrotrophic, and/or aerobic iron-oxidizing bacteria. Some isolated environments support chemistry and mineralogy analogous to processes involved in BIF deposition, and their study can aid in untangling the factors that lead to iron precipitation. One such process analog system occurs at Okuoku-hachikurou (OHK) Onsen in Akita Prefecture, Japan. OHK is an iron- and CO 2 -rich, circumneutral hot spring that produces a range of precipitated mineral textures containing fine laminae of aragonite and iron oxides that resemble BIF fabrics. Here, we have performed 16S rRNA gene amplicon sequencing of microbial communities across the range of microenvironments in OHK to describe the microbial diversity present and to gain insight into the cycling of iron, oxygen, and carbon in this ecosystem. These analyses suggest that productivity at OHK is based on aerobic iron-oxidizing Gallionellaceae. In contrast to other BIF analog sites, Cyanobacteria, anoxygenic phototrophs, and iron-reducing micro-organisms are present at only low abundances. These observations support a hypothesis where low growth yields and the high stoichiometry of iron oxidized per carbon fixed by aerobic iron-oxidizing chemoautotrophs like Gallionellaceae result in accumulation of iron oxide phases without stoichiometric buildup of organic matter. This system supports little dissimilatory iron reduction, further setting OHK apart from other process analog sites where iron oxidation is primarily driven by phototrophic organisms. This positions OHK as a study area where the controls on primary productivity in iron-rich environments can be further elucidated. When compared with geological data, the metabolisms and mineralogy at

  12. Equilibrium carbon and hydrogen isotope fractionation in iron

    NASA Astrophysics Data System (ADS)

    Schauble, E. A.

    2009-12-01

    Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin

  13. Characterization of iron carbonate scales developed under carbon dioxide corrosion conditions

    NASA Astrophysics Data System (ADS)

    de Moraes, Flavio Dias

    1999-11-01

    Carbon steel CO2 corrosion is a common and very serious problem in the oil industry. It often results in severe damage to pipes and equipment. Besides controlling direct costs associated with loss of production and replacement or repair to the equipment damaged by corrosion, life and environmental safety must be protected with the thorough study of this type of corrosion. For a given type of steel, the CO2 corrosion rates are strongly influenced by many mechanical and environmental factors, such as flow velocity, temperature, gas-liquid ratio, oil-water ratio, CO2 partial pressure, and the chemical composition of the produced water. Under specific conditions, a corrosion product, the iron carbonate (FeCO3), can deposit over the corroding metal as a scale and dramatically reduce the CO2 corrosion rates on carbon steels. The ability to reliably predict the protective characteristics of such scales so that this knowledge may be used to mitigate the CO2 corrosion problem is the main objective of this research. CO2 corrosion tests performed under various CO2 corrosion flowing conditions in a flow loop were used to generate and study FeCO3 scales. In situ Electrochemical Impedance Spectroscopy (EIS) techniques were successfully used to monitor the development of the scales throughout the duration of the tests. The EIS monitoring enabled the identification of the type of scales being formed and the quantification of the protection they give. A procedure using EIS, SEM and X-ray diffraction was developed to electrochemically and morphologically characterize the scales formed. In this work, morphology of the scales was proved to be the most important characteristic related to CO2 corrosion protection, and temperature was found to be the main environmental parameter controlling the morphology of the scales. For the environmental conditions tested, a correlation was developed to predict the type of iron carbonate scales that would be formed and the amount of CO2 corrosion

  14. Effect of Carbon Type on Arsenic and Trichloroethylene Removal Capacity of Iron (Hydr)oxide Nanoparticle Impregnated Granulated Activated Carbon

    NASA Astrophysics Data System (ADS)

    Cooper, Anne Marie

    This study investigates the effect of the virgin granular activated carbon (GAC) on the properties of synthesized iron (hydr)oxide nanoparticles impregnated GAC (Fe-GAC) media and its ability to remove arsenate and organic trichloroethylene (TCE) from water. Fe-GAC media were synthesized from bituminous and lignite-based virgin GAC via three variations of a permanganate/Fe(II) synthesis method. Data obtained from an array of characterization techniques indicated that differences in pore size distribution and surface chemistry of the virgin GAC favor different reaction paths for the iron (hydr)oxide nanoparticles formation. Batch equilibrium isotherm testing (120 microg-As/L; 6 mg-TCE/L, 10 mM NaHCO3 at pH = 7.2 +/- 0.1 and pH = 8.2 +/- 0.1) showed arsenic removal capability was increased as a result of iron (nanoparticles) impregnation, while TCE removal properties were decreased in Fe-GAC media. This tradeoff was displayed by both lignite and bituminous Fe-GAC but was most pronounced in lignite-based Fe-GAC having the highest Fe content (13.4% Fe) which showed the most favorable Freundlich adsorption and intensity parameters for arsenic of Ka = 72.6 (microg-As/g-FeGAC)(L/microg-As)1/n, 1/n = 0.6; and least favorable adsorption for TCE of Ka = 0.8 (mg-TCE/g-FeGAC)(L/mg-TCE)1/n, 1/n = 4.47. It was concluded that iron content was the main factor contributing to enhanced arsenic removal and that this was affected by base GAC properties such as pore size distribution and surface functional groups. However high Fe content can result in pore blockage; reduction in available adsorption sites for organic co-contaminants; and have a significant effect on the Fe-GACs overall adsorption capacity.

  15. Temporal fluctuations in grain size, organic materials and iron concentrations in intertidal surface sediment of San Francisco Bay

    USGS Publications Warehouse

    Thomson-Becker, E. A.; Luoma, S.N.

    1985-01-01

    The physical and chemical characteristics of the oxidized surface sediment in an estuary fluctuate temporally in response to physical forces and apparently-fluctuating inputs. These characteristics, which include grain size and concentrations of organic materials and iron, will influence both trace-metal geochemistry and bioavailability. Temporal trends in the abundance of fine particles, total organic carbon content (TOC), absorbance of extractable organic material (EOM), and concentration of extractable iron in the sediment of San Francisco Bay were assessed using data sets containing approximately monthly samples for periods of two to seven years. Changes in wind velocity and runoff result in monthly changes in the abundance of fine particles in the intertidal zone. Fine-grained particles are most abundant in the late fall/early winter when runoff is elevated and wind velocities are low; particles are coarser in the summer when runoff is low and wind velocities are consistently high. Throughout the bay, TOC is linearly related to fine particle abundance (r = 0.61). Temporal variability occurs in this relationship, as particles are poor in TOC relative to percent of fine particles in the early rainy season. Iron-poor particles also appear to enter the estuary during high runoff periods; while iron is enriched on particle surfaces in the summer. Concentrations of extractable iron and absorbance of EOM vary strongly from year to year. Highest absorbances of EOM occurred in the first year following the drought in 1976-77, and in 1982 and 1983 when river discharge was unusually high. Extractable-iron concentrations were also highest in 1976-77, but were very low in 1982 and 1983. ?? 1985 Dr W. Junk Publishers.

  16. The Evolution of Sulfide in Shallow Aquatic Ecosystem Sediments: An Analysis of the Roles of Sulfate, Organic Carbon, and Iron and Feedback Constraints Using Structural Equation Modeling

    NASA Astrophysics Data System (ADS)

    Pollman, C. D.; Swain, E. B.; Bael, D.; Myrbo, A.; Monson, P.; Shore, M. D.

    2017-11-01

    The generation of elevated concentrations of sulfide in sediment pore waters that are toxic to rooted macrophytes is problematic in both marine and freshwaters. In marine waters, biogeochemical conditions that lead to toxic levels of sulfide generally relate to factors that affect oxygen dynamics or the sediment iron concentration. In freshwaters, increases in surface water sulfate have been implicated in decline of Zizania palustris (wild rice), which is important in wetlands across the Great Lakes region of North America. We developed a structural equation (SE) model to elucidate key variables that govern the evolution of sulfide in pore waters in shallow aquatic habitats that are potentially capable of supporting wild rice. The conceptual basis for the model is the hypothesis that dissimilatory sulfate reduction is limited by the availability of both sulfate and total organic carbon (TOC) in the sediment. The conceptual model also assumes that pore water sulfide concentrations are constrained by the availability of pore water iron and that sediment iron supports the supply of dissolved iron to the pore water. A key result from the SE model is that variations in three external variables (sulfate, sediment TOC, and sediment iron) contribute nearly equally to the observed variations in pore water sulfide. As a result, management efforts to mitigate against the toxic effects of pore water sulfide on macrophytes such as wild rice should approach defining a protective sulfate threshold as an exercise tailored to the geochemistry of each site that quantitatively considers the effects of ambient concentrations of sediment Fe and TOC.

  17. Bifunctional catalyst of graphite-encapsulated iron compound nanoparticle for magnetic carbon nanotubes growth by chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Saraswati, Teguh Endah; Prasiwi, Oktaviana Dewi Indah; Masykur, Abu; Anwar, Miftahul

    2017-01-01

    The carbon nanotube has widely taken great attractive in carbon nanomaterial research and application. One of its preparation methods is catalytic chemical vapor deposition (CCVD) using catalyst i.e. iron, nickel, etc. Generally, except the catalyst, carbon source gasses as the precursor are still required. Here, we report the use of the bifunctional material of Fe3O4/C which has an incorporated core/shell structures of carbon-encapsulated iron compound nanoparticles. The bifunctional catalyst was prepared by submerged arc discharge that simply performed using carbon and carbon/iron oxide electrodes in ethanol 50%. The prepared material was then used as a catalyst in thermal chemical vapor deposition at 800°C flown with ethanol vapor as the primer carbon source in a low-pressure condition. This catalyst might play a dual role as a catalyst and secondary carbon source for growing carbon nanotubes at the time. The synthesized products were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The successful formation of carbon nanotubes was assigned by the shifted X-ray diffracted peak of carbon C(002), the iron oxides of Fe3O4 and γ-Fe2O3, and the other peaks which were highly considered to the other carbon allotropes with sp2 hybridization structures. The other assignment was studied by electron microscopy which successfully observed the presence of single-wall carbon nanotubes. In addition, the as-prepared carbon nanotubes have a magnetic property which was induced by the remaining of metal catalyst inside the CNT.

  18. Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

    NASA Technical Reports Server (NTRS)

    Nealson, K. H.; Saffarini, D.

    1994-01-01

    Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

  19. Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters.

    PubMed

    Sjöstedt, Carin S; Gustafsson, Jon Petter; Köhler, Stephan J

    2010-11-15

    A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

  20. Environmental Controls of Soil Organic Carbon in Soils Across Amazonia

    NASA Astrophysics Data System (ADS)

    Quesada, Carlos Alberto; Paz, Claudia; Phillips, Oliver; Nonato Araujo Filho, Raimundo; Lloyd, Jon

    2015-04-01

    (kaolinitic) and thus the clay plus silt fraction was the best correlate for SOC but with crystalline iron oxides (dithionite-citrate minus ammonium oxalate - oxalic acid extractable iron) being also correlated to SOC in these soils (R2 = 0.74). Most of SOC in these soils was found on the clay+silt fraction and in stable, clay rich aggregates. However, SOC of high activity clays and other less weathered soils such as Alisols, Cambisols and Plinthosols showed no correlation with particle size or iron oxides, being mostly stabilized by aluminium complexes. We found SOC of these soils to be better explained by a three way interaction among soil pH, carbon quality and dithionite-citrate extractable Al (R2 = 0.85). Consistent with this observation, SOC in the less weathered soils was mostly found in the colloidal fraction (75%). SOC of Podzols and Arenosols on the other hand had only a small but significant influence from their clay plus silt fraction (R2 = 0.31), with particulate organic matter accounting for most of its SOC.

  1. Saccharides enhance iron bioavailability to Southern Ocean phytoplankton

    PubMed Central

    Hassler, Christel S.; Nichols, Carol Mancuso; Butler, Edward C. V.; Boyd, Philip W.

    2011-01-01

    Iron limits primary productivity in vast regions of the ocean. Given that marine phytoplankton contribute up to 40% of global biological carbon fixation, it is important to understand what parameters control the availability of iron (iron bioavailability) to these organisms. Most studies on iron bioavailability have focused on the role of siderophores; however, eukaryotic phytoplankton do not produce or release siderophores. Here, we report on the pivotal role of saccharides—which may act like an organic ligand—in enhancing iron bioavailability to a Southern Ocean cultured diatom, a prymnesiophyte, as well as to natural populations of eukaryotic phytoplankton. Addition of a monosaccharide (>2 nM of glucuronic acid, GLU) to natural planktonic assemblages from both the polar front and subantarctic zones resulted in an increase in iron bioavailability for eukaryotic phytoplankton, relative to bacterioplankton. The enhanced iron bioavailability observed for several groups of eukaryotic phytoplankton (i.e., cultured and natural populations) using three saccharides, suggests it is a common phenomenon. Increased iron bioavailability resulted from the combination of saccharides forming highly bioavailable organic associations with iron and increasing iron solubility, mainly as colloidal iron. As saccharides are ubiquitous, present at nanomolar to micromolar concentrations, and produced by biota in surface waters, they also satisfy the prerequisites to be important constituents of the poorly defined “ligand soup,” known to weakly bind iron. Our findings point to an additional type of organic ligand, controlling iron bioavailability to eukaryotic phytoplankton—a key unknown in iron biogeochemistry. PMID:21169217

  2. Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  3. Electrochemistry of Simple Organometallic Models of Iron-Iron Hydrogenases in Organic Solvent and Water.

    PubMed

    Gloaguen, Frederic

    2016-01-19

    Synthetic models of the active site of iron-iron hydrogenases are currently the subjects of numerous studies aimed at developing H2-production catalysts based on cheap and abundant materials. In this context, the present report offers an electrochemist's view of the catalysis of proton reduction by simple binuclear iron(I) thiolate complexes. Although these complexes probably do not follow a biocatalytic pathway, we analyze and discuss the interplay between the reduction potential and basicity and how these antagonist properties impact the mechanisms of proton-coupled electron transfer to the metal centers. This question is central to any consideration of the activity at the molecular level of hydrogenases and related enzymes. In a second part, special attention is paid to iron thiolate complexes holding rigid and unsaturated bridging ligands. The complexes that enjoy mild reduction potentials and stabilized reduced forms are promising iron-based catalysts for the photodriven evolution of H2 in organic solvents and, more importantly, in water.

  4. Calcification response of Pleurochrysis carterae to iron concentrations in batch incubations: implication for the marine biogeochemical cycle

    NASA Astrophysics Data System (ADS)

    Zou, Xiang; Sun, Shiyong; Lin, Sen; Shen, Kexuan; Dong, Faqin; Tan, Daoyong; Nie, Xiaoqin; Liu, Mingxue; Wei, Jie

    2017-12-01

    Calcified coccolithophores, a diverse and widely distributed group of marine microalgae, produce biogenic calcite in the form of coccoliths located on the cell surface. Using batch incubations of the coccolithophorid Pleurochrysis carterae, we investigated the responses of this calcification process to iron concentrations by changing the iron supply in the initial culture media from a normal concentration to 1 ppm (parts per million), 5 ppm, and 10 ppm. Time-dependent measurements of cell population, production of inorganic carbon (coccoliths), and organic carbon (organic cellular components) showed that elevated iron supply in the growth medium of P. carterae stimulates carbon sequestration by increasing growth along enhanced photosynthetic activity and calcification. In addition, the acquired time-dependent UV-Vis and FT-IR spectra revealed that iron fertilization-enhanced coccolith calcification is accompanied by a crystalline phase transition from calcite to aragonite or amorphous phase. Our results suggest that iron concentration has a significant influence on the marine carbon cycle of coccolithophores.

  5. Stability of iron-bearing carbonates in the deep Earth’s interior

    DOE PAGES

    Cerantola, Valerio; Bykova, Elena; Kupenko, Ilya; ...

    2017-07-19

    The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth’s lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. We investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mossbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth’s geotherm at pressures to B 50 GPa FeCO 3 partially dissociates to form various iron oxides. Furthermore, at higher pressures FeCO 3 forms two new structures— tetrairon(III) orthocarbonate Femore » $$3+\\atop{4}$$C 3O 12 and diiron(II) diiron(III) tetracarbonate Fe$$2+\\atop{2}$$ Fe$$3+\\atop{2}$$C 4 O 13, both phases containing CO 4 tetrahedra. Fe 4 C 4 O 13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth’s lower mantle.« less

  6. Impacts of dyebath auxiliaries on the reductive discoloration of Acid Orange 7 dye by high-carbon iron filings.

    PubMed

    Kumar, Raja; Sinha, Alok

    This study proposed that the physicochemical effects of common dyebath auxiliaries on the bulk dye solution as well as on the iron surface can influence the reductive discoloration of effluent containing Acid Orange 7 (AO7) dye using high-carbon iron filings. Sodium chloride increased the discoloration rate because of the pitting corrosion on the iron surface, triggered by chloride anion. 'Salting out' effect of ammonium sulfate improved the reaction rate up to a certain concentration, beyond which it could compete with dye molecules for the reactive sites, as revealed by formed sulfite and sulfide. Urea drastically reduced the discoloration rates by its chaotropic effect on the bulk solution and by wrapping around the iron surface. Organic acids, namely acetic acid and citric acid, stimulated iron corrosion to improve the discoloration rates. The discoloration reaction was biphasic with an initial fast reaction phase, where in every case more than 70% discoloration was observed within 5 min of reaction, preceding a slow reaction phase. The experimental data could be well described using biphasic kinetics equation (R(2)> 0.997 in all cases) and a biphasic equation was developed considering the individual impact of co-existing auxiliaries on AO7 discoloration.

  7. Removal of 2-ClBP from soil-water system using activated carbon supported nanoscale zerovalent iron.

    PubMed

    Zhang, Wei; Yu, Tian; Han, Xiaolin; Ying, Weichi

    2016-09-01

    We explored the feasibility and removal mechanism of removing 2-chlorobiphenyl (2-ClBP) from soil-water system using granular activated carbon (GAC) impregnated with nanoscale zerovalent iron (reactive activated carbon or RAC). The RAC samples were successfully synthesized by the liquid precipitation method. The mesoporous GAC based RAC with low iron content (1.32%) exhibited higher 2-ClBP removal efficiency (54.6%) in the water phase. The result of Langmuir-Hinshelwood kinetic model implied that the different molecular structures between 2-ClBP and trichloroethylene (TCE) resulted in more difference in dechlorination reaction rates on RAC than adsorption capacities. Compared to removing 2-ClBP in the water phase, RAC removed the 2-ClBP more slowly in the soil phase due to the significant external mass transfer resistance. However, in the soil phase, a better removal capacity of RAC was observed than its base GAC because the chemical dechlorination played a more important role in total removal process for 2-ClBP. This important result verified the effectiveness of RAC for removing 2-ClBP in the soil phase. Although reducing the total RAC removal rate of 2-ClBP, soil organic matter (SOM), especially the soft carbon, also served as an electron transfer medium to promote the dechlorination of 2-ClBP in the long term. Copyright © 2016. Published by Elsevier B.V.

  8. Carbon nanotube synthesis via the catalytic chemical vapor deposition of methane in the presence of iron, molybdenum, and iron-molybdenum alloy thin layer catalysts

    NASA Astrophysics Data System (ADS)

    Yahyazadeh, Arash; Khoshandam, Behnam

    In this study, we documented the catalytic chemical vapor deposition synthesis of carbon nanotubes (CNTs) using ferrocene and molybdenum hexacarbonyl as catalyst nanoparticle precursors and methane as a nontoxic and economical carbon source for the first time. Field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, wavelength dispersive X-ray spectrometry and transmission electron microscopy of the thin layer catalyst as a simple and cost effective catalyst preparation after methane decomposition reaction, along with Fourier transform infrared spectroscopy and Raman spectroscopy confirmed the growth of CNTs, from bimetallic nanoparticles, which are converted into iron-molybdenum alloy nanoparticles at 700 °C for pretreatment by hydrogen after chemical vapor deposition of thin layers. An investigation of the weight percentages of the chemical elements present in the CNTs synthesized from iron-molybdenum catalyst using quartz sheet substrate at 750 °C, confirmed a significant carbon yield of 75.4% which represents high catalyst activity. Additionally, multi-walled carbon nanotubes (∼16-55 nm in diameter and 1.2 μm in length) were observed in the iron-molybdenum alloy sample after methane decomposition reaction at 750 °C for 35 min. To show the role of iron and molybdenum coated on silicon substrate as two thin layer catalysts, samples were considered for CNTs growth (diameter ∼47-69 nm) at 800 °C and 830 °C, respectively. Moreover, the effect of hydrogen pretreatment was evaluated in terms of active metal coating properly. The best graphitic structure due to Raman spectroscopy outcomes (ID/IG ratio) was obtained for iron coated on a quartz sheet, which was estimated at 0.8505. Thermogravimetric analysis proved the thermal stability of the synthesized CNTs using iron thin-layer catalyst up to 350 °C.

  9. Enhanced Fenton-like removal of nitrobenzene via internal microelectrolysis in nano zerovalent iron/activated carbon composite.

    PubMed

    Hu, Sihai; Wu, Yaoguo; Yao, Hairui; Lu, Cong; Zhang, Chengjun

    2016-01-01

    The efficiency of Fenton-like catalysis using nano zerovalent iron (nZVI) is limited by nZVI aggregation and activity loss due to inactive ferric oxide forming on the nZVI surface, which hinders electron transfer. A novel iron-carbon composite catalyst consisting of nZVI and granular activated carbon (GAC), which can undergo internal iron-carbon microelectrolysis spontaneously, was successfully fabricated by the adsorption-reduction method. The catalyst efficiency was evaluated in nitrobenzene (NB) removal via the Fenton-like process (H2O2-nZVI/GAC). The results showed that nZVI/GAC composite was good for dispersing nZVI on the surface of GAC, which permitted much better removal efficiency (93.0%) than nZVI (31.0%) or GAC (20.0%) alone. Moreover, iron leaching decreased from 1.28 to 0.58 mg/L after reaction of 240 min and the oxidation kinetic of the Fenton-like reaction can be described well by the second-order reaction kinetic model (R2=0.988). The composite catalyst showed sustainable catalytic ability and GAC performed as a medium for electron transfer in internal iron-carbon microelectrolysis to promote Fe2+ regeneration and Fe3+/Fe2+ cycles. Therefore, this study represents an important method to design a low cost and high efficiency Fenton-like catalyst in practical application.

  10. Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity.

    PubMed

    Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David

    2011-10-10

    A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

    2008-01-01

    Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

  12. Atomistic modeling of carbon Cottrell atmospheres in bcc iron

    NASA Astrophysics Data System (ADS)

    Veiga, R. G. A.; Perez, M.; Becquart, C. S.; Domain, C.

    2013-01-01

    Atomistic simulations with an EAM interatomic potential were used to evaluate carbon-dislocation binding energies in bcc iron. These binding energies were then used to calculate the occupation probability of interstitial sites in the vicinity of an edge and a screw dislocation. The saturation concentration due to carbon-carbon interactions was also estimated by atomistic simulations in the dislocation core and taken as an upper limit for carbon concentration in a Cottrell atmosphere. We obtained a maximum concentration of 10 ± 1 at.% C at T = 0 K within a radius of 1 nm from the dislocation lines. The spatial carbon distributions around the line defects revealed that the Cottrell atmosphere associated with an edge dislocation is denser than that around a screw dislocation, in contrast with the predictions of the classical model of Cochardt and colleagues. Moreover, the present Cottrell atmosphere model is in reasonable quantitative accord with the three-dimensional atom probe data available in the literature.

  13. Organic iron (III) complexing ligands during an iron enrichment experiment in the western subarctic North Pacific

    NASA Astrophysics Data System (ADS)

    Kondo, Yoshiko; Takeda, Shigenobu; Nishioka, Jun; Obata, Hajime; Furuya, Ken; Johnson, William Keith; Wong, C. S.

    2008-06-01

    Complexation of iron (III) with natural organic ligands was investigated during a mesoscale iron enrichment experiment in the western subarctic North Pacific (SEEDS II). After the iron infusions, ligand concentrations increased rapidly with subsequent decreases. While the increases of ligands might have been partly influenced by amorphous iron colloids formation (12-29%), most in-situ increases were attributable to the <200 kDa fraction. Dilution of the fertilized patch may have contributed to the rapid decreases of the ligands. During the bloom decline, ligand concentration increased again, and the high concentrations persisted for 10 days. The conditional stability constant was not different between inside and outside of the fertilized patch. These results suggest that the chemical speciation of the released iron was strongly affected by formation of the ligands; the production of ligands observed during the bloom decline will strongly impact the iron cycle and bioavailability in the surface water.

  14. Removal of polybrominated diphenyl ethers by biomass carbon-supported nanoscale zerovalent iron particles: influencing factors, kinetics, and mechanism.

    PubMed

    Fu, Rongbing; Xu, Zhen; Peng, Lin; Bi, Dongsu

    2016-12-01

    In this study, nanoscale zerovalent iron (NZVI) immobilized on biomass carbon was used for the high efficient removal of BDE 209. NZVI supported on biomass carbon minimized the aggregation of NZVI particles resulting in the increased reaction performance. The proposed removal mechanism included the adsorption of BDE 209 on the surface or interior of the biomass carbon NZVI (BC-NZVI) particles and the subsequent debromination of BDE 209 by NZVI while biomass carbon served as an electron shuttle. BC-NZVI particles and the interaction between BC-NZVI particles and BDE 209 were characterized by TEM, XRD, and XPS. The removal reaction followed a pseudo-first-order rate expression under different reaction conditions, and the k obs was higher than that of other NZVI-supported materials. The debromination of BDE 209 by BC-NZVI was a stepwise process from nona-BDE to DE. A proposed pathway suggested that supporting NZVI on biomass carbon has potential as a promising technique for in situ organic-contaminated groundwater remediation.

  15. Co-hydrothermal treatment of fallen leaves with iron sludge to prepare magnetic iron product and solid fuel.

    PubMed

    Gu, Lin; Li, Binglian; Wen, Haifeng; Zhang, Xin; Wang, Liang; Ye, Jianfeng

    2018-06-01

    The hydrothermal carbonization (HTC) was performed on Metasequoia Leaves (ML) in the presence of iron sludge, both of which were generated as solid residuals. The relations between sludge, char's properties and operating conditions were systemically investigated. Iron sludge primarily catalyzed the efficient formation of char with higher heating value (HHV) becoming 1.15-1.65 times of ML (18.21 MJ/kg) and was meanwhile reduced to magnetite. The hydrated Fe ions in octahedron crystals acted as nucleophiles facilitating the dehydration and decarboxylation reactions. The increased HHV is found strong temperature dependent while prolonging the residence time is more preferable for low organic acids generation. Thermogravimetric analysis confirmed the iron sludge enhanced conversion of volatile to fixed carbon. The as-prepared solid char showed better stability after catalytic HTC treatment, having ignition temperature increased from 253 to 426 °C as compared to the char prepared without iron sludge addition. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. 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.

  17. Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters

    DOE PAGES

    Jubb, Aaron M.; Eskelsen, Jeremy R.; Yin, Xiangping Lisa; ...

    2018-04-04

    Here, massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with amore » suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe 2+Fe 2 3+O 4) nanoparticles (<5 nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.« less

  18. Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters

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

    Jubb, Aaron M.; Eskelsen, Jeremy R.; Yin, Xiangping Lisa

    Here, massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with amore » suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe 2+Fe 2 3+O 4) nanoparticles (<5 nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.« less

  19. Microbial Community Response to Warming and Correlations to Organic Carbon Degradation in an Arctic Tundra Soil

    NASA Astrophysics Data System (ADS)

    Yang, Z.; Yang, S.; Zhou, J.; Wullschleger, S. D.; Graham, D. E.; Yang, Y.; Gu, B.

    2016-12-01

    Climate warming increases microbial activity and thus decomposition of soil organic carbon (SOC) stored in Arctic tundra, but changes in microbial community and its correlations to SOC decomposition are poorly understood. Using a microbial functional gene array (GeoChip 5.0), we examined the microbial functional community structure changes with temperature (-2 and +8 °C) in an anoxic incubation experiment with a high-centered polygon trough soil from Barrow, Alaska. Through a 122-day incubation, we show that functional community structure was significantly altered (P < 0.05) by 8 °C warming, with functional diversity decreasing in response to warming and rapid degradation of the labile soil organic substrates. In contrast, microbial community structure was largely unchanged by -2 °C incubation. In the organic layer soil, gene abundances associated with fermentation, methanogenesis, and iron reduction all decreased significantly (P < 0.05) following the incubation at 8 °C. These observations corroborate strongly with decreased methane and reducing sugar production rates and iron reduction during the incubation. These results demonstrate a rapid and sensitive microbial response to increasing soil temperature, and suggest important roles of microbial communities in moderating SOC degradation and iron cycling in warming Arctic tundra.

  20. Iron-catalyzed hydrogenation of bicarbonates and carbon dioxide to formates.

    PubMed

    Zhu, Fengxiang; Zhu-Ge, Ling; Yang, Guangfu; Zhou, Shaolin

    2015-02-01

    The catalytic hydrogenation of carbon dioxide and bicarbonate to formate has been explored extensively. The vast majority of the known active catalyst systems are based on precious metals. Herein, we describe an effective, phosphine-free, air- and moisture-tolerant catalyst system based on Knölker's iron complex for the hydrogenation of bicarbonate and carbon dioxide to formate. The catalyst system can hydrogenate bicarbonate at remarkably low hydrogen pressures (1-5 bar). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Relative contribution of iron reduction to sediments organic matter mineralization in contrasting habitats of a shallow eutrophic freshwater lake.

    PubMed

    Chen, Mo; Jiang, He-Long

    2016-06-01

    Iron reduction is one of the important organic matter (OM) mineralization pathway in sediments. Here we investigated the rates and the relative contribution of iron reduction to OM mineralization in Zhushan bay (ZSB, cyanobacterial bloom biomass (CBB)-dominated habitats) and East Taihu Lake (ETL, submerged macrophypes (SM)-dominated habitats) of Lake Taihu, China. Anaerobic microcosm incubation revealed that the rate of iron reduction at ZSB (4.42 μmol cm(-3) d(-1)) in summer was almost 1.5 times higher than at ETL (3.13 μmol cm(-3) d(-1)). Iron reduction accounted for 66.5% (ZSB) and 31.8% (ETL) of total anaerobic carbon mineralization, respectively. No detectable methanogenesis was found at ZSB, while methanogenesis was responsible for 16.7% of total anaerobic respiration in sediments of ETL. Geochemical analysis of solid phase constituents indicated that ZSB surface sediments experienced highly oxidizing conditions with much higher amorphous Fe(III) (71 mmol m(-2)) than ETL (11 mmol m(-2)). Conversely, AVS inventories at ETL (38 mmol m(-2)) were up to 30 times higher than at ZSB (1.27 mmol m(-2)), indicating significant sulfate reduction in sediments of ETL. Overall results suggested that varying carbon sources and distinct geochemical characterizations of the sediments in contrasting habitats significantly influenced the rate of iron reduction and the pathway of C mineralization in a large freshwater lake. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Iron Catalyst Chemistry in High Pressure Carbon Monoxide Nanotube Reactor

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Povitsky, Alexander; Dateo, Christopher; Gokcen, Tahir; Smalley, Richard E.

    2001-01-01

    The high-pressure carbon monoxide (HiPco) technique for producing single wall carbon nanotubes (SWNT) is analyzed using a chemical reaction model coupled with properties calculated along streamlines. Streamline properties for mixing jets are calculated by the FLUENT code using the k-e turbulent model for pure carbon monixide. The HiPco process introduces cold iron pentacarbonyl diluted in CO, or alternatively nitrogen, at high pressure, ca. 30 atmospheres into a conical mixing zone. Hot CO is also introduced via three jets at angles with respect to the axis of the reactor. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Cluster reaction rates are from Krestinin, et aI., based on shock tube measurements. Another model is from classical cluster theory given by Girshick's team. The calculations are performed on streamlines that assume that a cold mixture of Fe(CO)5 in CO is introduced along the reactor axis. Then iron forms clusters that catalyze the formation of SWNTs from the Boudouard reaction on Fe-containing clusters by reaction with CO. To simulate the chemical process along streamlines that were calculated by the fluid dynamics code FLUENT, a time history of temperature and dilution are determined along streamlines. Alternative catalyst injection schemes are also evaluated.

  3. Effects of iron on optical properties of dissolved organic matter.

    PubMed

    Poulin, Brett A; Ryan, Joseph N; Aiken, George R

    2014-09-02

    Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV-vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV-vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV-vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios (E2:E3) and spectral slope ratios (SR) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation-emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.

  4. Effects of iron on optical properties of dissolved organic matter

    USGS Publications Warehouse

    Poulin, Brett; Ryan, Joseph N.; Aiken, George R.

    2014-01-01

    Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV–vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV–vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV–vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios (E2:E3) and spectral slope ratios (SR) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation–emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.

  5. Biogeochemical reactive transport of carbon, nitrogen and iron in the hyporheic zone

    NASA Astrophysics Data System (ADS)

    Dwivedi, D.; Steefel, C. I.; Newcomer, M. E.; Arora, B.; Spycher, N.; Hammond, G. E.; Moulton, J. D.; Fox, P. M.; Nico, P. S.; Williams, K. H.; Dafflon, B.; Carroll, R. W. H.

    2017-12-01

    To understand how biogeochemical processes in the hyporheic zone influence carbon and nitrogen cycling as well as stream biogeochemistry, we developed a biotic and abiotic reaction network and integrated it into a reactive transport simulator - PFLOTRAN. Three-dimensional reactive flow and transport simulations were performed to describe the hyporheic exchange of fluxes from and within an intra-meander region encompassing two meanders of East River in the East Taylor watershed, Colorado. The objectives of this study were to quantify (1) the effect of transience on the export of carbon, nitrogen, and iron; and (2) the biogeochemical transformation of nitrogen and carbon species as a function of the residence time. The model was able to capture reasonably well the observed trends of nitrate and dissolved oxygen values that decreased as well as iron (Fe (II)) values that increased along the meander centerline away from the stream. Hyporheic flow paths create lateral redox zonation within intra-meander regions, which considerably impact nitrogen export into the stream system. Simulation results further demonstrated that low water conditions lead to higher levels of dissolved iron in groundwater, which (Fe (II)> 80%) is exported to the stream on the downstream side during high water conditions. An important conclusion from this study is that reactive transport models representing spatial and temporal heterogeneities are required to identify important factors that contribute to the redox gradients at riverine scales.

  6. Heterogeneous catalytic ozonation of dibutyl phthalate in aqueous solution in the presence of iron-loaded activated carbon.

    PubMed

    Huang, Yuanxing; Cui, Chenchen; Zhang, Daofang; Li, Liang; Pan, Ding

    2015-01-01

    Iron-loaded activated carbon was prepared and used as catalyst in heterogeneous catalytic ozonation of dibutyl phthalate (DBP). The catalytic activity of iron-loaded activated carbon was investigated under various conditions and the mechanisms of DBP removal were deduced. Characterization of catalyst indicated that the iron loaded on activated carbon was mainly in the form of goethite, which reduced its surface area, pore volume and pore diameter. The presence of metals on activated carbon positively contributed to its catalytic activity in ozonation of DBP. Iron loading content of 15% and initial water pH of 8 achieved highest DBP removal among all the tried conditions. Catalyst dosage of 10 mg L(-1) led to approximately 25% of increase in DBP (initial concentration 2 mg L(-1)) removal in 60 min as compared with ozone alone, and when catalyst dosage increased to 100 mg L(-1), the DBP removal was further improved by 46%. Based on a comparison of reaction rates for direct and indirect transformation of DBP, the increased removal of DBP in this study likely occurred via transformation of ozone into hydroxyl radicals on the catalyst surface. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Chemical Degradation of the Cathodic Electrical Contact Between Carbon and Cast Iron in Aluminum Production Cells

    NASA Astrophysics Data System (ADS)

    Brassard, Martin; Désilets, Martin; Soucy, Gervais; Bilodeau, Jean-François; Forté, Martin

    2017-06-01

    The cathodic carbon to cast iron electrical contact degradation is one of the factors to consider in the cathode voltage drop (CVD) increase over the lifetime of aluminum production cells. Lab-scale experiments were carried out to study the cast iron to carbon interface chemical degradation and the impact of important cell parameters like temperature and bath chemistry. Laboratory degradation results were compared with industrial samples. A thermoelectric Ansys numerical model was then used to predict the effect of cast iron surface degradation over CVD. Results show that the aluminum formation on the cast iron surface and its subsequent diffusion creates an immiscible mixture of Fe-Al metal alloy and electrolytic bath. Disparities were also observed between industrial samples taken from two different technologies, suggesting that the degradation can be slowed down. Thermoelectric calculations finally revealed that the impact of the contact resistance augmentation is by far greater than the cast iron degradation.

  8. The effect of carbon type on arsenic and trichloroethylene removal capabilities of iron (hydr)oxide nanoparticle-impregnated granulated activated carbons.

    PubMed

    Cooper, Anne Marie; Hristovski, Kiril D; Möller, Teresia; Westerhoff, Paul; Sylvester, Paul

    2010-11-15

    This study investigates the impact of the type of virgin granular activated carbon (GAC) media used to synthesize iron (hydr)oxide nanoparticle-impregnated granular activated carbon (Fe-GAC) on its properties and its ability to remove arsenate and organic trichloroethylene (TCE) from water. Two Fe-GAC media were synthesized via a permanganate/ferrous ion synthesis method using bituminous and lignite-based virgin GAC. Data obtained from an array of characterization techniques (pore size distribution, surface charge, etc.) in correlation with batch equilibrium tests, and continuous flow modeling suggested that GAC type and pore size distribution control the iron (nanoparticle) contents, Fe-GAC synthesis mechanisms, and contaminant removal performances. Pore surface diffusion model calculations predicted that lignite Fe-GAC could remove ∼6.3 L g(-1) dry media and ∼4 L g(-1) dry media of water contaminated with 30 μg L(-1) TCE and arsenic, respectively. In contrast, the bituminous Fe-GAC could remove only ∼0.2 L/g dry media for TCE and ∼2.8 L/g dry media for As of the same contaminated water. The results show that arsenic removal capability is increased while TCE removal is decreased as a result of Fe nanoparticle impregnation. This tradeoff is related to several factors, of which changes in surface properties and pore size distributions appeared to be the most dominant. Copyright © 2010 Elsevier B.V. All rights reserved.

  9. Liquid Phase Plasma Synthesis of Iron Oxide Nanoparticles on Nitrogen-Doped Activated Carbon Resulting in Nanocomposite for Supercapacitor Applications.

    PubMed

    Lee, Heon; Lee, Won-June; Park, Young-Kwon; Ki, Seo Jin; Kim, Byung-Joo; Jung, Sang-Chul

    2018-03-25

    Iron oxide nanoparticles supported on nitrogen-doped activated carbon powder were synthesized using an innovative plasma-in-liquid method, called the liquid phase plasma (LPP) method. Nitrogen-doped carbon (NC) was prepared by a primary LPP reaction using an ammonium chloride reactant solution, and an iron oxide/NC composite (IONCC) was prepared by a secondary LPP reaction using an iron chloride reactant solution. The nitrogen component at 3.77 at. % formed uniformly over the activated carbon (AC) surface after a 1 h LPP reaction. Iron oxide nanoparticles, 40~100 nm in size, were impregnated homogeneously over the NC surface after the LPP reaction, and were identified as Fe₃O₄ by X-ray photoelectron spectroscopy and X-ray diffraction. NC and IONCCs exhibited pseudo-capacitive characteristics, and their specific capacitance and cycling stability were superior to those of bare AC. The nitrogen content on the NC surface increased the compatibility and charge transfer rate, and the composites containing iron oxide exhibited a lower equivalent series resistance.

  10. Effects of chloride ions on corrosion of ductile iron and carbon steel in soil environments.

    PubMed

    Song, Yarong; Jiang, Guangming; Chen, Ying; Zhao, Peng; Tian, Yimei

    2017-07-31

    Chloride is reported to play a significant role in corrosion reactions, products and kinetics of ferrous metals. To enhance the understanding of the effects of soil environments, especially the saline soils with high levels of chloride, on the corrosion of ductile iron and carbon steel, a 3-month corrosion test was carried out by exposing ferrous metals to soils of six chloride concentrations. The surface morphology, rust compositions and corrosion kinetics were comprehensively studied by visual observation, scanning electron microscopy (SEM), X-Ray diffraction (XRD), weight loss, pit depth measurement, linear polarization and electrochemical impedance spectroscopy (EIS) measurements. It showed that chloride ions influenced the characteristics and compositions of rust layers by diverting and participating in corrosion reactions. α-FeOOH, γ-FeOOH and iron oxides were major corrosion products, while β-Fe 8 O 8 (OH) 8 Cl 1.35 rather than β-FeOOH was formed when high chloride concentrations were provided. Chloride also suppressed the decreasing of corrosion rates, whereas increased the difficulty in the diffusion process by thickening the rust layers and transforming the rust compositions. Carbon steel is more susceptible to chloride attacks than ductile iron. The corrosion kinetics of ductile iron and carbon steel corresponded with the probabilistic and bilinear model respectively.

  11. Susceptibility of Permafrost Soil Organic Carbon under Warming Climate

    NASA Astrophysics Data System (ADS)

    Yang, Z.; Wullschleger, S. D.; Liang, L.; Graham, D. E.; Gu, B.

    2015-12-01

    Degradation of soil organic carbon (SOC) that has been stored in permafrost is a key concern under warming climate because it could provide a positive feedback. Studies and conceptual models suggest that SOC degradation is largely controlled by the decomposability of SOC, but it is unclear exactly what portions of SOC are susceptible to rapid breakdown and what mechanisms may be involved in SOC degradation. Using a suite of analytical techniques, we examined the dynamic consumption and production of labile SOC compounds, including sugars, alcohols, and small molecular weight organic acids in incubation experiments (up to 240 days at either -2 or 8 °C) with a tundra soil under anoxic conditions, where SOC respiration and iron(III) reduction were monitored. We observe that sugars and alcohols are main components in SOC accounting for initial rapid release of CO2 and CH4 through anaerobic fermentation, whereas the fermentation products such as acetate and formate are subsequently utilized as primary substrates for methanogenesis. Iron(III) reduction is correlated to acetate production and methanogenesis, suggesting its important roles as an electron acceptor in tundra SOC respiration. These observations corroborate strongly with the glucose addition during incubation, in which rapid CO2 and CH4 production is observed concurrently with rapid production and consumption of organics such as acetate. Thus, the biogeochemical processes we document here are pertinent to understanding the accelerated SOC decomposition with temperature and could provide basis for model predicting feedbacks to climate warming in the Arctic.

  12. Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron.

    PubMed

    Zhang, Xianlan; Deng, Baolin; Guo, Jing; Wang, Yang; Lan, Yeqing

    2011-04-01

    Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT. Copyright © 2010 Elsevier Ltd. All rights reserved.

  13. Well-defined iron catalyst for improved hydrogenation of carbon dioxide and bicarbonate.

    PubMed

    Ziebart, Carolin; Federsel, Christopher; Anbarasan, Pazhamalai; Jackstell, Ralf; Baumann, Wolfgang; Spannenberg, Anke; Beller, Matthias

    2012-12-26

    The most efficient, stable, and easy-to-synthesize non-noble metal catalyst system for the reduction of CO(2) and bicarbonates is presented. In the presence of the iron(II)-fluoro-tris(2-(diphenylphosphino)phenyl)phosphino]tetrafluoroborate complex 3, the hydrogenation of bicarbonates proceeds in good yields with high catalyst productivity and activity (TON > 7500, TOF > 750). High-pressure NMR studies of the hydrogenation of carbon dioxide demonstrate that the corresponding iron-hydridodihydrogen complex 4 is crucial in the catalytic cycle.

  14. Weak overturning circulation and increased iron fertilization maximized carbon storage in the glacial ocean

    NASA Astrophysics Data System (ADS)

    Muglia, J.; Skinner, L.; Schmittner, A.

    2017-12-01

    Circulation changes have been suggested to play an important role in the sequestration of atmospheric CO2 in the glacial ocean. However, previous studies have resulted in contradictory results regarding the strength of the Atlantic Meridional Overturning Circulation (AMOC) and three-dimensional, quantitative reconstructions of the glacial ocean constrained by multiple proxies remain lacking. Here we simulate the modern and glacial ocean using a coupled, global, three-dimensional, physical-biogeochemical model constrained simultaneously by d13C, radiocarbon, and d15N to explore the effects of AMOC differences and Southern Ocean iron fertilization on the distributions of these isotopes and ocean carbon storage. We show that d13C and radiocarbon data sparsely sampled at the locations of existing glacial sediment cores can be used to reconstruct the modern AMOC accurately. Applying this method to the glacial ocean we find that a surprisingly weak (6-9 Sv or about half of today's) and shallow AMOC maximizes carbon storage and best reproduces the sediment data. Increasing the atmospheric soluble iron flux in the model's Southern Ocean intensifies export production, carbon storage, and improves agreement with d13C and d15N reconstructions. Our best fitting model is a significant improvement compared with previous studies. It suggests that a weak and shallow AMOC and enhanced iron fertilization conspired to maximize carbon storage in the glacial ocean.

  15. Iron Amendment and Fenton Oxidation of MTBE-Spent Granular Activated Carbon

    EPA Science Inventory

    Fenton-driven regeneration of Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves Fe amendment to the GAC to catalyze H2O2 reactions and to enhance the rate of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, fer...

  16. Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

    2018-06-01

    Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

  17. Growing Carbon Nanotubes

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

    None

    In situ transmission electron microscope (TEM) video (accelerated 10 times) of nucleation and self-organization of a high-density carbon nanotube network from catalytic iron nanoparticles, forming a vertically aligned forest.

  18. "Conjugate channeling" effect in dislocation core diffusion: carbon transport in dislocated BCC iron.

    PubMed

    Ishii, Akio; Li, Ju; Ogata, Shigenobu

    2013-01-01

    Dislocation pipe diffusion seems to be a well-established phenomenon. Here we demonstrate an unexpected effect, that the migration of interstitials such as carbon in iron may be accelerated not in the dislocation line direction ξ, but in a conjugate diffusion direction. This accelerated random walk arises from a simple crystallographic channeling effect. c is a function of the Burgers vector b, but not ξ, thus a dislocation loop possesses the same everywhere. Using molecular dynamics and accelerated dynamics simulations, we further show that such dislocation-core-coupled carbon diffusion in iron has temperature-dependent activation enthalpy like a fragile glass. The 71° mixed dislocation is the only case in which we see straightforward pipe diffusion that does not depend on dislocation mobility.

  19. Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Povitsky, Alexander; Dateo, Christopher; Gokcen, Tahir; Willis, Peter A.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

  20. Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor.

    PubMed

    Scott, Carl D; Povitsky, Alexander; Dateo, Christopher; Gökçen, Tahir; Willis, Peter A; Smalley, Richard E

    2003-01-01

    The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

  1. Determination of natural organic matter and iron binding capacity in fen samples

    NASA Astrophysics Data System (ADS)

    Kügler, Stefan; Cooper, Rebecca E.; Frieder Mohr, Jan; Wichard, Thomas; Küsel, Kirsten

    2017-04-01

    Natural organic matter (NOM) plays an important role in ecosystem processes such as soil carbon stabilization, nutrient availability and metal complexation. Iron-NOM-complexes, for example, are known to increase the solubility and, as a result, the bioavailability of iron in natural environments leading to several effects on the microbial community. Due to the various functions of NOM in natural environments, there is a high level of interest in the characterization of the molecular composition. The complexity of NOM presents a significant challenge in the elucidation of its composition. However, the development and utilization of high resolution mass spectrometry (HR-MS) as a tool to detect single compounds in complex samples has spearheaded the effort to elucidate the composition of NOM. Over the past years, the accuracy of ion cyclotron- or Orbitrap mass spectrometers has increased dramatically resulting in the possibility to obtain a mass differentiation of the large number of compounds in NOM. Together these tools provide significant and powerful insight into the molecular composition of NOM. In the current study, we aim to understand abiotic and biotic interactions between NOM and metals, such as iron, found in the Schlöppnerbrunnen fen (Fichtelgebirge, Germany) and how these interactions impact the microbial consortia. We characterized the dissolved organic matter (DOM) as well as basic chemical parameters in the iron-rich (up to 20 mg (g wt peat)-1), slightly acidic (pH 4.8) fen to gain more information about DOM-metal interactions. This minerotrophic peatland connected to the groundwater has received Fe(II) released from the surrounding soils in the Lehstenbach catchment. Absorption spectroscopy (AAS), differential pulse polarography (DPP) and high resolution electrospray ionization mass spectrometry (HR-ESI-Orbitrap-MS) was applied to characterize the molecular composition of DOM in the peat water extract (PWE). We identified typical patterns for DOM

  2. Seagrass-Mediated Phosphorus and Iron Solubilization in Tropical Sediments

    PubMed Central

    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

  3. Chelating agent-assisted heat treatment of a carbon-supported iron oxide nanoparticle catalyst for PEMFC.

    PubMed

    Liu, Shyh-Jiun; Huang, Chia-Hung; Huang, Chun-Kai; Hwang, Weng-Sing

    2009-08-28

    Iron complexes were supported on commercial carbon black and heat treated to create FeO(x)/C catalysts that showed a larger normalized current density and normalized power density than commercial Pt/C catalysts; the coordination number of the iron complexes used affected the formation of the active site for oxygen reduction in PEMFC.

  4. CO synthesized from the central one-carbon pool as source for the iron carbonyl in O2-tolerant [NiFe]-hydrogenase

    PubMed Central

    Bürstel, Ingmar; Siebert, Elisabeth; Zebger, Ingo; Friedrich, Bärbel

    2016-01-01

    Hydrogenases are nature’s key catalysts involved in both microbial consumption and production of molecular hydrogen. H2 exhibits a strongly bonded, almost inert electron pair and requires transition metals for activation. Consequently, all hydrogenases are metalloenzymes that contain at least one iron atom in the catalytic center. For appropriate interaction with H2, the iron moiety demands for a sophisticated coordination environment that cannot be provided just by standard amino acids. This dilemma has been overcome by the introduction of unprecedented chemistry—that is, by ligating the iron with carbon monoxide (CO) and cyanide (or equivalent) groups. These ligands are both unprecedented in microbial metabolism and, in their free form, highly toxic to living organisms. Therefore, the formation of the diatomic ligands relies on dedicated biosynthesis pathways. So far, biosynthesis of the CO ligand in [NiFe]-hydrogenases was unknown. Here we show that the aerobic H2 oxidizer Ralstonia eutropha, which produces active [NiFe]-hydrogenases in the presence of O2, employs the auxiliary protein HypX (hydrogenase pleiotropic maturation X) for CO ligand formation. Using genetic engineering and isotope labeling experiments in combination with infrared spectroscopic investigations, we demonstrate that the α-carbon of glycine ends up in the CO ligand of [NiFe]-hydrogenase. The α-carbon of glycine is a building block of the central one-carbon metabolism intermediate, N10-formyl-tetrahydrofolate (N10-CHO-THF). Evidence is presented that the multidomain protein, HypX, converts the formyl group of N10-CHO-THF into water and CO, thereby providing the carbonyl ligand for hydrogenase. This study contributes insights into microbial biosynthesis of metal carbonyls involving toxic intermediates. PMID:27930319

  5. Size-dependent surface phase change of lithium iron phosphate during carbon coating

    NASA Astrophysics Data System (ADS)

    Wang, Jiajun; Yang, Jinli; Tang, Yongji; Liu, Jian; Zhang, Yong; Liang, Guoxian; Gauthier, Michel; Karen Chen-Wiegart, Yu-Chen; Norouzi Banis, Mohammad; Li, Xifei; Li, Ruying; Wang, Jun; Sham, T. K.; Sun, Xueliang

    2014-03-01

    Carbon coating is a simple, effective and common technique for improving the conductivity of active materials in lithium ion batteries. However, carbon coating provides a strong reducing atmosphere and many factors remain unclear concerning the interface nature and underlying interaction mechanism that occurs between carbon and the active materials. Here, we present a size-dependent surface phase change occurring in lithium iron phosphate during the carbon coating process. Intriguingly, nanoscale particles exhibit an extremely high stability during the carbon coating process, whereas microscale particles display a direct visualization of surface phase changes occurring at the interface at elevated temperatures. Our findings provide a comprehensive understanding of the effect of particle size during carbon coating and the interface interaction that occurs on carbon-coated battery material—allowing for further improvement in materials synthesis and manufacturing processes for advanced battery materials.

  6. A field investigation on transport of carbon-supported nanoscale zero-valent iron (nZVI) in groundwater.

    PubMed

    Busch, J; Meißner, T; Potthoff, A; Bleyl, S; Georgi, A; Mackenzie, K; Trabitzsch, R; Werban, U; Oswald, S E

    2015-10-01

    The application of nanoscale zero-valent iron (nZVI) for subsurface remediation of groundwater contaminants is a promising new technology, which can be understood as alternative to the permeable reactive barrier technique using granular iron. Dechlorination of organic contaminants by zero-valent iron seems promising. Currently, one limitation to widespread deployment is the fast agglomeration and sedimentation of nZVI in colloidal suspensions, even more so when in soils and sediments, which limits the applicability for the treatment of sources and plumes of contamination. Colloid-supported nZVI shows promising characteristics to overcome these limitations. Mobility of Carbo-Iron Colloids (CIC) - a newly developed composite material based on finely ground activated carbon as a carrier for nZVI - was tested in a field application: In this study, a horizontal dipole flow field was established between two wells separated by 5.3m in a confined, natural aquifer. The injection/extraction rate was 500L/h. Approximately 1.2kg of CIC was suspended with the polyanionic stabilizer carboxymethyl cellulose. The suspension was introduced into the aquifer at the injection well. Breakthrough of CIC was observed visually and based on total particle and iron concentrations detected in samples from the extraction well. Filtration of water samples revealed a particle breakthrough of about 12% of the amount introduced. This demonstrates high mobility of CIC particles and we suggest that nZVI carried on CIC can be used for contaminant plume remediation by in-situ formation of reactive barriers. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Iron content of soils as a precipitation proxy

    NASA Astrophysics Data System (ADS)

    Dzombak, R.; Sheldon, N. D.

    2016-12-01

    Given that different iron phases form under different precipitation and drainage regimes, soil iron content could be used as a proxy for both volume and seasonality of precipitation. Constraining these factors is important for predicting future precipitation trends, especially for a warmer climate that will likely see more frequent extreme weather events. Specifically, using paleoprecipitation data from periods of higher temperatures and atmospheric CO2 concentrations helps inform models of future `greenhouse' climate. Forty-five modern samples from across the continental United States were analyzed, with MAP ranging from 200 to 1200 mm yr-1 and MAT ranging from 5 to 22°C. Soil types included Alfisols (N=15), Inceptisols (N=8), Mollisols (N=15), and Aridisols (N=7), and ranged from seasonally wet to well-drained. Analytical techniques included combustion-elemental analysis and organic carbon isotope analysis, a sequential iron extraction modified with a sodium hypochlorite step for the extraction of organic matter-bound iron, and the extraction of iron sulfides. The sequential extractions yield five different `pools' of iron found in sediment: crystalline iron oxides (e.g., goethite, hematite), magnetite, carbonate-bound, organic matter-bound, and labile/easily reducible iron minerals (e.g., ferrihydrite). Analysis by ICP-OES yielded a strong relationship between magnetite-bound iron and MAP, and fair relationships between the other iron pools and MAP. Individual soil orders tended to show stronger relationships to the iron pools than all soils analyzed together, potentially indicating the need for separate proxy relationships for each soil order. Pyrite concentrations were well below 1% by weight for these soils, suggesting that none of these soils has a long enough wet season to encourage its formation and that the presence vs. absence of pyrite in paleosols may be a useful proxy for soil moisture state. In contrast to some earlier work, no significant

  8. Carbon Solubility in Silicon-Iron-Bearing Metals during Core Formation on Mercury

    NASA Technical Reports Server (NTRS)

    Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Ross, D. Kent; Rapp, Jennifer F.; Danielson, Lisa R.; Keller, Lindsay P.; Righter, Kevin

    2016-01-01

    Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft showed the surface of Mercury has high S abundances (approximately 4 wt%) and low Iron(II) Oxide abundances (less than 2 wt%). Based on these extreme values, the oxygen fugacity of Mercury's surface materials was estimated to be approximately 3 to 7 log(sub 10) units below the IW buffer (Delta IW-3 to Delta IW-7). This highly reducing nature of the planet has resulted in a large core and relatively thin mantle, extending to only approximately 420 km depth (corresponding to a core-mantle boundary pressure of approximately 4-7 GPa) within the planet. Furthermore, MESSENGER results have suggested the presence of carbon on the surface of the planet. Previous experimental results from have also suggested the possibility of a primary floatation crust on Mercury composed of graphite, produced after a global magma ocean event. With these exotic conditions of this compositional end-member planet, it begs the question, what is the core composition of Mercury? Although no definitive conclusion has been reached, previous studies have made advances towards answering this question. Riner et al. and Chen et al. looked at iron sulfide systems and implemented various crystallization and layered core scenarios to try and determine the composition and structure of Mercury's core. Malavergne et al. examined core crystallization scenarios in the presence of sulfur and silicon. Hauck et al. used the most recent geophysical constraints from the MESSENGER spacecraft to model the internal structure of Mercury, including the core, in a iron-sulfur-silicon system. More recently, Chabot et al. conducted a series of metal-silicate partitioning experiments in a iron-sulfur-silicon system. These results showed the core of Mercury has the potential to contain more than 15 wt% silicon. However, with the newest results from MESSENGER's low altitude campaign, carbon is another

  9. Organic carbon isotope constraints on the dissolved organic carbon (DOC) reservoir at the Cryogenian-Ediacaran transition

    NASA Astrophysics Data System (ADS)

    Jiang, Ganqing; Wang, Xinqiang; Shi, Xiaoying; Zhang, Shihong; Xiao, Shuhai; Dong, Jin

    2010-10-01

    Prominent negative carbonate carbon isotope (δ 13C carb) anomalies from some Ediacaran successions are accompanied by invariant or decoupled organic carbon isotope (δ 13C org) values and have been interpreted as resulting from the remineralization of a large dissolved organic carbon (DOC) reservoir capable of buffering carbon isotopes of organic matter. This inferred oceanic DOC reservoir was thought to have initiated with the onset of Cryogenian glaciations (ca. 720 Ma) and lasted for millions of years until the late Ediacaran Period (< 560 Ma). Carbon isotope analyses of the basal Doushantuo Formation (ca. 635 Ma) in south China reveal that (1) the cap carbonate has δ 13C org around -26‰ (VPDB) and relatively low Δδ 13C (22 ± 2‰) and (2) the overlying organic-rich black shale and shaly dolostone have more negative δ 13C org (-28‰ to -35‰) and higher Δδ 13C (28‰-30‰). Both δ 13C carb and δ 13C org show a + 6‰ shift within a 4-m-thick interval overlying the Doushantuo cap carbonate. The δ 13C org values of the cap carbonate are associated with low TOC (mostly < 0.1%); their paleoceanographic significance requires further tests in other Ediacaran basins. The co-varying positive shift in δ 13C carb and δ 13C org following cap carbonate deposition is best interpreted as resulting from a rapid increase in organic carbon burial, which may have resulted in the rise of oxygen and heralded the first appearance of animals a few meters above the Doushantuo cap carbonate. The data suggest that a large oceanic DOC reservoir did not exist in the early Ediacaran ocean. Excess oceanic DOC required to explain the Ediacaran Shuram and upper Doushantuo δ 13C excursions, if it existed, had to be developed during the Ediacaran Period after cap carbonate deposition.

  10. Microbial Communities Associated with Biogenic Iron Oxide Mineralization in Circumneutral pH Environments

    NASA Astrophysics Data System (ADS)

    Chan, C. S.; Banfield, J. F.

    2002-12-01

    Lithotrophic growth on iron is a metabolism that has been found in a variety of neutral pH environments and is likely important in sustaining life in microaerophilic solutions, especially those low in organics. The composition of the microbial communities, especially the organisms that are responsible for iron oxidation, and carbon and nitrogen fixation, are not known, yet the ability to recognize these contributions is vital to our understanding of iron cycling in natural environments. Our approach has been to study the microbial community structure, mineralogy, and geochemistry of ~20 cm thick, 100's meters long, fluffy iron oxide-encrusted biological mats growing in the Piquette Mine tunnel, and to compare the results to those from geochemically similar environments. In situ measurements (Hydrolab) and geochemical characterization of bulk water samples and peepers (dialysis sampling vials) indicate that the environment is microaerobic, with micromolar levels of iron, high carbonate and sulfate, and typical groundwater nitrate and nitrite concentrations. 16S rDNA clone libraries show that the microbial mat and water contain communities with considerable diversity within the Bacterial domain, a large proportion of Nitrospira and Betaproteobacteria, and no Archaea. Because clone library data are not necessarily indicative of actual abundance, fluorescence in-situ hybridization (FISH) was performed on water, mat, and sediment samples from the Piquette mine and two circumneutral iron- and carbonate-rich springs in the Oregon Cascade Range. Domain- and phylum-level probes were chosen based on the clone library results (Nitrospira, Beta- and Gammaproteobacteria, Acidobacteria, Actinobacteria, Chloroflexi, and Planctomyces). FISH data reveal spatial associations between specific microbial groups and mineralized structures. The organisms responsible for making the mineralized sheaths that compose the bulk of the iron oxide mat are Betaproteobacteria (probably Leptothrix

  11. Zero-valent iron particles embedded on the mesoporous silica-carbon for chromium (VI) removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Xiong, Kun; Gao, Yuan; Zhou, Lin; Zhang, Xianming

    2016-09-01

    Nanoscale zero-valent iron (nZVI) particles were embedded on the walls of mesoporous silica-carbon (MSC) under the conditions of high-temperature carbonization and reduction and used to remove chromium (VI) from aqueous solution. The structure and textural properties of nZVI-MSC were characterized by the powder X-ray diffraction, transmission electron microscopy and N2 adsorption and desorption. The results show that nZVI-MSC has highly ordered mesoporous structure and large surface area, indistinguishable with that of MSC. Compared with the support MSC and iron particles supported on the activated carbon (nZVI/AC), nZVI-MSC exhibited much higher Cr(VI) removal efficiency with about 98 %. The removal process obeys a pseudo first-order model. Such excellent performance of nZVI-MSC could be ascribed to the large surface and iron particles embedded on the walls of the MSC, forming an intimate contact with the MSC. It is proposed that this feature might create certain micro-electrode on the interface of iron particles and MSC, which prevented the formation of metal oxide on the surface and provided fresh Fe surface for Cr(VI) removal.

  12. IRON OPTIMIZATION FOR FENTON-DRIVEN OXIDATION OF MTBE-SPENT GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton-driven chemical regeneration of granular activated carbon (GAC) is accomplished through the addition of H2O2 and iron (Fe) to spent GAC. The overall objective of this treatment process is to transform target contaminants into less toxic byproducts, re-establish the sorpti...

  13. Effect of accelerated carbonation and zero valent iron on metal leaching from bottom ash.

    PubMed

    Nilsson, M; Andreas, L; Lagerkvist, A

    2016-05-01

    About 85% of the ashes produced in Sweden originated from the incineration of municipal solid waste and biofuel. The rest comes from the thermal treatment of recycled wood, peat, charcoal and others. About 68% of all ashes annually produced in Sweden are used for constructions on landfills, mainly slopes, roads and embankments, and only 3% for construction of roads and working surfaces outside the landfills (SCB, 2013). Since waste bottom ash (BA) often has similar properties to crushed bedrock or gravel, it could be used for road constructions to a larger extent. However, the leaching of e.g. Cr, Cu, Mo, Pb and Zn can cause a threat to the surrounding environment if the material is used as it is. Carbonation is a commonly used pre-treatment method, yet it is not always sufficient. As leaching from aged ash is often controlled by adsorption to iron oxides, increasing the number of Fe oxide sorption sites can be a way to control the leaching of several critical elements. The importance of iron oxides as sorption sites for metals is known from both mineralogical studies of bottom ash and from the remediation of contaminated soil, where iron is used as an amendment. In this study, zero valent iron (Fe(0)) was added prior to accelerated carbonation in order to increase the number of adsorption sites for metals and thereby reduce leaching. Batch, column and pHstat leaching tests were performed and the leaching behaviour was evaluated with multivariate data analysis. It showed that leaching changed distinctly after the tested treatments, in particular after the combined treatment. Especially, the leaching of Cr and Cu clearly decreased as a result of accelerated carbonation. The combination of accelerated carbonation with Fe(0) addition reduced the leaching of Cr and Cu even further and reduced also the leaching of Mo, Zn, Pb and Cd compared to untreated BA. Compared with only accelerated carbonation, the Fe(0) addition significantly reduced the leaching of Cr, Cu and Mo

  14. Properties and effects of remaining carbon from waste plastics gasifying on iron scale reduction.

    PubMed

    Zhang, Chongmin; Chen, Shuwen; Miao, Xincheng; Yuan, Hao

    2011-06-01

    The carbonous activities of three kinds of carbon-bearing materials gasified from plastics were tested with coal coke as reference. The results showed that the carbonous activities of these remaining carbon-bearing materials were higher than that of coal-coke. Besides, the fractal analyses showed that the porosities of remaining carbon-bearing materials were higher than that of coal-coke. It revealed that these kinds of remaining carbon-bearing materials are conducive to improve the kinetics conditions of gas-solid phase reaction in iron scale reduction. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  15. The Organization of Controller Motifs Leading to Robust Plant Iron Homeostasis

    PubMed Central

    Agafonov, Oleg; Selstø, Christina Helen; Thorsen, Kristian; Xu, Xiang Ming; Drengstig, Tormod; Ruoff, Peter

    2016-01-01

    Iron is an essential element needed by all organisms for growth and development. Because iron becomes toxic at higher concentrations iron is under homeostatic control. Plants face also the problem that iron in the soil is tightly bound to oxygen and difficult to access. Plants have therefore developed special mechanisms for iron uptake and regulation. During the last years key components of plant iron regulation have been identified. How these components integrate and maintain robust iron homeostasis is presently not well understood. Here we use a computational approach to identify mechanisms for robust iron homeostasis in non-graminaceous plants. In comparison with experimental results certain control arrangements can be eliminated, among them that iron homeostasis is solely based on an iron-dependent degradation of the transporter IRT1. Recent IRT1 overexpression experiments suggested that IRT1-degradation is iron-independent. This suggestion appears to be misleading. We show that iron signaling pathways under IRT1 overexpression conditions become saturated, leading to a breakdown in iron regulation and to the observed iron-independent degradation of IRT1. A model, which complies with experimental data places the regulation of cytosolic iron at the transcript level of the transcription factor FIT. Including the experimental observation that FIT induces inhibition of IRT1 turnover we found a significant improvement in the system’s response time, suggesting a functional role for the FIT-mediated inhibition of IRT1 degradation. By combining iron uptake with storage and remobilization mechanisms a model is obtained which in a concerted manner integrates iron uptake, storage and remobilization. In agreement with experiments the model does not store iron during its high-affinity uptake. As an iron biofortification approach we discuss the possibility how iron can be accumulated even during high-affinity uptake. PMID:26800438

  16. “Conjugate Channeling” Effect in Dislocation Core Diffusion: Carbon Transport in Dislocated BCC Iron

    PubMed Central

    Ishii, Akio; Li, Ju; Ogata, Shigenobu

    2013-01-01

    Dislocation pipe diffusion seems to be a well-established phenomenon. Here we demonstrate an unexpected effect, that the migration of interstitials such as carbon in iron may be accelerated not in the dislocation line direction , but in a conjugate diffusion direction. This accelerated random walk arises from a simple crystallographic channeling effect. is a function of the Burgers vector b, but not , thus a dislocation loop possesses the same everywhere. Using molecular dynamics and accelerated dynamics simulations, we further show that such dislocation-core-coupled carbon diffusion in iron has temperature-dependent activation enthalpy like a fragile glass. The 71° mixed dislocation is the only case in which we see straightforward pipe diffusion that does not depend on dislocation mobility. PMID:23593255

  17. Effects of Carbon Addition on Iron and Phosphorus in a Highly Weathered Tropical Soil

    NASA Astrophysics Data System (ADS)

    Liptzin, D.; Silver, W. L.

    2008-12-01

    In the highly weathered iron (Fe)-rich soils of wet tropical forests, Fe may play a key role in controlling ecosystem processes because of its interactions with carbon (C) and phosphorus (P). The high NPP typical of tropical forests contributes significantly to the global C cycle. In Fe-rich tropical soils, NPP is thought to be limited by P. The periodic reducing conditions that occur in upland tropical soils may be associated with pulses of increased P availability because of the release of Fe-bound P during iron reduction. While little is known about the factors controlling Fe reduction in soils, it is likely that C availability plays a role. Typically, only simple C sources like acetate or glucose have been used to examine this limitation. However, the source of much of the C in nature is the complex mixture of organic compounds leached from leaves and litter. To investigate the linkages between Fe, C, and P, we compared the effects adding either acetate (200 mg C/L) or leaf leachate in low (50-100 mg C/L) or high (150-200 mg C/L) concentrations to incubated soils from a tropical rain forest in Puerto Rico under ambient atmospheric conditions. We measured pools of iron and phosphorus as well as pH at four time points over a month. Both Fe(II) and pH exhibited significant treatment effects, but not until the last sampling date. At this time, the Fe(II) concentration could explain 49% of the variability in soil pH. The pH was significantly higher in the acetate treatments than both the leaf leachate treatments. While Fe(II) concentration was significantly higher in the acetate treatment than the control and low leaf leachate treatment, there was no difference compared to the high leaf leachate treatment After one month microbial biomass P had increased significantly while the NaOH extractable organic P had decreased significantly. These changes suggest the rapid microbial uptake of P liberated from Fe. In conclusion, microbes appear to utilize more complex C in

  18. Modeling the bloom evolution and carbon flows during SOIREE: Implications for future in situ iron-enrichments in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Hannon, E.; Boyd, P. W.; Silvoso, M.; Lancelot, C.

    The impact of a mesoscale in situ iron-enrichment experiment (SOIREE) on the planktonic ecosystem and biological pump in the Australasian-Pacific sector of the Southern Ocean was investigated through model simulations over a period of 60-d following an initial iron infusion. For this purpose we used a revised version of the biogeochemical SWAMCO model ( Lancelot et al., 2000), which describes the cycling of C, N, P, Si, Fe through aggregated chemical and biological components of the planktonic ecosystem in the high nitrate low chlorophyll (HNLC) waters of the Southern Ocean. Model runs were conducted for both the iron-fertilized waters and the surrounding HNLC waters, using in situ meteorological forcing. Validation was performed by comparing model predictions with observations recorded during the 13-d site occupation of SOIREE. Considerable agreement was found for the magnitude and temporal trends in most chemical and biological variables (the microbial food web excepted). Comparison of simulations run for 13- and 60-d showed that the effects of iron fertilization on the biota were incomplete over the 13-d monitoring of the SOIREE bloom. The model results indicate that after the vessel departed the SOIREE site there were further iron-mediated increases in properties such as phytoplankton biomass, production, export production, and uptake of atmospheric CO 2, which peaked 20-30 days after the initial iron infusion. Based on model simulations, the increase in net carbon production at the scale of the fertilized patch (assuming an area of 150 km2) was estimated to 9725 t C by day 60. Much of this production accumulated in the upper ocean, so that the predicted downward export of particulate organic carbon (POC) only represented 22% of the accumulated C in the upper ocean. Further model runs that implemented improved parameterization of diatom sedimentation (i.e. including iron-mediated diatom sinking rate, diatom chain-forming and aggregation) suggested that the

  19. [Organic carbon and carbon mineralization characteristics in nature forestry soil].

    PubMed

    Yang, Tian; Dai, Wei; An, Xiao-Juan; Pang, Huan; Zou, Jian-Mei; Zhang, Rui

    2014-03-01

    Through field investigation and indoor analysis, the organic carbon content and organic carbon mineralization characteristics of six kinds of natural forest soil were studied, including the pine forests, evergreen broad-leaved forest, deciduous broad-leaved forest, mixed needle leaf and Korean pine and Chinese pine forest. The results showed that the organic carbon content in the forest soil showed trends of gradual decrease with the increase of soil depth; Double exponential equation fitted well with the organic carbon mineralization process in natural forest soil, accurately reflecting the mineralization reaction characteristics of the natural forest soil. Natural forest soil in each layer had the same mineralization reaction trend, but different intensity. Among them, the reaction intensity in the 0-10 cm soil of the Korean pine forest was the highest, and the intensities of mineralization reaction in its lower layers were also significantly higher than those in the same layers of other natural forest soil; comparison of soil mineralization characteristics of the deciduous broad-leaved forest and coniferous and broad-leaved mixed forest found that the differences of litter species had a relatively strong impact on the active organic carbon content in soil, leading to different characteristics of mineralization reaction.

  20. Tuning Organic Carbon Dioxide Absorbents for Carbonation and Decarbonation

    PubMed Central

    Rajamanickam, Ramachandran; Kim, Hyungsoo; Park, Ji-Woong

    2015-01-01

    The reaction of carbon dioxide with a mixture of a superbase and alcohol affords a superbase alkylcarbonate salt via a process that can be reversed at elevated temperatures. To utilize the unique chemistry of superbases for carbon capture technology, it is essential to facilitate carbonation and decarbonation at desired temperatures in an easily controllable manner. Here, we demonstrate that the thermal stabilities of the alkylcarbonate salts of superbases in organic solutions can be tuned by adjusting the compositions of hydroxylic solvent and polar aprotic solvent mixtures, thereby enabling the best possible performances to be obtained from the various carbon dioxide capture agents based on these materials. The findings provides valuable insights into the design and optimization of organic carbon dioxide absorbents. PMID:26033537

  1. Stability of organic carbon in deep soil layers controlled by fresh carbon supply.

    PubMed

    Fontaine, Sébastien; Barot, Sébastien; Barré, Pierre; Bdioui, Nadia; Mary, Bruno; Rumpel, Cornelia

    2007-11-08

    The world's soils store more carbon than is present in biomass and in the atmosphere. Little is known, however, about the factors controlling the stability of soil organic carbon stocks and the response of the soil carbon pool to climate change remains uncertain. We investigated the stability of carbon in deep soil layers in one soil profile by combining physical and chemical characterization of organic carbon, soil incubations and radiocarbon dating. Here we show that the supply of fresh plant-derived carbon to the subsoil (0.6-0.8 m depth) stimulated the microbial mineralization of 2,567 +/- 226-year-old carbon. Our results support the previously suggested idea that in the absence of fresh organic carbon, an essential source of energy for soil microbes, the stability of organic carbon in deep soil layers is maintained. We propose that a lack of supply of fresh carbon may prevent the decomposition of the organic carbon pool in deep soil layers in response to future changes in temperature. Any change in land use and agricultural practice that increases the distribution of fresh carbon along the soil profile could however stimulate the loss of ancient buried carbon.

  2. The Iron Metallome in Eukaryotic Organisms

    PubMed Central

    Dlouhy, Adrienne C.; Outten, Caryn E.

    2013-01-01

    This chapter is focused on the iron metallome in eukaryotes at the cellular and subcellular level, including properties, utilization in metalloproteins, trafficking, storage, and regulation of these processes. Studies in the model eukaryote Saccharomyces cerevisiae and mammalian cells will be highlighted. The discussion of iron properties will center on the speciation and localization of intracellular iron as well as the cellular and molecular mechanisms for coping with both low iron bioavailability and iron toxicity. The section on iron metalloproteins will emphasize heme, iron-sulfur cluster, and non-heme iron centers, particularly their cellular roles and mechanisms of assembly. The section on iron uptake, trafficking, and storage will compare methods used by yeast and mammalian cells to import iron, how this iron is brought into various organelles, and types of iron storage proteins. Regulation of these processes will be compared between yeast and mammalian cells at the transcriptional, post-transcriptional, and post-translational levels. PMID:23595675

  3. Disassembling Iron Availability to Phytoplankton

    PubMed Central

    Shaked, Yeala; Lis, Hagar

    2012-01-01

    The bioavailability of iron to microorganisms and its underlying mechanisms have far reaching repercussions to many natural systems and diverse fields of research, including ocean biogeochemistry, carbon cycling and climate, harmful algal blooms, soil and plant research, bioremediation, pathogenesis, and medicine. Within the framework of ocean sciences, short supply and restricted bioavailability of Fe to phytoplankton is thought to limit primary production and curtail atmospheric CO2 drawdown in vast ocean regions. Yet a clear-cut definition of bioavailability remains elusive, with elements of iron speciation and kinetics, phytoplankton physiology, light, temperature, and microbial interactions, to name a few, all intricately intertwined into this concept. Here, in a synthesis of published and new data, we attempt to disassemble the complex concept of iron bioavailability to phytoplankton by individually exploring some of its facets. We distinguish between the fundamentals of bioavailability – the acquisition of Fe-substrate by phytoplankton – and added levels of complexity involving interactions among organisms, iron, and ecosystem processes. We first examine how phytoplankton acquire free and organically bound iron, drawing attention to the pervasiveness of the reductive uptake pathway in both prokaryotic and eukaryotic autotrophs. Turning to acquisition rates, we propose to view the availability of various Fe-substrates to phytoplankton as a spectrum rather than an absolute “all or nothing.” We then demonstrate the use of uptake rate constants to make comparisons across different studies, organisms, Fe-compounds, and environments, and for gaging the contribution of various Fe-substrates to phytoplankton growth in situ. Last, we describe the influence of aquatic microorganisms on iron chemistry and fate by way of organic complexation and bio-mediated redox transformations and examine the bioavailability of these bio-modified Fe species. PMID:22529839

  4. Influences of iron and calcium carbonate on wastewater treatment performances of algae based reactors.

    PubMed

    Zhao, Zhimiao; Song, Xinshan; Wang, Wei; Xiao, Yanping; Gong, Zhijie; Wang, Yuhui; Zhao, Yufeng; Chen, Yu; Mei, Mengyuan

    2016-09-01

    The influences of iron and calcium carbonate (CaCO3) addition in wastewater treatments reactors performance were investigated. Adding different concentrations of Fe(3+) (5, 10, 30 and 50mmol/m(3)), iron and CaCO3 powder led to changes in algal characteristics and physico-chemical and microbiological properties. According to the investigation results, nutrient removal efficiency in algae based reactors was obviously increased by the addition of 10mmol/m(3) Fe(3+), iron (5mmol/m(3)) and CaCO3 powder (0.2gm(-3)) and the removal efficiencies of BOD5, TN, and TP in Stage 2 were respectively increased by 28%, 8.9%, and 22%. The improvements in physico-chemical performances were verified by microbial community tests (bacteria quantity, activity and community measured in most probable number, extracellular enzymes activity, and Biolog Eco Plates). Microbial variations indicated the coexistence of Fe ions and carbonate-bicarbonate, which triggered the synergistic effect of physico-chemical action and microbial factors in algae based reactors. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. A Mesoproterozoic iron formation

    NASA Astrophysics Data System (ADS)

    Canfield, Donald E.; Zhang, Shuichang; Wang, Huajian; Wang, Xiaomei; Zhao, Wenzhi; Su, Jin; Bjerrum, Christian J.; Haxen, Emma R.; Hammarlund, Emma U.

    2018-04-01

    We describe a 1,400 million-year old (Ma) iron formation (IF) from the Xiamaling Formation of the North China Craton. We estimate this IF to have contained at least 520 gigatons of authigenic Fe, comparable in size to many IFs of the Paleoproterozoic Era (2,500–1,600 Ma). Therefore, substantial IFs formed in the time window between 1,800 and 800 Ma, where they are generally believed to have been absent. The Xiamaling IF is of exceptionally low thermal maturity, allowing the preservation of organic biomarkers and an unprecedented view of iron-cycle dynamics during IF emplacement. We identify tetramethyl aryl isoprenoid (TMAI) biomarkers linked to anoxygenic photosynthetic bacteria and thus phototrophic Fe oxidation. Although we cannot rule out other pathways of Fe oxidation, iron and organic matter likely deposited to the sediment in a ratio similar to that expected for anoxygenic photosynthesis. Fe reduction was likely a dominant and efficient pathway of organic matter mineralization, as indicated by organic matter maturation by Rock Eval pyrolysis combined with carbon isotope analyses: Indeed, Fe reduction was seemingly as efficient as oxic respiration. Overall, this Mesoproterozoic-aged IF shows many similarities to Archean-aged (>2,500 Ma) banded IFs (BIFs), but with an exceptional state of preservation, allowing an unprecedented exploration of Fe-cycle dynamics in IF deposition.

  6. On the synthesis and magnetic properties of multiwall carbon nanotube-superparamagnetic iron oxide nanoparticle nanocomposites.

    PubMed

    Narayanan, T N; Mary, A P Reena; Shaijumon, M M; Ci, Lijie; Ajayan, P M; Anantharaman, M R

    2009-02-04

    Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT-SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at approximately 110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT-SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT-SPION composite can be envisaged as a good agent for various biomedical applications.

  7. Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride

    DOE PAGES

    Martinez, Jorge L.; Lin, Hsiu-Jung; Lee, Wei-Tsung; ...

    2017-09-21

    The new iron(IV) nitride complex PhB( iPr 2Im) 3Fe≡N reacts with two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB( iPr 2Im) 3Fe(CN)(N 2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr 2N-C≡C-N iPr 2. The iron complex is in equilibrium with an N 2- free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C 6F 5) 3 provides the cyanoborane derivative.

  8. Physiological and Proteomic Analysis of Escherichia coli Iron-Limited Chemostat Growth

    PubMed Central

    Folsom, James Patrick; Parker, Albert E.

    2014-01-01

    Iron bioavailability is a major limiter of bacterial growth in mammalian host tissue and thus represents an important area of study. Escherichia coli K-12 metabolism was studied at four levels of iron limitation in chemostats using physiological and proteomic analyses. The data documented an E. coli acclimation gradient where progressively more severe iron scarcity resulted in a larger percentage of substrate carbon being directed into an overflow metabolism accompanied by a decrease in biomass yield on glucose. Acetate was the primary secreted organic by-product for moderate levels of iron limitation, but as stress increased, the metabolism shifted to secrete primarily lactate (∼70% of catabolized glucose carbon). Proteomic analysis reinforced the physiological data and quantified relative increases in glycolysis enzyme abundance and decreases in tricarboxylic acid (TCA) cycle enzyme abundance with increasing iron limitation stress. The combined data indicated that E. coli responds to limiting iron by investing the scarce resource in essential enzymes, at the cost of catabolic efficiency (i.e., downregulating high-ATP-yielding pathways containing enzymes with large iron requirements, like the TCA cycle). Acclimation to iron-limited growth was contrasted experimentally with acclimation to glucose-limited growth to identify both general and nutrient-specific acclimation strategies. While the iron-limited cultures maximized biomass yields on iron and increased expression of iron acquisition strategies, the glucose-limited cultures maximized biomass yields on glucose and increased expression of carbon acquisition strategies. This study quantified ecologically competitive acclimations to nutrient limitations, yielding knowledge essential for understanding medically relevant bacterial responses to host and to developing intervention strategies. PMID:24837288

  9. Chemical oxygen demand removal efficiency and limited factors study of aminosilicone polymers in a water emulsion by iron-carbon micro-electrolysis.

    PubMed

    Yang, Shangyuan; Liang, Zhiwei; Yu, Huadong; Wang, Yunlong; Chen, Yingxu

    2014-02-01

    Micro-electrolysis was applied in the present study to investigate the effect of pH, iron-carbon mass ratio, contact time, and treatment batch on the removal efficiency of chemical oxygen demand (COD) within an aminosilicone emulsion. The results exhibited that the removal efficiency of COD decreased linearly with the batch increase, and this tendency was consistent under the various conditions. The adsorption of activated carbons contributes a large portion to the elimination of COD within the aminosilicone emulsion. The oxidation action of iron-carbon micro-electrolysis was proven and the aminosilicone emulsion's COD removal contribution was approximately 16%. Aminosilicone polymers were adsorbed on the surface of activated carbons and iron chips, which contributes to the decline of COD removal efficiency and limits the contribution of oxidation action.

  10. Microbial fuel cells equipped with an iron-plated carbon-felt anode and Shewanella oneidensis MR-1 with corn steep liquor as a fuel.

    PubMed

    Phansroy, Nichanan; Khawdas, Wichean; Watanabe, Keigo; Aso, Yuji; Ohara, Hitomi

    2018-05-12

    A single chamber type microbial fuel cell (MFC) with 100 mL of chamber volume and 50 cm 2 of air-cathode was developed in this study wherein a developed iron-plated carbon-felt anode and Shewanella oneidensis MR-1 were used. The performance of the iron-plated carbon-felt anode and the possibility of corn steep liquor (CSL) as a fuel, which was the byproduct of corn wet milling and contained lactic acid, was investigated here. MFCs equipped with iron-plated or non-plated carbon-felt anodes exhibited maximum current densities of 443 or 302 mA/m 2 using 10 g/L of reagent-grade lactic acid, respectively. In addition, using centrifuged CSL without insoluble ingredients or non-centrifuged CSL as a fuel, the maximum current densities of the MFCs with iron-plated carbon-felt anode were 321 or 158 mA/m 2 , respectively. This report demonstrated the effect of iron-plated carbon-felt anode for electricity generation of MFC using S. oneidensis MR-1 and the performance of CSL as a fuel. Copyright © 2018 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  11. Storage of Organic and Inorganic Carbon in Human Settlements

    NASA Astrophysics Data System (ADS)

    Churkina, G.

    2009-12-01

    It has been shown that urban areas have carbon density comparable with tropical forest. Carbon density of urban areas may be even higher, because the density of organic carbon only was taking into account. Human settlements store carbon in two forms such as organic and inorganic. Carbon is stored in organic form in living biomass such as trees, grasses or in artifacts derived from biomass such as wooden furniture, building structures, paper, clothes and shoes made from natural materials. Inorganic carbon or fossil carbon, meanwhile, is primarily stored in objects fabricated by people like concrete, plastic, asphalt, and bricks. The key difference between organic and inorganic forms of carbon is how they return to the gaseous state. Organic carbon can be returned to the atmosphere without applying additional artificial energy through decomposition of organic matter, whereas energy input such as burning is needed to release inorganic carbon. In this study I compare inorganic with organic carbon storage, discuss their carbon residence time, decomposition rates, and possible implications for carbon emissions.

  12. Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

    PubMed

    Zeng, Zhirui; Tice, Michael M

    2018-01-01

    Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms. Key Words: Microbial iron reduction-Micropore-Electron transfer strategies-Microbial carbonate. Astrobiology 18, 28-36.

  13. Impacts of amount of impregnated iron in granular activated carbon on arsenate adsorption capacities and kinetics.

    PubMed

    Chang, Qigang; Lin, Wei; Ying, Wei-Chi

    2012-06-01

    Iron-impregnated granular activated carbons (Fe-GAC) can remove arsenic effectively from water. In this study, Fe-GACs with iron content of 1.64 to 28.90% were synthesized using a new multi-step procedure for the investigation of effects of iron amount on arsenic adsorption capacities and kinetics. Langmuir model satisfactorily fit arsenic adsorption on Fe-GACs. The maximum arsenic adsorption capacity (q(m)) increased significantly with iron impregnation and reached 1,867 to 1,912 microg/g with iron content of 9.96 to 13.59%. Further increase of iron content (> 13.59%) caused gradual decrease of q(m). It was found that the amount of impregnated iron showed little impact on the affinity for arsenate. Kinetic study showed that the amount of impregnated iron affected the arsenic intraparticle diffusion rate greatly. The pseudo-second-order kinetic model fit arsenic adsorption kinetics on Fe-GACs better than the pseudo-first-order model. The arsenic adsorption rate increased with increasing of iron content from 1.64% to 13.59%, and then decreased with more impregnated iron (13.59 to 28.90%).

  14. Efficiency of small scale carbon mitigation by patch iron fertilization

    NASA Astrophysics Data System (ADS)

    Sarmiento, J. L.; Slater, R. D.; Dunne, J.; Gnanadesikan, A.; Hiscock, M. R.

    2009-11-01

    While nutrient depletion scenarios have long shown that the high-latitude High Nutrient Low Chlorophyll (HNLC) regions are the most effective for sequestering atmospheric carbon dioxide, recent simulations with prognostic biogeochemical models have suggested that only a fraction of the potential drawdown can be realized. We use a global ocean biogeochemical general circulation model developed at GFDL and Princeton to examine this and related issues. We fertilize two patches in the North and Equatorial Pacific, and two additional patches in the Southern Ocean HNLC region north of the biogeochemical divide and in the Ross Sea south of the biogeochemical divide. We obtain by far the greatest response to iron fertilization at the Ross Sea site. Here the CO2 remains sequestered on century time-scales and the efficiency of fertilization remains almost constant no matter how frequently iron is applied as long as it is confined to the growing season. The second most efficient site is in the Southern Ocean. Here the biological response to iron fertilization is comparable to the Ross Sea, but the enhanced biological uptake of CO2 is more spread out in the vertical and thus less effective at leading to removal of CO2 from the atmosphere. The North Pacific site has lower initial nutrients and thus a lower efficiency. Fertilization of the Equatorial Pacific leads to an expansion of the suboxic zone and a striking increase in denitrification that causes a sharp reduction in overall surface biological export production and CO2 uptake. The impacts on the oxygen distribution and surface biological export are less prominent at other sites, but nevertheless still a source of concern. The century time scale retention of iron in these models greatly increases the long-term biological response to iron addition as compared with models in which the added iron is rapidly scavenged from the ocean.

  15. The effects of redox fluctuation on iron-organic matter interactions in wet tropical soils

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, A.; Campbell, A.; Lin, Y.; Nico, P. S.; Silver, W. L.; Pett-Ridge, J.

    2016-12-01

    Two-thirds of the C in the terrestrial biosphere is stored as soil organic C, and much of this is stabilized via iron (Fe) mineral-organic matter (OM) associations that are susceptible to redox effects. The rapid C cycling typical of wet tropical ecosystems- driven by ample moisture and temperature- may also be fueled by a characteristically dynamic redox environment. Yet the net result of altered tropical soil climate and fluctuating soil redox regimes on Fe-organic matter associations is poorly understood. In this study, we hypothesized that the timing of redox transitions (frequency of O2 introduction and ferrous iron (Fe2+) generation) will lead to differences in Fe (oxyhydr)oxide mineral crystallinity and C degradation rates and alter the proportion of organic C associated with iron minerals. Surface soils from a humid tropical forest in Puerto Rico were incubated for 44 days under four redox regimes: (1) static anoxic, (2) static oxic, (3) 4 days anoxic, 4 days oxic, and (4) 4 days anoxic, 8 days oxic. Replicate microcosms were harvested at multiple time points, including before and after a redox switch (oxic to anoxic or vice versa). Selective chemical extractions, bulk Fe K-edge EXAFS and STXM/NEXAFS spectromicroscopy were used to comprehensively probe treatment effects on Fe and C speciation. Static redox conditions had a significant effect on Fe2+ and dissolved organic carbon (DOC) concentrations, and prolonged anoxia promoted reductive dissolution of Fe-oxides and an increase in amorphous or short-range ordered (SRO) Fe oxides. Preferential dissolution of this less-crystalline Fe pool was more prominent during rapid redox switches from oxic to anoxic conditions, and coincided with increased DOC. Bulk Fe K-edge EXAFS spectroscopy identified Fe3+ as the dominant Fe species in all treatments and indicated O/N atoms in the first Fe co-ordination sphere and features similar to SRO Fe-oxide phases (e.g. ferrihydrite or nano-goethite) in the second co

  16. Organic carbon and reducing conditions lead to cadmium immobilization by secondary Fe mineral formation in a pH-neutral soil.

    PubMed

    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.

  17. Extrapolating existing soil organic carbon data to estimate soil organic carbon stocks below 20 cm

    Treesearch

    An-Min Wu; Cinzia Fissore; Charles H. Perry; An-Min Wu; Brent Dalzell; Barry T. Wilson

    2015-01-01

    Estimates of forest soil organic carbon stocks across the US are currently developed from expert opinion in STATSGO/SSURGO and linked to forest type. The results are reported to the US EPA as the official United States submission to the UN Framework Convention on Climate Change. Beginning in 2015, however, estimates of soil organic carbon (SOC) stocks will be based on...

  18. [Distribution of soil organic carbon storage and carbon density in Gahai Wetland ecosystem].

    PubMed

    Ma, Wei-Wei; Wang, Hui; Huang, Rong; Li, Jun-Zhen; Li, De-Yu

    2014-03-01

    The profile distribution and accumulation characteristics of organic carbon of four typical marshes (herbaceous peat, marsh wetland, mountain wetland, subalpine meadow) were studied in Gahai Wetlands of Gannan in July 2011. The results showed that the soil bulk densities of the four typical marshes ranged from 0.22 to 1.29 g x cm(-3). The content of soil organic carbon in the herbaceous peat was higher than in other types, with its average content of organic carbon (286. 80 g x kg(-1)) being about 2.91, 4.99, 7.31 times as much as that of the marsh wetland, mountain wetland and subalpine meadow, respectively. The average organic carbon densities were in order of herbaceous peat > subalpine meadow > marsh wetland > mountain wetland, with the highest in the 0-10 cm layer. The change of organic carbon density along the soil profile was basically in accordance with the organic carbon content in the four typical marshes, but fluctuated with soil depth. There were obviously two carbon storage layers (0-10 and 20-40 cm, respectively) in the four typical marshes. The amounts of organic carbon stored in the 0-60 cm layer of the four typical marshes were 369.46, 278.83, 276.16, 292.23 t x hm(-2), respectively. The total amount of organic carbon stored in the 0-60 cm of the four typical marshes was about 9.50 x 10(6) t.

  19. Enhanced Adsorption of Selenium Ions from Aqueous Solution Using Iron Oxide Impregnated Carbon Nanotubes

    PubMed Central

    Bakather, Omer Y.; Khraisheh, Majeda; Nasser, Mustafa S.

    2017-01-01

    The aim of this research was to investigate the potential of raw and iron oxide impregnated carbon nanotubes (CNTs) as adsorbents for the removal of selenium (Se) ions from wastewater. The original and modified CNTs with different loadings of Fe2O3 nanoparticles were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffractometer (XRD), Brunauer, Emmett, and Teller (BET) surface area analyzer, thermogravimetric analysis (TGA), zeta potential, and energy dispersive X-ray spectroscopy (EDS). The adsorption parameters of the selenium ions from water using raw CNTs and iron oxide impregnated carbon nanotubes (CNT-Fe2O3) were optimized. Total removal of 1 ppm Se ions from water was achieved when 25 mg of CNTs impregnated with 20 wt.% of iron oxide nanoparticles is used. Freundlich and Langmuir isotherm models were used to study the nature of the adsorption process. Pseudo-first and pseudo-second-order models were employed to study the kinetics of selenium ions adsorption onto the surface of iron oxide impregnated CNTs. Maximum adsorption capacity of the Fe2O3 impregnated CNTs, predicted by Langmuir isotherm model, was found to be 111 mg/g. This new finding might revolutionize the adsorption treatment process and application by introducing a new type of nanoadsorbent that has super adsorption capacity towards Se ions. PMID:28555093

  20. Atmospheric iron supply and enhanced vertical carbon flux in the NE subarctic Pacific: Is there a connection?

    NASA Astrophysics Data System (ADS)

    Boyd, P. W.; Wong, C. S.; Merrill, J.; Whitney, F.; Snow, J.; Harrison, P. J.; Gower, J.

    1998-09-01

    Recent studies have confirmed the relationship between iron supply and phytoplankton growth rates in all three high-nitrate low-chlorophyll (HNLC) oceanic provinces. However, there is little evidence, so far, of the role of iron in altering the efficiency of the biological pump via increased downward export of particulate organic carbon (POC). The NE subarctic Pacific is unique among HNLC regions in that long time series pelagic observations and deep-moored sediment trap records exist which may provide the best opportunity thus far to test aspects of the iron hypothesis. Episodic elevated levels of chlorophyll a (> 2.0 μg L-1) were observed 6 times between 1964 and 1976 at the former site of Ocean Station Papa (OSP). In addition, between 1984 and 1990 on at least three occasions, concurrent pulses of POC and biogenic silica were recorded in deep-moored traps at OSP. Possible explanations for these events, such as lateral advection of more productive waters, iron-mediated blooms, or grazing by salp swarms are discussed and tested using an existing downward POC flux model. Owing to the episodic nature of such events, no available data are sufficiently comprehensive to unequivocally rule out any of these explanations. Nevertheless, from the data available, the occurrence of pelagic or deep water pulses, approximately once every 3 years, are most consistent with iron-mediated diatom blooms, and of the sinking of POC and biogenic silica (from such a bloom) to depth, respectively. A comparison of the timing of these iron-mediated pulses with that of the transport probabilities of atmospheric dust supply from Asia and Alaska provides an opportunity to assess the likelihood of a coupling between the atmosphere and the ocean.

  1. Effect of Iron and Carbonation of the Diffusion of Iodine and Rhenium in Waste Encasement Concrete and Soil Fill Material under Hydraulically Unsaturated Conditions

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

    Wellman, Dawn M.; Parker, Kent E.; Powers, Laura

    2008-07-31

    Assessing long-term performance of Category 3 cement wasteforms and accurate prediction for radionuclide encasement requires knowledge of the radionuclide-cement interactions and mechanisms of retention (i.e. sorption or precipitation). A set of sediment-concrete half-cell diffusion experiments was conducted under unsaturated conditions (4% and 7% by weight moisture content) using carbonated and non-carbonated concrete-soil half-cells. Results indicate the behavior of rhenium and iodine release was comparable within a given half-cell test. Diffusivity in soil is a function of moisture content; a 3% increase in moisture content affords a one to two order of magnitude increase in diffusivity. Release of iodine and rheniummore » was 1 to 3 orders of magnitude less from non-carbonated, relative to carbonated, concrete monoliths. Inclusion of iron in non-carbonate monoliths resulted in the lowest concrete diffusivity values for both iodine and rhenium. This suggests that in the presence of iron, iodine and rhenium are converted to reduced species, which are less soluble and better retained within the concrete monolith. The release of iodine and rhenium was greatest from iron-bearing, carbonated concrete monoliths, suggesting carbonation negates the effect of iron on the retention of iodine and rhenium within concrete monoliths. This is likely due to enhanced formation of microcracks in the presence of iron, which provide preferential paths for contaminant migration. Although the release of iodine and rhenium were greatest from carbonated concrete monoliths containing iron, the migration of iodine and rhenium within a given half-cell is dependent on the moisture content, soil diffusivity, and diffusing species.« less

  2. Reactive adsorption of SO2 on activated carbons with deposited iron nanoparticles.

    PubMed

    Arcibar-Orozco, Javier A; Rangel-Mendez, J Rene; Bandosz, Teresa J

    2013-02-15

    The effect of iron particle size anchored on the surface of commercial activated carbon on the removal of SO(2) from a gas phase was studied. Nanosize iron particles were deposited using forced hydrolysis of FeCl(3) with or without H(3)PO(4) as a capping agent. Dynamic adsorption experiments were carried out on either dry or pre-humidified materials and the adsorption capacities were calculated. The surface of the initial and exhausted materials was extensively characterized by microscopic, porosity, thermogravimetric and surface chemistry. The results indicate that the SO(2) adsorption capacity increased two and half times after the prehumidification process owing to the formation of H(2)SO(4) in the porous system. Iron species enhance the SO(2) adsorption capacity only when very small nanoparticles are deposited on the pore walls as a thin layer. Large iron nanoparticles block the ultramicropores decreasing the accessibility of the active sites and consuming oxygen that rest adsorption centers for SO(2) molecules. Iron nanoparticles of about 3-4 nm provide highly dispersed adsorption sites for SO(2) molecules and thus increase the adsorption capacity of about 80%. Fe(2)(SO(4))(3) was detected on the surface of exhausted samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Role of a gas phase in the kinetics of zinc and iron reduction with carbon from slag melts

    NASA Astrophysics Data System (ADS)

    Chumarev, V. M.; Selivanov, E. N.

    2013-03-01

    The influence of the mass transfer conditions in the gas phase having formed at the carbon-slag melt interface on CO regeneration is approximately estimated in the framework of a two-stage scheme of metal reduction from slag melts by carbon. The effect of zinc vapors on the combined reduction of iron and zinc from slags is considered. The influence of the slag composition and temperature on the critical concentration of zinc oxide above which no iron forms as an individual phase is explained.

  4. Continuously increasing δ98Mo values in Neoarchean black shales and iron formations from the Hamersley Basin

    NASA Astrophysics Data System (ADS)

    Kurzweil, Florian; Wille, Martin; Schoenberg, Ronny; Taubald, Heinrich; Van Kranendonk, Martin J.

    2015-09-01

    We present Mo-, C- and O-isotope data from black shales, carbonate- and oxide facies iron formations from the Hamersley Group, Western Australia, that range in age from 2.6 to 2.5 billion years. The data show a continuous increase from near crustal δ98Mo values of around 0.50‰ for the oldest Marra Mamba and Wittenoom formations towards higher values of up to 1.51‰ for the youngest sample of the Brockman Iron Formation. Thereby, the trend in increasing δ98Mo values is portrayed by both carbonate facies iron formations and black shales. Considering the positive correlation between Mo concentration and total organic carbon, we argue that this uniformity is best explained by molybdate adsorption onto organic matter in carbonate iron formations and scavenging of thiomolybdate onto sulfurized organic matter in black shales. A temporal increase in the seawater δ98Mo over the period 2.6-2.5 Ga is observed assuming an overall low Mo isotope fractionation during both Mo removal processes. Oxide facies iron formations show lowest Mo concentrations, lowest total organic carbon and slightly lower δ98Mo compared to nearly contemporaneous black shales. This may indicate that in iron formation settings with very low organic matter burial rates, the preferential adsorption of light Mo isotopes onto Fe-(oxyhydr)oxides becomes more relevant. A similar Mo-isotope pattern was previously found in contemporaneous black shales and carbonates of the Griqualand West Basin, South Africa. The consistent and concomitant increase in δ98Mo after 2.54 billion years ago suggests a more homogenous distribution of seawater molybdate with uniform isotopic composition in various depositional settings within the Hamersley Basin and the Griqualand West Basin. The modeling of the oceanic Mo inventory in relation to the Mo in- and outflux suggests that the long-term build-up of an isotopically heavy seawater Mo reservoir requires a sedimentary sink for isotopically light Mo. The search for this

  5. Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media

    NASA Astrophysics Data System (ADS)

    Busch, Jan; Meißner, Tobias; Potthoff, Annegret; Oswald, Sascha E.

    2014-08-01

    Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50 = 2.4 μm) are investigated in column tests using columns of 40 cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5 mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from - 62 mV to - 80 mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions.

  6. Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media.

    PubMed

    Busch, Jan; Meißner, Tobias; Potthoff, Annegret; Oswald, Sascha E

    2014-08-01

    Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50=2.4μm) are investigated in column tests using columns of 40cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from -62mV to -80mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Inferring Absorbing Organic Carbon Content from AERONET Data

    NASA Technical Reports Server (NTRS)

    Arola, A.; Schuster, G.; Myhre, G.; Kazadzis, S.; Dey, S.; Tripathi, S. N.

    2011-01-01

    Black carbon, light-absorbing organic carbon (often called brown carbon) and mineral dust are the major light-absorbing aerosols. Currently the sources and formation of brown carbon aerosol in particular are not well understood. In this study we estimated globally the amount of light absorbing organic carbon and black carbon from AERONET measurements. We find that the columnar absorbing organic carbon (brown carbon) levels in biomass burning regions of South-America and Africa are relatively high (about 15-20 magnesium per square meters during biomass burning season), while the concentrations are significantly lower in urban areas in US and Europe. However, we estimated significant absorbing organic carbon amounts from the data of megacities of newly industrialized countries, particularly in India and China, showing also clear seasonality with peak values up to 30-35 magnesium per square meters during the coldest season, likely caused by the coal and biofuel burning used for heating. We also compared our retrievals with the modeled organic carbon by global Oslo CTM for several sites. Model values are higher in biomass burning regions than AERONET-based retrievals, while opposite is true in urban areas in India and China.

  8. Hydrothermal synthesis of carbonyl iron-carbon nanocomposite: Characterization and electromagnetic performance

    NASA Astrophysics Data System (ADS)

    Pourabdollahi, Hakimeh; Zarei, Ali Reza

    In this research, the electromagnetic absorption properties of the carbonyl iron-carbon (CI/C) nanocomposite prepared via hydrothermal reaction using glucose as carbon precursor was studied in the range of 8.2-12.4 GHz. In hydrothermal reaction, glucose solution containing CI particles, placed in autoclave for 4 h under 453 K. Using surface coating technology is a method that prevents Cl oxidation and improves CI electromagnetic absorption. The structure, morphology and magnetic performances of the prepared nanocomposites were characterized by X-ray diffraction (XRD), energy dispersive spectrometry (EDS), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The electromagnetic properties including complex permittivity (εr), the permeability (μr), dielectric loss, magnetic loss, reflection loss, and attenuation constant were investigated using a vector network analyzer. For The CI/C nanocomposite, the bandwidth of -10 dB and -20 dB were obtained in the frequency range of 9.8-12.4 and 11.0-11.8 GHz, respectively. As well as, the reflection loss was -46.69 dB at the matching frequency of 11.5 GHz, when the matching thickness was 1.3 mm. While for CI particles the reflection loss for 4.4 mm thickness was -16.86 dB at the matching frequency of 12.3 GHz. The results indicate that the existence layer of carbon on carbonyl iron enhance the electromagnetic absorbing properties. Therefore, this nanocomposite can be suitable for in the radar absorbing coatings.

  9. Abundance, size distributions and trace-element binding of organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

    NASA Astrophysics Data System (ADS)

    Stolpe, Björn; Guo, Laodong; Shiller, Alan M.; Aiken, George R.

    2013-03-01

    Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of colloids and organic matter in the transport of trace elements in Northern high latitude watersheds influenced by permafrost. Concentrations of dissolved organic carbon (DOC), selected elements (Al, Si, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Ba, Pb, U), and UV-absorbance spectra were measured in 0.45 μm filtered samples. 'Nanocolloidal size distributions' (0.5-40 nm, hydrodynamic diameter) of humic-type and chromophoric dissolved organic matter (CDOM), Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb were determined by on-line coupling of flow field-flow fractionation (FFF) to detectors including UV-absorbance, fluorescence, and ICP-MS. Total dissolved and nanocolloidal concentrations of the elements varied considerably between the rivers and between spring flood and late summer base flow. Data on specific UV-absorbance (SUVA), spectral slopes, and the nanocolloidal fraction of the UV-absorbance indicated a decrease in aromaticity and size of CDOM from spring flood to late summer. The nanocolloidal size distributions indicated the presence of different 'components' of nanocolloids. 'Fulvic-rich nanocolloids' had a hydrodynamic diameter of 0.5-3 nm throughout the sampling season; 'organic/iron-rich nanocolloids' occurred in the <8 nm size range during the spring flood; whereas 'iron-rich nanocolloids' formed a discrete 4-40 nm components during summer base flow. Mn, Co, Ni, Cu and Zn were distributed between the nanocolloid components depending on the stability constant of the metal (+II)-organic complexes, while stronger association of Cr to the iron-rich nanocolloids was attributed to the higher oxidation states of Cr (+III or +IV). Changes in total dissolved element concentrations, size and composition of CDOM, and occurrence and size of organic/iron and iron-rich nanocolloids were related to variations in their sources from either the upper organic

  10. Southern Ocean Iron Experiment (SOFex)

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

    Coale, Kenneth H.

    The Southern Ocean Iron Experiment (SOFeX) was an experiment decades in the planning. It's implementation was among the most complex ship operations that SIO has been involved in. The SOFeX field expedition was successful in creating and tracking two experimentally enriched areas of the Southern Ocean, one characterized by low silicic acid, one characterized by high silicic acid. Both experimental sites were replete with abundant nitrate. About 100 scientists were involved overall. The major findings of this study were significant in several ways: (1) The productivity of the southern ocean is limited by iron availability. (2) Carbon uptake and fluxmore » is therefore controlled by iron availability (3) In spite of low silicic acid, iron promotes non-silicious phytoplankton growth and the uptake of carbon dioxide. (4) The transport of fixed carbon from the surface layers proceeds with a C:N ratio that would indicate differential remineralization of nitrogen at shallow depths. (5) These finding have major implications for modeling of carbon export based on nitrate utilization. (6) The general results of the experiment indicate that, beyond other southern ocean enrichment experiments, iron inputs have a much wider impact of productivity and carbon cycling than previously demonstrated. Scientific presentations: Coale, K., Johnson, K, Buesseler, K., 2002. The SOFeX Group. Eos. Trans. AGU 83(47) OS11A-0199. Coale, K., Johnson, K. Buesseler, K., 2002. SOFeX: Southern Ocean Iron Experiments. Overview and Experimental Design. Eos. Trans. AGU 83 (47) OS22D-01. Buesseler, K.,et al. 2002. Does Iron Fertilization Enhance Carbon Sequestration? Particle flux results from the Southern Ocean Iron Experiment. Eos. Trans. AGU 83 (47), OS22D-09. Johnson, K. et al. 2002. Open Ocean Iron Fertilization Experiments From IronEx-I through SOFeX: What We Know and What We Still Need to Understand. Eos. Trans. AGU 83 (47), OS22D-12. Coale, K. H., 2003. Carbon and Nutrient Cycling During the

  11. Evolution reversed: the ability to bind iron restored to the N-lobe of the murine inhibitor of carbonic anhydrase by strategic mutagenesis.

    PubMed

    Mason, Anne B; Judson, Gregory L; Bravo, Maria Cristina; Edelstein, Andrew; Byrne, Shaina L; James, Nicholas G; Roush, Eric D; Fierke, Carol A; Bobst, Cedric E; Kaltashov, Igor A; Daughtery, Margaret A

    2008-09-16

    The murine inhibitor of carbonic anhydrase (mICA) is a member of the superfamily related to the bilobal iron transport protein transferrin (TF), which binds a ferric ion within a cleft in each lobe. Although the gene encoding ICA in humans is classified as a pseudogene, an apparently functional ICA gene has been annotated in mice, rats, cows, pigs, and dogs. All ICAs lack one (or more) of the amino acid ligands in each lobe essential for high-affinity coordination of iron and the requisite synergistic anion, carbonate. The reason why ICA family members have lost the ability to bind iron is potentially related to acquiring a new function(s), one of which is inhibition of certain carbonic anhydrase (CA) isoforms. A recombinant mutant of the mICA (W124R/S188Y) was created with the goal of restoring the ligands required for both anion (Arg124) and iron (Tyr188) binding in the N-lobe. Absorption and fluorescence spectra definitively show that the mutant binds ferric iron in the N-lobe. Electrospray ionization mass spectrometry confirms the presence of both ferric iron and carbonate. At the putative endosomal pH of 5.6, iron is released by two slow processes indicative of high-affinity coordination. Induction of specific iron binding implies that (1) the structure of mICA resembles those of other TF family members and (2) the N-lobe can adopt a conformation in which the cleft closes when iron binds. Because the conformational change in the N-lobe indicated by metal binding does not impact the inhibitory activity of mICA, inhibition of CA was tentatively assigned to the C-lobe. Proof of this assignment is provided by limited trypsin proteolysis of porcine ICA.

  12. Two Iron Complexes as Homogeneous and Heterogeneous Catalysts for the Chemical Fixation of Carbon Dioxide.

    PubMed

    Karan, Chandan Kumar; Bhattacharjee, Manish

    2018-04-16

    Two new bimetallic iron-alkali metal complexes of amino acid (serine)-based reduced Schiff base ligand were synthesized and structurally characterized. Their efficacy as catalysts for the chemical fixation of carbon dioxide was explored. The heterogeneous version of the catalytic reaction was developed by the immobilization of these homogeneous bimetallic iron-alkali metal complexes in an anion-exchange resin. The resin-bound complexes can be used as recyclable catalysts up to six cycles.

  13. Iron Sulfide Minerals Record Microbe-Mineral Interactions in Anoxic Environments

    NASA Astrophysics Data System (ADS)

    Picard, A.; Gartman, A.; Cosmidis, J.; Clarke, D. R.; Girguis, P. R.

    2017-12-01

    The precipitation of most minerals in low-temperature environments on Earth is directly or indirectly influenced by the presence of organic substances and/or microbial biomass. Notably, the influence of microorganisms on the formation of Mn and Fe oxides/oxyhydroxides at the surface of the Earth has been well characterized (Chan et al., 2011; Estes et al., 2017). However, an oxygenated atmosphere is a unique feature of planet Earth. It is therefore critical for the search of life on other planetary bodies to characterize microbe-mineral interactions that form in anoxic conditions. Here we explore the role of microorganisms on the formation of iron sulfide minerals, which form under anoxic conditions. On modern Earth, sulfate-reducing microorganisms (SRM) are the major source of dissolved sulfide in low-temperature sedimentary environments. We experimentally demonstrate that SRM play a role in the nucleation and growth of iron sulfide minerals by acting as organic templates. The physical characteristics of the resulting minerals are different from those formed under abiotic conditions. Moreover, upon forming, iron sulfide minerals become associated with organic carbon, producing a potential organo-mineral signature. We also evaluate how the presence of various organic substances affect the formation of abiotic minerals and how this could produce false biosignatures that could be mistaken as biogenic minerals. Chan, C.S., Fakra, S.C., Emerson, D., Fleming, E.J. and Edwards, K.J. (2011) Lithotrophic iron-oxidizing bacteria produce organic stalks to control mineral growth: implications for biosignature formation. Isme Journal 5, 717-727. Estes, E.R., Andeer, P.F., Nordlund, D., Wankel, S.D. and Hansel, C.M. (2017) Biogenic manganese oxides as reservoirs of organic carbon and proteins in terrestrial and marine environments. Geobiology 15, 158-172.

  14. Does DOM properties or the amount of DOC induces iron reduction in topsoil porewater?

    NASA Astrophysics Data System (ADS)

    Szalai, Zoltán; Ringer, Marianna; Kiss, Klaudia; Perényi, Katalin; Jakab, Gergely

    2017-04-01

    Iron content of porewater in hydromorphic soils shows high temporal variability. This usually correlates with dissolved organic carbon (DOC) content, but the correlation can be weak in some cases. Some studies suggest that ferrous iron stabilizes organic carbon in dissolved state. On the contrary, other papers report about dissolved iron stabilization by dissolved organic matter (DOM). Present study focuses on this apparent contradiction and on the interaction of organic carbon and iron in hydromorphic soils. Studied gleyic Phaeozems (3 profiles) and mollic Gleysols (3 profiles) are located in Geresdi-dombság (Hungary) and in Danube-Tisza Interfluve (Hungary) respectively. Dynamics of porewater pH, EH, have been recorded by field stations at 20, 40 and 100 cm depth during the growing season with 10 min temporal resolution. Porewater occasionally have also been sampled in each depth. The presence of ferrous iron was detected by dipyridil field test. DOC, dissolved nitrogen (DN) and iron were measured by TOC analyser and fl-AAS. Molecular size and molecular weight were measured by photon correlation spectroscope (DLS and SLS). Textural and mineralogical properties of studied soils were also determined. Relationships among studied parameters were tested by Spearman's rank correlation. The seasonal dynamics of redox potential is primarily controlled by saturation, but spatial differences are also driven by vegetation. The environment is usually reductive for iron oxides between March and July, but intensive daily redox fluctuations could be measured in June and July in some topsoils. Short term temporal variability of redox conditions is depended on the physiological activity of plants. Most of the papers published a range between +100 and +50 mV for iron reduction in aquatic systems. Topsoil porewater measurements show three redox ranges where concentration of dissolved iron has been increased: +320 to +200, +80 to +20 and below-160 mV. These ranges were identified

  15. Organic carbon and nitrogen concentrations and annual organic carbon load of six selected rivers of the United States

    USGS Publications Warehouse

    Malcolm, R.L.; Durum, W.H.

    1976-01-01

    The organic carbon load during 1969-70 of each of the six rivers in this study is substantial. The 3.4-billion-kilogram (3.7-million-ton) and 47-million-kilogram (52-thousandton) annual organic carbon loads of the Mississippi River and the Brazos River (Tex.), respectively, were approximately equally distributed between dissolved and suspended phases, whereas the 725-million-kilogram (79.8-million-ton) organic load of the Missouri River was primarily in the suspended phase. The major portion of the 6.4-million-kilogram (7.3 thousand-ton) and the 19-million-kilogram (21-thousand-ton) organic carbon loads of the Sopchoppy River (Fla.) and the Neuse River (N.C.), respectively, was in the dissolved phase. DOC (dissolved organic carbon) concentrations in most rivers were usually less than 8 milligrams per litre. SOC (suspended organic carbon) concentrations fluctuated markedly with discharge, ranging between 1 and 14 percent, by weight, in sediment of most rivers. DOC concentrations were found to be independent of discharge, whereas SOC and SIC (suspended inorganic carbon) concentrations were positively correlated with discharge. Seasonal fluctuations in DOC and SOC were exhibited by the Missouri, Neuse, Ohio, and Brazos Rivers, but both SOC and DOC concentrations were relatively constant throughout the year in the Mississippi and Sopchoppy Rivers. The carbon-nitrogen ratio in the sediment phase of all river waters averaged less than 8 1 as compared with 12:1 or greater for most soils. This high nitrogen content shows a nitrogen enrichment of the stream sediment over that in adjacent soils, which suggests that different decomposition and humification processes are operating in streams than in the soils. The abundance of organic material in the dissolved and suspended phase of all river waters in this study indicate a large capacity factor for various types of organic reactivity within all streams and the quantitative importance of organic constituents in relation to the

  16. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  17. Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation

    NASA Astrophysics Data System (ADS)

    Zeng, Zhirui; Tice, Michael M.

    2018-01-01

    Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms.

  18. Manganese, Iron, and sulfur cycling in Louisiana continental shelf sediments

    EPA Science Inventory

    Sulfate reduction is considered the primary pathway for organic carbon remineralization on the northern Gulf of Mexico Louisiana continental shelf (LCS) where bottom waters are seasonally hypoxic, yet limited information is available on the importance of iron and manganese cyclin...

  19. In-Lake Processes Offset Increased Terrestrial Inputs of Dissolved Organic Carbon and Color to Lakes

    PubMed Central

    Köhler, Stephan J.; Kothawala, Dolly; Futter, Martyn N.; Liungman, Olof; Tranvik, Lars

    2013-01-01

    Increased color in surface waters, or browning, can alter lake ecological function, lake thermal stratification and pose difficulties for drinking water treatment. Mechanisms suggested to cause browning include increased dissolved organic carbon (DOC) and iron concentrations, as well as a shift to more colored DOC. While browning of surface waters is widespread and well documented, little is known about why some lakes resist it. Here, we present a comprehensive study of Mälaren, the third largest lake in Sweden. In Mälaren, the vast majority of water and DOC enters a western lake basin, and after approximately 2.8 years, drains from an eastern basin. Despite 40 years of increased terrestrial inputs of colored substances to western lake basins, the eastern basin has resisted browning over this time period. Here we find the half-life of iron was far shorter (0.6 years) than colored organic matter (A420 ; 1.7 years) and DOC as a whole (6.1 years). We found changes in filtered iron concentrations relate strongly to the observed loss of color in the western basins. In addition, we observed a substantial shift from colored DOC of terrestrial origin, to less colored autochthonous sources, with a substantial decrease in aromaticity (-17%) across the lake. We suggest that rapid losses of iron and colored DOC caused the limited browning observed in eastern lake basins. Across a wider dataset of 69 Swedish lakes, we observed greatest browning in acidic lakes with shorter retention times (< 1.5 years). These findings suggest that water residence time, along with iron, pH and colored DOC may be of central importance when modeling and projecting changes in brownification on broader spatial scales. PMID:23976946

  20. Adsorption of low concentration ceftazidime from aqueous solutions using impregnated activated carbon promoted by Iron, Copper and Aluminum

    NASA Astrophysics Data System (ADS)

    Hu, Xiang; Zhang, Hua; Sun, Zhirong

    2017-01-01

    In this paper, three impregnated activated carbon IAC (AC-Cu, AC-Fe, and AC-Al) promoted by Iron, Copper and Aluminum were used for adsorption of ceftazidime. Iron(III), Copper(II) and Aluminum(III) nitrate were used as an impregnant. The IACs were characterized by scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) surface area analyzer, Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS).The influence of factors, such as ion strength, pH, temperature, initial concentration, and concentration of natural organic matter organic matter on the adsorption process were studied. The adsorption kinetics and isotherms of ceftazidime were studied for the three IACs. The results showed that the adsorption was accurately represented by pseudo-second order model. Under different temperature, the maximum adsorption quantity of ceftazidime on AC-Cu calculated by pseudo-second order kinetic model were 200.0 mg g-1 (298 K), 196.1 mg g-1 (303 K) and 185.2 mg g-1 (308 K). It was much higher than that of AC-Fe and AC-Al. And the process was controlled by both film diffusion and intra particle mass transport. The results also showed that, the Freundlich and Temkin isotherm fit the adsorption well.

  1. Equilibrium and kinetics of adsorption of phosphate onto iron-doped activated carbon.

    PubMed

    Wang, Zhengfang; Nie, Er; Li, Jihua; Yang, Mo; Zhao, Yongjun; Luo, Xingzhang; Zheng, Zheng

    2011-08-01

    Two series of activated carbons modified by Fe (II) and Fe (III) (denoted as AC/N-Fe(II) and AC/N-Fe(III)), respectively, were used as adsorbents for the removal of phosphate in aqueous solutions. The synthesized adsorbent materials were investigated by different experimental analysis means. The adsorption of phosphate on activated carbons has been studied in kinetic and equilibrium conditions taking into account the adsorbate concentration, temperature, and solution pH as major influential factors. Maximum removals of phosphate are obtained in the pH range of 3.78-6.84 for both adsorbents. Langmuir isotherm adsorption equation well describes the experimental adsorption isotherms. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Results suggest that the main phase formed in AC/N-Fe(II) and AC/N-Fe(III) is goethite and akaganeite, respectively; the presence of iron oxides significantly affected the surface area and the pore structure of the activated carbon. Studies revealed that iron-doped activated carbons were effective in removing phosphate. AC/N-Fe(II) has a higher phosphate removal capacity than AC/N-Fe(III), which could be attributed to its better intra-particle diffusion and higher binding energy. The activation energy for adsorption was calculated to be 22.23 and 10.89 kJ mol(-1) for AC/N-Fe(II) and AC/N-Fe(III), respectively. The adsorption process was complex; both surface adsorption and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.

  2. A Re-evaluation of the Ferrozine Method for Dissolved Iron: The Effect of Organic Interferences

    NASA Astrophysics Data System (ADS)

    Balind, K.; Barber, A.; Gelinas, Y.

    2016-12-01

    Among the most commonly used analytical methods in geochemistry is the ferrozine method for determining dissolved iron concentration in water (1). This cheap and easy-to-use spectrophotometric method involves a complexing agent (ferrozine), a reducing agent (hydroxylamine-HCl) and buffer (ammonium acetate with ammonium hydroxide). Previous studies have demonstrated that complex organic matter (OM) originating from the Suwannee River did not lead to a significantly underestimation of the measured iron content in OM amended iron solutions (2). The authors concluded that this method could be used even in organic rich (i.e., 25 mg/L) waters. Here we compare the concentration of Fe measured using this spectrophotometric method to the total Fe as measured by ICP-MS in the presence/absence of specific organic molecules to ascertain if they interfere with the ferrozine method. We show that certain molecules with hydroxyl and carboxyl functional groups as well as multi-dentate chelating species have a significant effect on the measured iron concentrations. Two possible mechanisms likely are responsible for the inefficiency of this method in the presence of specific organic molecules; 1) incomplete reduction of Fe(III) bound to organic molecules, or 2) competition between the OM and ferrozine for the available iron. We address these possibilities separately by varying the experimental conditions. These methodological artifacts may have far reaching implications due to the extensive use of this method. Stookey, L. L., Anal. Chem., 42, 779 (1970). Viollier, E., et al., Applied Geochem., 15, 785 (2000).

  3. Low-carbon transition of iron and steel industry in China: carbon intensity, economic growth and policy intervention.

    PubMed

    Yu, Bing; Li, Xiao; Qiao, Yuanbo; Shi, Lei

    2015-02-01

    As the biggest iron and steel producer in the world and one of the highest CO2 emission sectors, China's iron and steel industry is undergoing a low-carbon transition accompanied by remarkable technological progress and investment adjustment, in response to the macroeconomic climate and policy intervention. Many drivers of the CO2 emissions of the iron and steel industry have been explored, but the relationships between CO2 abatement, investment and technological expenditure, and their connections with the economic growth and governmental policies in China, have not been conjointly and empirically examined. We proposed a concise conceptual model and an econometric model to investigate this crucial question. The results of regression, Granger causality test and impulse response analysis indicated that technological expenditure can significantly reduce CO2 emissions, and that investment expansion showed a negative impact on CO2 emission reduction. It was also argued with empirical evidence that a good economic situation favored CO2 abatement in China's iron and steel industry, while achieving CO2 emission reduction in this industrial sector did not necessarily threaten economic growth. This shed light on the dispute over balancing emission cutting and economic growth. Regarding the policy aspects, the year 2000 was found to be an important turning point for policy evolution and the development of the iron and steel industry in China. The subsequent command and control policies had a significant, positive effect on CO2 abatement. Copyright © 2014. Published by Elsevier B.V.

  4. Mechanistic investigations of Se(VI) treatment in anoxic groundwater using granular iron and organic carbon: an EXAFS study.

    PubMed

    Gibson, Blair D; Blowes, David W; Lindsay, Matthew B J; Ptacek, Carol J

    2012-11-30

    The removal of aqueous Se(VI) from a simulated groundwater by granular iron (GI), organic carbon (OC), and a mixture of these reactive materials (GI-OC) was evaluated in laboratory batch experiments. The experiments were performed under anoxic conditions to simulate subsurface treatment. A total reaction time of 120 h (5 d) was chosen to investigate the rapid changes in speciation occurring over reaction times that are reasonable for permeable reactive barrier (PRB) systems. After 120 h, concentrations of Se decreased by >90% in the GI system, 15% in the OC system and 35% in the GI-OC mixture. Analysis of the materials after contact with Se using synchrotron-radiation based X-ray absorption spectroscopy (XAS) indicated the presence of Se(IV) and Se(0) on the margins of GI grains after 6h with evidence of SeO and SeSe bonding, whereas Se(VI) was not observed. After 72 h, Se(0) was the only form of Se present in the GI experiments. In the OC batches, the XAS analysis indicated binding consistent with sorption of aqueous Se(VI) onto the OC with only minor reduction to Se(IV) and Se(0) after 120 h. Selenium XAS spectra collected for the GI-OC mixture were consistent with spectra for Se(IV) and Se(0) on both the margins of GI grains and OC particles, suggesting that the presence of dissolved Fe may have mediated the reduction of sorbed Se(VI). The results suggest that the application of granular Fe is effective at inducing aqueous Se removal in anoxic conditions through reductive precipitation processes. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Carbon-11 radiolabeling of iron-oxide nanoparticles for dual-modality PET/MR imaging

    NASA Astrophysics Data System (ADS)

    Sharma, Ramesh; Xu, Youwen; Kim, Sung Won; Schueller, Michael J.; Alexoff, David; Smith, S. David; Wang, Wei; Schlyer, David

    2013-07-01

    Dual-modality imaging, using Magnetic Resonance Imaging (MRI) and Positron Emission Tomography (PET) simultaneously, is a powerful tool to gain valuable information correlating structure with function in biomedicine. The advantage of this dual approach is that the strengths of one modality can balance the weaknesses of the other. However, success of this technique requires developing imaging probes suitable for both. Here, we report on the development of a nanoparticle labeling procedure via covalent bonding with carbon-11 PET isotope. Carbon-11 in the form of [11C]methyl iodide was used as a methylation agent to react with carboxylic acid (-COOH) and amine (-NH2) functional groups of ligands bound to the nanoparticles (NPs). The surface coating ligands present on superparamagnetic iron-oxide nanoparticles (SPIO NPs) were radiolabeled to achieve dual-modality PET/MR imaging capabilities. The proof-of-concept dual-modality PET/MR imaging using the radiolabeled SPIO NPs was demonstrated in an in vivo experiment.Dual-modality imaging, using Magnetic Resonance Imaging (MRI) and Positron Emission Tomography (PET) simultaneously, is a powerful tool to gain valuable information correlating structure with function in biomedicine. The advantage of this dual approach is that the strengths of one modality can balance the weaknesses of the other. However, success of this technique requires developing imaging probes suitable for both. Here, we report on the development of a nanoparticle labeling procedure via covalent bonding with carbon-11 PET isotope. Carbon-11 in the form of [11C]methyl iodide was used as a methylation agent to react with carboxylic acid (-COOH) and amine (-NH2) functional groups of ligands bound to the nanoparticles (NPs). The surface coating ligands present on superparamagnetic iron-oxide nanoparticles (SPIO NPs) were radiolabeled to achieve dual-modality PET/MR imaging capabilities. The proof-of-concept dual-modality PET/MR imaging using the radiolabeled

  6. Origin of life and iron-rich clays

    NASA Technical Reports Server (NTRS)

    Hartman, H. H.

    1986-01-01

    The premise that life began with self-replicating iron-rich clays is explored. In association with these clays and UV light, polar organic molecules, such as oxalic acid, were synthesized. The carbonaceous chondrites have both iron-rich clays and organic molecules. It is convenient to classify meteoritic organic matter into 3 categories: insoluble polymer, hydrocarbons and polar organics (soluble in water). Recent work on the delta D, delta N-15 and delta C-13 has made it clear that these three fractions have been made by three different mechanisms. A significant fraction of the insoluble polymer has a delta-D which suggests that it was made in an interstellar medium. The hydrocarbons seem to have been made on a parent body by a Fischer-Tropsch mechanism. The polar organics were probably synthesized in a mixture of carbonate (NH4)2CO3, Fe(++) ion and liquid water by radiolysis. In a set of experiments the radiolysis of (NH4)2CO3 in the presence and absence of Fe(++) ion has been examined. The synthesis of glycine in the presence of Fe(++) ion is 3-4 times that in the absence of ferrous ion. The effects of the addition of hydrocarbons to this mixture are explored. Iron-rich clays at low temperature and pressure are synthesized. So far the results are not sufficiently crystalline to look for replication. It should be noted that organic chelating agents such as oxalic acid do increase the crystallinity of the clays but not sufficiently. The hydrothermal synthesis of iron-rich clays is being examined.

  7. Thermodynamically controlled preservation of organic carbon in floodplains

    NASA Astrophysics Data System (ADS)

    Boye, Kristin; Noël, Vincent; Tfaily, Malak M.; Bone, Sharon E.; Williams, Kenneth H.; Bargar, John R.; Fendorf, Scott

    2017-06-01

    Organic matter decomposition in soils and terrestrial sediments has a prominent role in the global carbon cycle. Carbon stocks in anoxic environments, such as wetlands and the subsurface of floodplains, are large and presumed to decompose slowly. The degree of microbial respiration in anoxic environments is typically thought to depend on the energetics of available terminal electron acceptors such as nitrate or sulfate; microbes couple the reduction of these compounds to the oxidation of organic carbon. However, it is also possible that the energetics of the organic carbon itself can determine whether it is decomposed. Here we examined water-soluble organic carbon by Fourier-transform ion-cyclotron-resonance mass spectrometry to compare the chemical composition and average nominal oxidation state of carbon--a metric reflecting whether microbial oxidation of organic matter is thermodynamically favourable--in anoxic (sulfidic) and oxic (non-sulfidic) floodplain sediments. We observed distinct minima in the average nominal oxidation state of water-soluble carbon in sediments exhibiting anoxic, sulfate-reducing conditions, suggesting preservation of carbon compounds with nominal oxidation states below the threshold that makes microbial sulfate reduction thermodynamically favourable. We conclude that thermodynamic limitations constitute an important complement to other mechanisms of carbon preservation, such as enzymatic restrictions and mineral association, within anaerobic environments.

  8. Anodic aluminium oxide membranes used for the growth of carbon nanotubes.

    PubMed

    López, Vicente; Morant, Carmen; Márquez, Francisco; Zamora, Félix; Elizalde, Eduardo

    2009-11-01

    The suitability of anodic aluminum oxide (AAO) membranes as template supported on Si substrates for obtaining organized iron catalyst for carbon nanotube (CNT) growth has been investigated. The iron catalyst was confined in the holes of the AAO membrane. CVD synthesis with ethylene as carbon source led to a variety of carbon structures (nanotubes, helices, bamboo-like, etc). In absence of AAO membrane the catalyst was homogeneously distributed on the Si surface producing a high density of micron-length CNTs.

  9. Soil Organic Carbon and Its interaction with Minerals in Two Hillslopes with Different Climates and Erosion Processes

    NASA Astrophysics Data System (ADS)

    Wang, X.; Yoo, K.; Wackett, A. A.; Gutknecht, J.; Amundson, R.; Heimsath, A. M.

    2017-12-01

    Climate and topography have been widely recognized as important factors regulating soil organic carbon (SOC) dynamics but their interactive effects on SOC storage and its pools remain poorly constrained. Here we aimed to evaluate SOC storages and carbon-mineral interactions along two hillslope transects with moderately different climates (MAP: 549 mm vs. 816 mm) in Southeastern Australia. We sampled soil along the convex (eroding)-to-convergent (depositional) continuum at each hillslope transect and conducted size and density fractionation of these samples. In responses to the difference in climate factor, SOC inventories of eroding soils were twice as large at the wetter site compared with the drier site but showed little difference between two sites in depositional soils. These trends in SOC inventories were primarily controlled by SOC concentrations and secondarily by soil thicknesses. Similar patterns were observed for mineral associated organic carbon (MOC), and the abundances of MOC were controlled by the two independently operating processes affecting MOC concentration and fine-heavy fraction minerals. The contents and species of secondary clay and iron oxide minerals, abundances of particulate organic carbon, and bioturbation affected MOC concentrations. In contrast, the abundances of fine-heavy fraction minerals were impacted by erosion mechanisms that uniquely responded to regional- and micro- climate conditions. Consequently, topographic influences on SOC inventories and carbon-mineral interactions were more strongly pronounced in the drier climate where vegetation and erosion mechanisms were sensitive to microclimate. Our results highlight the significance of understanding topography and erosional processes in capturing climatic effects on soil carbon dynamics.

  10. Effect of iron on the dissolution of bovine enamel powder in vitro by carbonated beverages.

    PubMed

    Kato, Melissa Thiemi; Maria, Andrea Gutierrez; Sales-Peres, Sílvia Helena de Carvalho; Buzalaf, Marília Afonso Rabelo

    2007-07-01

    The aim of this study was to evaluate, in vitro, the effect of iron on the dissolution of bovine enamel powder, when added to two carbonated beverages. Powdered enamel was produced by griding enamel fragments of bovine incisor in a steel pestle and mortar. Particles between 75 and 106 microm were selected using appropriated meshes. At time zero, the carbonated beverage (Coke or Sprite Zero) was added to powdered enamel (1 mg enamel powder/10 microL of beverage) and vortexed for 30 s. The sample was immediately centrifuged (11,000 rpm) for 30 s and the supernatant was removed at 1 min 40 s. This procedure was repeated five times with the beverage containing increasing ferrous sulphate concentrations (1.25, 2.5, 5, 10, 15, 30 and 60 mmol/L). The phosphate released in the medium was analysed spectrophotometrically. Data were analysed using ANOVA and Tukey's test (p<0.05). When iron at 30 and 60 mmol/L was added to Coke, a significant reduction in the dissolution of powdered enamel was observed when compared to control (11 and 17%, respectively), while lower iron concentrations did not have any effect on enamel powder dissolution. Regarding Sprite Zero, iron concentrations up to 10 mmol/L had no significant effect, while higher concentrations significantly increased enamel powder dissolution. The results suggest that iron can interfere with the dissolution of dental enamel powder in the presence of acidic beverages and the type of acid in these beverages seems to modulate this effect.

  11. Wet Deposition Flux of Reactive Organic Carbon

    NASA Astrophysics Data System (ADS)

    Safieddine, S.; Heald, C. L.

    2016-12-01

    Reactive organic carbon (ROC) is the sum of non-methane volatile organic compounds (NMVOCs) and primary and secondary organic aerosols (OA). ROC plays a key role in driving the chemistry of the atmosphere, affecting the hydroxyl radical concentrations, methane lifetime, ozone formation, heterogeneous chemical reactions, and cloud formation, thereby impacting human health and climate. Uncertainties on the lifecycle of ROC in the atmosphere remain large. In part this can be attributed to the large uncertainties associated with the wet deposition fluxes. Little is known about the global magnitude of wet deposition as a sink of both gas and particle phase organic carbon, making this an important area for research and sensitivity testing in order to better understand the global ROC budget. In this study, we simulate the wet deposition fluxes of the reactive organic carbon of the troposphere using a global chemistry transport model, GEOS-Chem. We start by showing the current modeled global distribution of ROC wet deposition fluxes and investigate the sensitivity of these fluxes to variability in Henry's law solubility constants and spatial resolution. The average carbon oxidation state (OSc) is a useful metric that depicts the degree of oxidation of atmospheric reactive carbon. Here, we present for the first time the simulated gas and particle phase OSc of the global troposphere. We compare the OSc in the wet deposited reactive carbon flux and the dry deposited reactive carbon flux to the OSc of atmospheric ROC to gain insight into the degree of oxidation in deposited material and, more generally, the aging of organic material in the troposphere.

  12. Efficiency of small scale carbon mitigation by patch iron fertilization

    NASA Astrophysics Data System (ADS)

    Sarmiento, J. L.; Slater, R. D.; Dunne, J.; Gnanadesikan, A.; Hiscock, M. R.

    2010-11-01

    While nutrient depletion scenarios have long shown that the high-latitude High Nutrient Low Chlorophyll (HNLC) regions are the most effective for sequestering atmospheric carbon dioxide, recent simulations with prognostic biogeochemical models have suggested that only a fraction of the potential drawdown can be realized. We use a global ocean biogeochemical general circulation model developed at GFDL and Princeton to examine this and related issues. We fertilize two patches in the North and Equatorial Pacific, and two additional patches in the Southern Ocean HNLC region north of the biogeochemical divide and in the Ross Sea south of the biogeochemical divide. We evaluate the simulations using observations from both artificial and natural iron fertilization experiments at nearby locations. We obtain by far the greatest response to iron fertilization at the Ross Sea site, where sea ice prevents escape of sequestered CO2 during the wintertime, and the CO2 removed from the surface ocean by the biological pump is carried into the deep ocean by the circulation. As a consequence, CO2 remains sequestered on century time-scales and the efficiency of fertilization remains almost constant no matter how frequently iron is applied as long as it is confined to the growing season. The second most efficient site is in the Southern Ocean. The North Pacific site has lower initial nutrients and thus a lower efficiency. Fertilization of the Equatorial Pacific leads to an expansion of the suboxic zone and a striking increase in denitrification that causes a sharp reduction in overall surface biological export production and CO2 uptake. The impacts on the oxygen distribution and surface biological export are less prominent at other sites, but nevertheless still a source of concern. The century time scale retention of iron in this model greatly increases the long-term biological response to iron addition as compared with simulations in which the added iron is rapidly scavenged from the

  13. Microbial formation of labile organic carbon in Antarctic glacial environments

    USGS Publications Warehouse

    Smith, H.J.; Foster, R.; McKnight, D.M.; Lisle, John T.; Littmann, S.; Kuypers, M.M.M.; Foreman, C.M.

    2017-01-01

    Roughly six petagrams of organic carbon are stored within ice worldwide. This organic carbon is thought to be of old age and highly bioavailable. Along with storage of ancient and new atmospherically deposited organic carbon, microorganisms may contribute substantially to the glacial organic carbon pool. Models of glacial microbial carbon cycling vary from net respiration to net carbon fixation. Supraglacial streams have not been considered in models although they are amongst the largest ecosystems on most glaciers and are inhabited by diverse microbial communities. Here we investigate the biogeochemical sequence of organic carbon production and uptake in an Antarctic supraglacial stream in the McMurdo Dry Valleys using nanometre-scale secondary ion mass spectrometry, fluorescence spectroscopy, stable isotope analysis and incubation experiments. We find that heterotrophic production relies on highly labile organic carbon freshly derived from photosynthetic bacteria rather than legacy organic carbon. Exudates from primary production were utilized by heterotrophs within 24 h, and supported bacterial growth demands. The tight coupling of microbially released organic carbon and rapid uptake by heterotrophs suggests a dynamic local carbon cycle. Moreover, as temperatures increase there is the potential for positive feedback between glacial melt and microbial transformations of organic carbon.

  14. The Role of Microbial Iron Reduction in the Formation of Proterozoic Molar Tooth Structures

    NASA Astrophysics Data System (ADS)

    Hodgskiss, M. S. W.; Kunzmann, M.; Halverson, G. P.; Poirier, A.

    2016-12-01

    Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger. Despite being volumetrically significant in carbonate rocks of this age, their formation and disappearance are poorly understood. Here, we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and pyrite contents for samples from ten regions spanning 1870-635 Ma. The iron isotopic composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or siliciclastic components in the host sediment, whereas carbon isotopes are indistinguishable. We interpret the isotopically light iron in molar tooth structures to have been produced by microbial iron reduction utilising Fe-oxyhydroxides and smectites. The microbial conversion of smectite to illite results in a volume reduction of clay minerals ( 30%), while locally increasing pore water alkalinity. Therefore, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and increase in the concentration of O2 in shallow seawater in the mid-Neoproterozoic.

  15. Carbon sequestration in soil by in situ catalyzed photo-oxidative polymerization of soil organic matter.

    PubMed

    Piccolo, Alessandro; Spaccini, Riccardo; Nebbioso, Antonio; Mazzei, Pierluigi

    2011-08-01

    Here we describe an innovative mechanism for carbon sequestration in soil by in situ photopolymerization of soil organic matter under biomimetic catalysis. Three different Mediterranean soils were added with a synthetic water-soluble iron-porphyrin, irradiated by solar light, and subjected first to 5 days incubation and, then, 15, and 30 wetting and drying (w/d) cycles. The in situ catalyst-assisted photopolymerization of soil organic carbon (SOC) increased water stability of soil aggregates both after 5 days incubation and 15 w/d cycles, but not after 30 w/d cycles. Particle-size distribution of all treated soils confirmed the induced soil physical improvement, by showing a concomitant lower yield of the clay-sized fraction and larger yields of either coarse sand- or fine sand-size fractions, depending on soil texture, though only after 5 days incubation. The gain in soil physical quality was reflected by the shift of OC content from small to large soil aggregates, thereby suggesting that photopolymerization stabilized OC by both chemical and physical processes. A further evidence of the carbon sequestration capacity of the photocatalytic treatment was provided by the significant reduction of CO(2) respired by all soils after both incubation and w/d cycles. Our findings suggest that "green" catalytic technologies may potentially be the bases for future practices to increase soil carbon stabilization and mitigate CO(2) emissions from arable soils.

  16. A method for quantifying bioavailable organic carbon in aquifer sediments

    USGS Publications Warehouse

    Rectanus, H.V.; Widdowson, M.; Novak, J.; Chapelle, F.

    2005-01-01

    The fact that naturally occurring microorganisms can biodegrade PCE and TCE allows the use of monitored natural attenuation (MNA) as a remediation strategy at chlorinated solvent-contaminated sites. Research at numerous chlorinated solvent sites indicates an active dechlorinating microbial population coupled with an ample supply of organic carbon are conditions needed to sustain reductive dechlorination. A series of extraction experiments was used to compare the ability of the different extractants to remove organic carbon from aquifer sediments. The different extractants included pyrophosphate, sodium hydroxide, and polished water. Pyrophosphate served as a mild extractant that minimally alters the organic structure of the extracted material. Three concentrations (0.1, 0.5, and 1%) of pyrophosphate extracted 18.8, 24.9, and 30.8% of sediment organic carbon, respectively. Under alkali conditions (0.5 N NaOH), which provided the harshest extractant, 30.7% of the sediment organic carbon was recovered. Amorphous organic carbon, measured by potassium persulfate oxidization, consisted of 44.6% of the sediment organic carbon and served as a baseline control for maximum carbon removal. Conversely, highly purified water provided a minimal extraction control and extracted 5.7% of the sediment organic carbon. The removal of organic carbon was quantified by aqueous TOC in the extract and residual sediment organic carbon content. Characterization of the organic carbon extracts by compositional analysis prior and after exposure to the mixed culture might indicate the type organic carbon and functional groups used and/or generated by the organisms. This is an abstract of a paper presented at the 8th International In Situ and On-Site Bioremediation Symposium (Baltimore, MD 6/6-9/2005).

  17. Influence of moderate pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing activated carbon.

    PubMed

    Wang, Zhengfang; Shi, Mo; Li, Jihua; Zheng, Zheng

    2014-03-01

    A novel adsorbent based on iron oxide dispersed over activated carbon (AC) were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron (denoted as AC-Fe and AC/O-Fe), resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%-46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe(II) after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe(II) by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/O-Fe, respectively. The results showed that the surface mass transfer and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  18. The role of the iron catalyst in the toxicity of multi-walled carbon nanotubes (MWCNTs).

    PubMed

    Visalli, Giuseppa; Facciolà, Alessio; Iannazzo, Daniela; Piperno, Anna; Pistone, Alessandro; Di Pietro, Angela

    2017-09-01

    This study aimed to investigate the role of iron, used as a catalyst, in the biological response to pristine and functionalized multi-walled carbon nanotubes (p/fMWCNTs) with an iron content of 2.5-2.8%. Preliminarily, we assessed the pro-oxidant activity of MWCNTs-associated iron by an abiotic test. To evaluate iron bioavailability, we measured intracellular redox-active iron in A549 cells exposed to both MWCNT suspensions and to the cell medium preconditioned by MWCNTs, in order to assess the iron dissolution rate under physiological conditions. Moreover, in exposed cells, we detected ROS levels, 8-oxo-dG and mitochondrial function. The results clearly highlighted that MWCNTs- associated iron was not redox-active and that iron leakage did not occur under physiological conditions, including the oxidative burst of specialized cells. Despite this, in MWCNTs exposed cells, higher level of intracellular redox-active iron was measured in comparison to control and a significant time-dependent ROS increase was observed (P<0.01). Higher levels of 8-oxo-dG, a marker of oxidative DNA damage, and decreased mitochondrial function, confirmed the oxidative stress induced by MWCNTs. Based on the results we believe that oxidative damage could be attributable to the release of endogenous redox-active iron. This was due to the damage of acidic vacuolar compartment caused by endocytosis-mediated MWCNT internalization. Copyright © 2017 Elsevier GmbH. All rights reserved.

  19. Investigation of reductive dechlorination supported by natural organic carbon

    USGS Publications Warehouse

    Rectanus, H.V.; Widdowson, M.A.; Chapelle, F.H.; Kelly, C.A.; Novak, J.T.

    2007-01-01

    Because remediation timeframes using monitored natural attenuation may span decades or even centuries at chlorinated solvent sites, new approaches are needed to assess the long-term sustainability of reductive dechlorination in ground water systems. In this study, extraction procedures were used to investigate the mass of indigenous organic carbon in aquifer sediment, and experiments were conducted to determine if the extracted carbon could support reductive dechlorination of chloroethenes. Aquifer sediment cores were collected from a site without an anthropogenic source of organic carbon where organic carbon varied from 0.02% to 0.12%. Single extraction results showed that 1% to 28% of sediment-associated organic carbon and 2% to 36% of the soft carbon were removed depending on nature and concentration of the extracting solution (Nanopure water; 0.1%, 0.5%, and 1.0% sodium pyrophosphate; and 0.5 N sodium hydroxide). Soft carbon is defined as organic carbon oxidized with potassium persulfate and is assumed to serve as a source of biodegradable carbon within the aquifer. Biodegradability studies demonstrated that 20% to 40% of extracted organic carbon was biodegraded aerobically and anaerobically by soil microorganisms in relatively brief tests (45 d). A five-step extraction procedure consisting of 0.1% pyrophosphate and base solutions was investigated to quantify bioavailable organic carbon. Using the extracted carbon as the sole electron donor source, tetrachloroethene was transformed to cis-1,2- dichloroethene and vinyl chloride in anaerobic enrichment culture experiments. Hydrogen gas was produced at levels necessary to sustain reductive dechlorination (>1 nM). ?? 2007 National Ground Water Association.

  20. Longevity of granular iron in groundwater treatment processes: corrosion product development.

    PubMed

    Kohn, Tamar; Livi, Kenneth J T; Roberts, A Lynn; Vikesland, Peter J

    2005-04-15

    Permeable reactive barriers employing iron as a reactive surface have received extensive attention. A remaining issue, however, relates to their longevity. As an integral part of a long-term column study conducted to examine the influence of inorganic cosolutes on iron reactivity toward chlorinated solvents and nitroaromatic compounds, Master Builder iron grains were characterized via scanning and transmission electron microscopy, electron energy loss spectroscopy (EELS), micro-Raman spectroscopy, and X-ray diffraction. Prior to exposure to carbonate solutions, the iron grains were covered by a surface scale that consisted of fayalite (Fe2SiO4), wüstite (FeO), magnetite (Fe3O4), maghemite (gamma-Fe2O3), and graphite. After 1100 days of exposure to solutions containing carbonate, other inorganic solutes, and organic contaminants, the wüstite, fayalite, and graphite of the original scale partially dissolved, and magnetite and iron carbonate hydroxide (Fe3(OH)2.2CO3) precipitated on top of the scale. Raman results indicate the presence of green rust (e.g., [Fe4(2+)Fe2(3+)(OH)12]-[CO3 x 2H2O]) toward the column outlet after 308 days of operation, although this mineral phase disappears at longer operation times. Grains extracted from a column exposed to a high concentration (20 mM) of sodium bicarbonate were more extensively weathered than those from columns exposed to 2 mM sodium bicarbonate. An iron carbonate hydroxide layer up to 100 microm thick was observed. Even though EELS analysis of iron carbonate hydroxide indicates that this is a redox-active phase, the thickness of this layer is presumed responsible for the previously observed decline in the reactivity of this column relative to low-bicarbonate columns. A silica-containing feed resulted in reduced reactivity toward TCE. Grains from this column had a strong enrichment of silicon in the precipitates, although no distinct silica-containing mineral phases were identified. The substitution of 2 mM calcium

  1. Structure and reactivity of ferrihydrite-soil organic carbon-calcium ternary complexes

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Adhikari, D.; Sowers, T.; Stuckey, J.; Poulson, S.; Sparks, D. L.

    2017-12-01

    Complete understanding about the interactions between soil organic carbon (SOC) and minerals is important for predicting the stability of SOC and its response to climate change. Recent studies have shown the importance of calcium (Ca)-bearing minerals and iron (Fe) oxide in associating with and stabilizing SOC. In this study, we have investigated the formation and reactivity of ferrihydrite-SOC-Ca ternary complexes. During the co-precipitation of ferrihydrite with SOC in the presence of Ca2+, 60% of SOC can be co-precipitated with ferrihydrite at a C/Fe (molar ratio) of up to 10, whereas the Ca/Fe ratio was saturated at 0.2. Increasing amount of Ca2+ did not affect the co-precipitation of SOC with ferrihydrite or the lability of ferrihydrite-bound SOC. In addition, microbial reduction of ferrihydrite and reductive release of ferrihydrite-bound SOC were not influenced by the presence of Ca, but the pathway for Fe mineral transformation during the reduction was affected by Ca. In the meantime, Fe reduction selectively released carboxylic-enriched SOC. As a comparison, the presence of SOC increased the incorporation of Ca into the structure of ferrihydrite. Our results indicate the formation of ferrihydrite-SOC-Ca complexes, with organic carbon bridging the ferrihydrite and Ca. Such ternary complexes potentially play an important role in regulating the interactions between SOC and mineral phases in soil.

  2. The effect of microbial activity and adsorption processes on groundwater dissolved organic carbon character and concentration

    NASA Astrophysics Data System (ADS)

    Meredith, K.; McDonough, L.; Oudone, P.; Rutlidge, H.; O'Carroll, D. M.; Andersen, M. S.; Baker, A.

    2017-12-01

    Balancing the terrestrial global carbon budget has proven to be a significant challenge. Whilst the movement of carbon in the atmosphere, rivers and oceans has been extensively studied, the potential for groundwater to act as a carbon source or sink through both microbial activity and sorption to and from mineral surfaces, is poorly understood. To investigate the biodegradable component of groundwater dissolved organic carbon (DOC), groundwater samples were collected from multiple coastal and inland sites. Water quality parameters such as pH, electrical conductivity, temperature, dissolved oxygen were measured in the field. Samples were analysed and characterised for their biodegradable DOC content using spectrofluorometric and Liquid Chromatography-Organic Carbon Detection (LC-OCD) techniques at set intervals within a 28 day period. Further to this, we performed laboratory sorption experiments on our groundwater samples using different minerals to examine the effect of adsorption processes on DOC character and concentration. Calcium carbonate, quartz and iron coated quartz were heated to 400ºC to remove potential carbon contamination, and then added at various known masses (0 mg to 10 g) to 50 mL of groundwater. Samples were then rotated for two hours, filtered at 0.2 μm and analysed by LC-OCD. This research forms part of an ongoing project which will assist in identifying the factors affecting the mobilisation, transport and removal of DOC in uncontaminated groundwater. By quantifying the relative importance of these processes, we can then determine whether the groundwater is a carbon source or sink. Importantly, this information will help guide policy and identify the need to include groundwater resources as part of the carbon economy.

  3. Removal of iron and manganese using granular activated carbon and zeolite in artificial barrier of riverbank filtration

    NASA Astrophysics Data System (ADS)

    Ismail, Abustan; Harmuni, Halim; Mohd, Remy Rozainy M. A. Z.

    2017-04-01

    Iron and Manganese was examined from riverbank filtration (RBF) and river water in Sungai Kerian, Lubok Buntar, Serdang Kedah. Water from the RBF was influenced by geochemical and hydro chemical processes in the aquifer that made concentrations of iron (Fe), and manganese (Mn) high, and exceeded the standard values set by the Malaysia Ministry of Health. Therefore, in order to overcome the problem, the artificial barrier was proposed to improve the performance of the RBF. In this study, the capability and performance of granular activated carbon, zeolite and sand were investigated in this research. The effects of dosage, shaking speed, pH and contact time on removal of iron and manganese were studied to determine the best performance. For the removal of iron using granular activated carbon (GAC) and zeolite, the optimum contact time was at 2 hours with 200rpm shaking speed with 5g and 10g at pH 5 with percentage removal of iron was 87.81% and 83.20% respectively. The removal of manganese and zeolite arose sharply in 75 minutes with 90.21% removal, with 100rpm shaking speed. The GAC gave the best performance with 99.39% removal of manganese. The highest removal of manganese was achieved when the adsorbent dosage increased to 10g with shaking speed of 200rpm.

  4. Carbon Isotopic Heterogeneity of Graphite in the San Juan Mass of the Campo Del Cielo IAB Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Maruoka, T.; Kurat, G.; Zinner, E.; Varela, M. E.; Ametrano, S. J.

    2003-01-01

    The origin of IAB iron meteorites is still a matter of debate. It is generally believed that iron meteorites originated from molten cores in small planetesimals because the fractionation trend of trace elements (e.g., Ir, Ge, Ga, etc. vs. Ni) for most iron meteorites can be more or less explained by fractional crystallization from metal melts. However, this process cannot produce trace element characteristics of the IAB (and other) iron meteorites. To explain these trace element abundance patterns, several models have been proposed. Although most of these models require a high temperature, clear evidence has recently been obtained for a sub-solidus formation of IAB iron meteorites from noble gas analyses. Moreover, heterogeneous distributions of some trace elements in metal and other phases also suggest a low temperature origin of at least some IAB iron meteorites. Here we use the carbon isotopic compositions of graphite to constrain the origin of IAB iron meteorites. Our data confirm a possible low temperature origin of IAB iron meteorites.

  5. Organic solvent regeneration of granular activated carbon

    NASA Astrophysics Data System (ADS)

    Cross, W. H.; Suidan, M. T.; Roller, M. A.; Kim, B. R.; Gould, J. P.

    1982-09-01

    The use of activated carbon for the treatment of industrial waste-streams was shown to be an effective treatment. The high costs associated with the replacement or thermal regeneration of the carbon have prohibited the economic feasibility of this process. The in situ solvent regeneration of activated carbon by means of organic solvent extraction was suggested as an economically alternative to thermal regeneration. The important aspects of the solvent regeneration process include: the physical and chemical characteristics of the adsorbent, the pore size distribution and energy of adsorption associated with the activated carbon; the degree of solubility of the adsorbate in the organic solvent; the miscibility of the organic solvent in water; and the temperature at which the generation is performed.

  6. A Global Assessment of Rain-Dissolved Organic Carbon

    NASA Astrophysics Data System (ADS)

    Safieddine, S.; Heald, C. L.

    2017-12-01

    Precipitation is the largest physical removal pathway of atmospheric organic carbon from the atmosphere. The removed carbon is transferred to the land and ocean in the form of dissolved organic carbon (DOC). Limited measurements have hindered efforts to characterize global DOC. In this poster presentation, we show the first simulated global DOC distribution based on a GEOS-Chem model simulation of the atmospheric reactive carbon budget. Over the ocean, simulated DOC concentrations are between 0.1 to 1 mgCL-1 with a total of 85 TgCyr-1 deposited. DOC concentrations are higher inland, ranging between 1 and 10 mgCL-1, producing a total of 188 TgCyr-1 terrestrial organic wet deposition. We compare the 2010 simulated DOC to a 30-year synthesis of available DOC measurements over different environments. Despite imperfect matching of observational and simulated time intervals, the model is able to reproduce much of the spatial variability of DOC (r= 0.63), with a low bias of 35%. We compare the global average carbon oxidation state (OSc) of both atmospheric and dissolved organic carbon, as a simple metric for describing the chemical composition of organics. In the global atmosphere reactive organic carbon (ROC) is dominated by hydrocarbons and ketones, and OSc, ranges from -1.8 to -0.6. In the dissolved form, formaldehyde, formic acid, primary and secondary semi-volatiles organic aerosol dominate the DOC concentrations. The increase in solubility upon oxidation leads to a global increase in OSc in rainwater with -0.6<=OSc <=0. This simulation provides new insight into the current model representation of the flow of atmospheric and rain-dissolved organic carbon, and new opportunities to use observations and simulations to understand the DOC reaching land and ocean.

  7. Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon

    USGS Publications Warehouse

    Weishaar, J.L.; Aiken, George R.; Bergamaschi, Brian A.; Fram, Miranda S.; Fujii, Roger; Mopper, K.

    2003-01-01

    Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.

  8. Evaluation of organic carbon analyzers for space application. [for water reclamation

    NASA Technical Reports Server (NTRS)

    1984-01-01

    The state-of-the-art technology for organic carbon analysis in space applications is evaluated. An investigation into total organic carbon (TOC) analysis has identified a variety of schemes which include different methods for: (1) separation of inorganic carbon from organic carbon and/or differentiation of inorganic carbon from organic carbon; (2) reaction of organic carbon to form a quantifiable species; and (3) detection and measurement of that species. Each method option is discussed.

  9. Systems analysis of iron metabolism: the network of iron pools and fluxes

    PubMed Central

    2010-01-01

    Background Every cell of the mammalian organism needs iron as trace element in numerous oxido-reductive processes as well as for transport and storage of oxygen. The very versatility of ionic iron makes it a toxic entity which can catalyze the production of radicals that damage vital membranous and macromolecular assemblies in the cell. The mammalian organism maintains therefore a complex regulatory network of iron uptake, excretion and intra-body distribution. Intracellular regulation in different cell types is intertwined with a global hormonal signalling structure. Iron deficiency as well as excess of iron are frequent and serious human disorders. They can affect every cell, but also the organism as a whole. Results Here, we present a kinematic model of the dynamic system of iron pools and fluxes. It is based on ferrokinetic data and chemical measurements in C57BL6 wild-type mice maintained on iron-deficient, iron-adequate, or iron-loaded diet. The tracer iron levels in major tissues and organs (16 compartment) were followed for 28 days. The evaluation resulted in a whole-body model of fractional clearance rates. The analysis permits calculation of absolute flux rates in the steady-state, of iron distribution into different organs, of tracer-accessible pool sizes and of residence times of iron in the different compartments in response to three states of iron-repletion induced by the dietary regime. Conclusions This mathematical model presents a comprehensive physiological picture of mice under three different diets with varying iron contents. The quantitative results reflect systemic properties of iron metabolism: dynamic closedness, hierarchy of time scales, switch-over response and dynamics of iron storage in parenchymal organs. Therefore, we could assess which parameters will change under dietary perturbations and study in quantitative terms when those changes take place. PMID:20704761

  10. Analytical method for dissolved-organic carbon fractionation

    USGS Publications Warehouse

    Leenheer, Jerry A.; Huffman, Edward W. D.

    1979-01-01

    A standard procedure for analytical-scale dissolved organic carbon fractionation is presented, whereby dissolved organic carbon in water is first fractionated by a nonionic macroreticular resin into acid, base, and neutral hydrophobic organic solute fractions, and next fractionated by ion-exchange resins into acid, base, and neutral hydrophilic solute fractions. The hydrophobic solutes are defined as those sorbed on a nonionic, acrylic-ester macroreticular resin and are differentiated into acid, base, and nautral fractions by sorption/desorption controlled by pH adjustment. The hydrophilic bases are next sorbed on strong-acid ion-exchange resin, followed by sorption of hydrophilic acids on a strong-base ion-exchange resin. Hydrophilic neutrals are not sorbed and remain dissolved in the deionized water at the end of the fractionation procedure. The complete fractionation can be performed on a 200-milliliter filtered water sample, whose dissolved organic carbon content is 5-25 mg/L and whose specific conductance is less than 2,000 μmhos/cm at 25°C. The applications of dissolved organic carbon fractionation analysis range from field studies of changes of organic solute composition with synthetic fossil fuel production, to fundamental studies of the nature of sorption processes.

  11. Comparison of activated carbon and iron/cerium modified activated carbon to remove methylene blue from wastewater.

    PubMed

    Cheng, Song; Zhang, Libo; Ma, Aiyuan; Xia, Hongying; Peng, Jinhui; Li, Chunyang; Shu, Jianhua

    2018-03-01

    The methylene blue (MB) removal abilities of raw activated carbon and iron/cerium modified raw activated carbon (Fe-Ce-AC) by adsorption were researched and compared. The characteristics of Fe-Ce-AC were examined by N 2 adsorption, zeta potential measurement, FTIR, Raman, XRD, XPS, SEM and EDS. After modification, the following phenomena occurred: The BET surface area, average pore diameter and total pore volume decreased; the degree of graphitization also decreased. Moreover, the presence of Fe 3 O 4 led to Fe-Ce-AC having magnetic properties, which makes it easy to separate from dye wastewater in an external magnetic field and subsequently recycle. In addition, the equilibrium isotherms and kinetics of MB adsorption on raw activated carbon and Fe-Ce-AC were systematically examined. The equilibrium adsorption data indicated that the adsorption behavior followed the Langmuir isotherm, and the pseudo-second-order model matched the kinetic data well. Compared with raw activated carbon, the maximum monolayer adsorption capacity of Fe-Ce-AC increased by 27.31%. According to the experimental results, Fe-Ce-AC can be used as an effective adsorbent for the removal of MB from dye wastewater. Copyright © 2017. Published by Elsevier B.V.

  12. Variations of iron flux and organic carbon remineralization in a subterranean estuary caused by interannual variations in recharge

    USGS Publications Warehouse

    Roy, Moutusi; Martin, Jonathan B.; Cable, Jaye E.; Smith, Christopher G.

    2013-01-01

    We determine the inter-annual variations in diagenetic reaction rates of sedimentary iron (Fe ) in an east Florida subterranean estuary and evaluate the connection between metal fluxes and recharge to the coastal aquifer. Over the three-year study period (from 2004 to 2007), the amount of Fe-oxides reduced at the study site decreased from 192 g/yr to 153 g/yr and associated organic carbon (OC) remineralization decreased from 48 g/yr to 38 g/yr. These reductions occurred although the Fe-oxide reduction rates remained constant around 1 mg/cm2/yr. These results suggest that changes in flow rates of submarine groundwater discharge (SGD) related to changes in precipitation may be important to fluxes of the diagenetic reaction products. Rainfall at a weather station approximately 5 km from the field area decreased from 12.6 cm/month to 8.4 cm/month from 2004 to 2007. Monthly potential evapotranspiration (PET) calculated from Thornthwaite’s method indicated potential evapotranspiration cycled from about 3 cm/month in the winter to about 15 cm/month in the summer so that net annual recharge to the aquifer decreased from 40 cm in 2004 to -10 cm in 2007. Simultaneously, with the decrease in recharge of groundwater, freshwater SGD decreased by around 20% and caused the originally 25 m wide freshwater seepage face to decrease in width by about 5 m. The smaller seepage face reduced the area under which Fe-oxides were undergoing reductive dissolution. Consequently, the observed decrease in Fe flux is controlled by hydrology of the subterranean estuary. These results point out the need to better understand linkages between temporal variations in diagenetic reactions and changes in flow within subterranean estuaries in order to accurately constrain their contribution to oceanic fluxes of solutes from subterranean estuaries.

  13. Thermodynamically controlled preservation of organic carbon in floodplains

    DOE PAGES

    Boye, Kristin; Noel, Vincent; Tfaily, Malak M.; ...

    2017-05-01

    Organic matter decomposition in soils and terrestrial sediments has a prominent role in the global carbon cycle. Carbon stocks in anoxic environments, such as wetlands and the subsurface of floodplains, are large and presumed to decompose slowly. The degree of microbial respiration in anoxic environments is typically thought to depend on the energetics of available terminal electron acceptors such as nitrate or sulfate; microbes couple the reduction of these compounds to the oxidation of organic carbon. But, it is also possible that the energetics of the organic carbon itself can determine whether it is decomposed. We examined water-soluble organic carbonmore » by Fourier-transform ion-cyclotron-resonance mass spectrometry to compare the chemical composition and average nominal oxidation state of carbon—a metric reflecting whether microbial oxidation of organic matter is thermodynamically favourable—in anoxic (sulfidic) and oxic (non-sulfidic) floodplain sediments. We also observed distinct minima in the average nominal oxidation state of water-soluble carbon in sediments exhibiting anoxic, sulfate-reducing conditions, suggesting preservation of carbon compounds with nominal oxidation states below the threshold that makes microbial sulfate reduction thermodynamically favourable. Finally, we show that thermodynamic limitations constitute an important complement to other mechanisms of carbon preservation, such as enzymatic restrictions and mineral association, within anaerobic environments.« less

  14. Thermodynamically controlled preservation of organic carbon in floodplains

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

    Boye, Kristin; Noel, Vincent; Tfaily, Malak M.

    Organic matter decomposition in soils and terrestrial sediments has a prominent role in the global carbon cycle. Carbon stocks in anoxic environments, such as wetlands and the subsurface of floodplains, are large and presumed to decompose slowly. The degree of microbial respiration in anoxic environments is typically thought to depend on the energetics of available terminal electron acceptors such as nitrate or sulfate; microbes couple the reduction of these compounds to the oxidation of organic carbon. But, it is also possible that the energetics of the organic carbon itself can determine whether it is decomposed. We examined water-soluble organic carbonmore » by Fourier-transform ion-cyclotron-resonance mass spectrometry to compare the chemical composition and average nominal oxidation state of carbon—a metric reflecting whether microbial oxidation of organic matter is thermodynamically favourable—in anoxic (sulfidic) and oxic (non-sulfidic) floodplain sediments. We also observed distinct minima in the average nominal oxidation state of water-soluble carbon in sediments exhibiting anoxic, sulfate-reducing conditions, suggesting preservation of carbon compounds with nominal oxidation states below the threshold that makes microbial sulfate reduction thermodynamically favourable. Finally, we show that thermodynamic limitations constitute an important complement to other mechanisms of carbon preservation, such as enzymatic restrictions and mineral association, within anaerobic environments.« less

  15. Erosion of organic carbon in the Arctic as a geological carbon dioxide sink.

    PubMed

    Hilton, Robert G; Galy, Valier; Gaillardet, Jérôme; Dellinger, Mathieu; Bryant, Charlotte; O'Regan, Matt; Gröcke, Darren R; Coxall, Helen; Bouchez, Julien; Calmels, Damien

    2015-08-06

    Soils of the northern high latitudes store carbon over millennial timescales (thousands of years) and contain approximately double the carbon stock of the atmosphere. Warming and associated permafrost thaw can expose soil organic carbon and result in mineralization and carbon dioxide (CO2) release. However, some of this soil organic carbon may be eroded and transferred to rivers. If it escapes degradation during river transport and is buried in marine sediments, then it can contribute to a longer-term (more than ten thousand years), geological CO2 sink. Despite this recognition, the erosional flux and fate of particulate organic carbon (POC) in large rivers at high latitudes remains poorly constrained. Here, we quantify the source of POC in the Mackenzie River, the main sediment supplier to the Arctic Ocean, and assess its flux and fate. We combine measurements of radiocarbon, stable carbon isotopes and element ratios to correct for rock-derived POC. Our samples reveal that the eroded biospheric POC has resided in the basin for millennia, with a mean radiocarbon age of 5,800 ± 800 years, much older than the POC in large tropical rivers. From the measured biospheric POC content and variability in annual sediment yield, we calculate a biospheric POC flux of 2.2(+1.3)(-0.9) teragrams of carbon per year from the Mackenzie River, which is three times the CO2 drawdown by silicate weathering in this basin. Offshore, we find evidence for efficient terrestrial organic carbon burial over the Holocene period, suggesting that erosion of organic carbon-rich, high-latitude soils may result in an important geological CO2 sink.

  16. Monolithic porous graphitic carbons obtained through catalytic graphitization of carbon xerogels

    NASA Astrophysics Data System (ADS)

    Kiciński, Wojciech; Norek, Małgorzata; Bystrzejewski, Michał

    2013-01-01

    Pyrolysis of organic xerogels accompanied by catalytic graphitization and followed by selective-combustion purification was used to produce porous graphitic carbons. Organic gels impregnated with iron(III) chloride or nickel(II) acetate were obtained through polymerization of resorcinol and furfural. During the pyrolysis stage graphitization of the gel matrix occurs, which in turn develops mesoporosity of the obtained carbons. The evolution of the carbon into graphitic structures is strongly dependent on the concentrations of the transition metal. Pyrolysis leads to monoliths of carbon xerogel characterized by substantially enhanced mesoporosity resulting in specific surface areas up to 400 m2/g. Removal of the amorphous carbon by selective-combustion purification reduces the xerogels' mesoporosity, occasionally causing loss of their mechanical strength. The graphitized carbon xerogels were investigated by means of SEM, XRD, Raman scattering, TG-DTA and N2 physisorption. Through this procedure well graphitized carbonaceous materials can be obtained as bulk pieces.

  17. Iron-filled multi-walled carbon nanotubes for terahertz applications: effects of interfacial polarization, screening and anisotropy.

    PubMed

    Sedelnikova, O V; Korovin, E Yu; Dorozhkin, K V; Kanygin, M A; Arkhipov, V E; Shubin, Yu V; Zhuravlev, V A; Suslyaev, V I; Bulusheva, L G; Okotrub, A V

    2018-04-27

    Interface interactions in multicomponent nanoparticles can affect electromagnetic properties of an absorbing system. In this work, we investigate the electromagnetic response of multi-walled carbon nanotubes (MWCNTs) filled with iron-containing nanoparticles (ICNs) in the terahertz frequency range. MWCNTs with different iron content have been synthesized by aerosol-assisted catalytic chemical vapour deposition method from toluene containing a certain quantity of ferrocene used as a catalyst. According to the x-ray diffraction analysis, encapsulated ICNs were mainly in the form of iron carbide. Thin composite films were prepared from the iron-filled MWCNTs and polymethylmethacrylate (PMMA) by casting and stretching methods. The composites showed an enhanced permittivity and anisotropy in the transmittance spectra when iron content increased. This behaviour was related to the mechanism based on electrical conductivity and polarization of ICNs and ICN/MWCNT interfaces. Since terahertz field penetrates inside MWCNTs, the filling of their cavities can be a way of varying the electromagnetic properties of MWCNT-containing composites.

  18. Iron-filled multi-walled carbon nanotubes for terahertz applications: effects of interfacial polarization, screening and anisotropy

    NASA Astrophysics Data System (ADS)

    Sedelnikova, O. V.; Korovin, E. Yu; Dorozhkin, K. V.; Kanygin, M. A.; Arkhipov, V. E.; Shubin, Yu V.; Zhuravlev, V. A.; Suslyaev, V. I.; Bulusheva, L. G.; Okotrub, A. V.

    2018-04-01

    Interface interactions in multicomponent nanoparticles can affect electromagnetic properties of an absorbing system. In this work, we investigate the electromagnetic response of multi-walled carbon nanotubes (MWCNTs) filled with iron-containing nanoparticles (ICNs) in the terahertz frequency range. MWCNTs with different iron content have been synthesized by aerosol-assisted catalytic chemical vapour deposition method from toluene containing a certain quantity of ferrocene used as a catalyst. According to the x-ray diffraction analysis, encapsulated ICNs were mainly in the form of iron carbide. Thin composite films were prepared from the iron-filled MWCNTs and polymethylmethacrylate (PMMA) by casting and stretching methods. The composites showed an enhanced permittivity and anisotropy in the transmittance spectra when iron content increased. This behaviour was related to the mechanism based on electrical conductivity and polarization of ICNs and ICN/MWCNT interfaces. Since terahertz field penetrates inside MWCNTs, the filling of their cavities can be a way of varying the electromagnetic properties of MWCNT-containing composites.

  19. Storage and release of organic carbon from glaciers and ice sheets

    NASA Astrophysics Data System (ADS)

    Hood, Eran; Battin, Tom J.; Fellman, Jason; O'Neel, Shad; Spencer, Robert G. M.

    2015-02-01

    Polar ice sheets and mountain glaciers, which cover roughly 11% of the Earth's land surface, store organic carbon from local and distant sources and then release it to downstream environments. Climate-driven changes to glacier runoff are expected to be larger than climate impacts on other components of the hydrological cycle, and may represent an important flux of organic carbon. A compilation of published data on dissolved organic carbon from glaciers across five continents reveals that mountain and polar glaciers represent a quantitatively important store of organic carbon. The Antarctic Ice Sheet is the repository of most of the roughly 6 petagrams (Pg) of organic carbon stored in glacier ice, but the annual release of glacier organic carbon is dominated by mountain glaciers in the case of dissolved organic carbon and the Greenland Ice Sheet in the case of particulate organic carbon. Climate change contributes to these fluxes: approximately 13% of the annual flux of glacier dissolved organic carbon is a result of glacier mass loss. These losses are expected to accelerate, leading to a cumulative loss of roughly 15 teragrams (Tg) of glacial dissolved organic carbon by 2050 due to climate change -- equivalent to about half of the annual flux of dissolved organic carbon from the Amazon River. Thus, glaciers constitute a key link between terrestrial and aquatic carbon fluxes, and will be of increasing importance in land-to-ocean fluxes of organic carbon in glacierized regions.

  20. Storage and release of organic carbon from glaciers and ice sheets

    USGS Publications Warehouse

    Hood, Eran; Battin, Tom J.; Fellman, Jason; O'Neel, Shad; Spencer, Robert G. M.

    2015-01-01

    Polar ice sheets and mountain glaciers, which cover roughly 11% of the Earth's land surface, store organic carbon from local and distant sources and then release it to downstream environments. Climate-driven changes to glacier runoff are expected to be larger than climate impacts on other components of the hydrological cycle, and may represent an important flux of organic carbon. A compilation of published data on dissolved organic carbon from glaciers across five continents reveals that mountain and polar glaciers represent a quantitatively important store of organic carbon. The Antarctic Ice Sheet is the repository of most of the roughly 6 petagrams (Pg) of organic carbon stored in glacier ice, but the annual release of glacier organic carbon is dominated by mountain glaciers in the case of dissolved organic carbon and the Greenland Ice Sheet in the case of particulate organic carbon. Climate change contributes to these fluxes: approximately 13% of the annual flux of glacier dissolved organic carbon is a result of glacier mass loss. These losses are expected to accelerate, leading to a cumulative loss of roughly 15 teragrams (Tg) of glacial dissolved organic carbon by 2050 due to climate change — equivalent to about half of the annual flux of dissolved organic carbon from the Amazon River. Thus, glaciers constitute a key link between terrestrial and aquatic carbon fluxes, and will be of increasing importance in land-to-ocean fluxes of organic carbon in glacierized regions.

  1. THE EFFECT OF PH AND DISSOLVED INORGANIC CARBON ON THE PROPERTIES OF IRON COLLOIDAL SUSPENSIONS

    EPA Science Inventory

    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....

  2. Impact on the Fe redox cycling of organic ligands released by Synechococcus PCC 7002, under different iron fertilization scenarios. Modeling approach

    NASA Astrophysics Data System (ADS)

    Samperio-Ramos, Guillermo; González-Dávila, Melchor; Santana-Casiano, J. Magdalena

    2018-06-01

    The kinetics of Fe redox transformations are of crucial importance in determining the bioavailability of iron, due to inorganic Fe(II) and Fe weakly organic complexes being the most easily assimilated species by phytoplankton. The role played by the natural organic ligands excreted by the cyanobacteria Synecococcus PCC 7002 on the iron redox chemistry was studied at different stages of growth, considering changes in the organic exudation of the cyanobacteria, associated with growth under two different scenarios of iron availability. The oxidation/reduction processes of iron were studied at nanomolar levels and under different physicochemical conditions of pH (7.2- 8.2), temperature (5- 35 °C) and salinity (10- 37). The presence of natural organic exudates of Synechococcus affected the redox behavior of iron. A pH-dependent and photo-induced Fe(III) reduction process was detected in the presence of exudates produced under Fe-Low conditions. Photolytic reactions also modified the reactivity of those exudates with respect to Fe(II), increasing its lifetime in seawater. Without light mediated processes, organic ligands excreted under iron deficient conditions intensified the Fe(II) oxidation at pH < 7.5. The organic exudates released under High-Fe conditions retarded the Fe(II) oxidation rate, as a function of DOC produced. The changes in the apparent oxidation rate were fitted to polynomial functions for both of the Fe-scenarios considered. A kinetic modeling approach to describe the speciation and the contribution of individual Fe(II) species to the overall oxidation rate was applied, considering the experimental data and delimiting the equilibrium and redox constants between iron and the major ligands present in solution. Two organic type ligands for the exudates of Synechococcus PCC 7002, with different iron-chelation properties were included in the model. The Fe(II) speciation was radically affected when organic ligands were considered. The individual

  3. Adsorption of Toluene and Paraxylene from Aqueous Solution Using Pure and Iron Oxide Impregnated Carbon Nanotubes: Kinetics and Isotherms Study

    PubMed Central

    Abbas, Aamir; Ihsanullah; Al-Baghli, Nadhir A. H.

    2017-01-01

    Multiwall carbon nanotubes (CNTs) and iron oxide impregnated carbon nanotubes (CNTs-iron oxide) were investigated for the adsorption of hazardous toluene and paraxylene (p-xylene) from aqueous solution. Pure CNTs were impregnated with iron oxides nanoparticles using wet impregnation technique. Various characterization techniques including thermogravimetric analysis, scanning electron microscopy, elemental dispersion spectroscopy, X-ray diffraction, and nitrogen adsorption analysis were used to study the thermal degradation, surface morphology, purity, and surface area of the materials. Batch adsorption experiments show that iron oxide impregnated CNTs have higher degree of removal of p-xylene (i.e., 90%) compared with toluene (i.e., 70%), for soaking time 2 h, with pollutant initial concentration 100 ppm, at pH 6 and shaking speed of 200 rpm at 25°C. Pseudo-second-order model provides better fitting for the toluene and p-xylene adsorption. Langmuir and Freundlich isotherm models demonstrate good fitting for the adsorption data of toluene and p-xylene. PMID:28386208

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

    NASA Astrophysics Data System (ADS)

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

    2018-03-01

    As the most abundant transition metal in the Earth's crust, iron is a key player in the planetary redox budget. Observations of iron minerals in the sedimentary record have been used to describe atmospheric and aqueous redox environments over the evolution of our planet; the most common method applied is iron speciation, a geochemical sequential extraction method in which proportions of different iron minerals are compared to calibrations from modern sediments to determine water-column redox state. Less is known about how this proxy records information through post-depositional processes, including diagenesis and metamorphism. To get insight into this, we examined how the iron mineral groups/pools (silicates, oxides, sulfides, etc.) and paleoredox proxy interpretations can be affected by known metamorphic processes. Well-known metamorphic reactions occurring in sub-chlorite to kyanite rocks are able to move iron between different iron pools along a range of proxy vectors, potentially affecting paleoredox results. To quantify the effect strength of these reactions, we examined mineralogical and geochemical data from two classic localities where Silurian-Devonian shales, sandstones, and carbonates deposited in a marine sedimentary basin with oxygenated seawater (based on global and local biological constraints) have been regionally metamorphosed from lower-greenschist facies to granulite facies: Waits River and Gile Mountain Formations, Vermont, USA and the Waterville and Sangerville-Vassalboro Formations, Maine, USA. Plotting iron speciation ratios determined for samples from these localities revealed apparent paleoredox conditions of the depositional water column spanning the entire range from oxic to ferruginous (anoxic) to euxinic (anoxic and sulfidic). Pyrrhotite formation in samples highlighted problems within the proxy as iron pool assignment required assumptions about metamorphic reactions and pyrrhotite's identification depended on the extraction techniques

  5. Increased iron availability resulting from increased CO2 enhances carbon and nitrogen metabolism in the economical marine red macroalga Pyropia haitanensis (Rhodophyta).

    PubMed

    Chen, Binbin; Zou, Dinghui; Yang, Yufeng

    2017-04-01

    Ocean acidification caused by rising CO 2 is predicted to increase the concentrations of dissolved species of Fe(II) and Fe(III), leading to the enhanced photosynthetic carbon sequestration in some algal species. In this study, the carbon and nitrogen metabolism in responses to increased iron availability under two CO 2 levels (390 μL L -1 and 1000 μL L -1 ), were investigated in the maricultivated macroalga Pyropia haitanensis (Rhodophyta). The results showed that, elevated CO 2 increased soluble carbonhydrate (SC) contents, resulting from enhanced photosynthesis and photosynthetic pigment synthesis in this algae, but declined its soluble protein (SP) contents, resulting in increased ratio of SC/SP. This enhanced photosynthesis performance and carbon accumulation was more significant under iron enrichment condition in seawater, with higher iron uptake rate at high CO 2 level. As a key essential biogenic element for algae, Fe-replete functionally contributed to P. haitanensis photosynthesis. Increased SC fundamentally provided carbon skeletons for nitrogen assimilation. The significant increase of carbon and nitrogen assimilation finally contributed to enhanced growth in this alga. This was also intuitively reflected by respiration that provided energy for cellular metabolism and algal growth. We propose that, in the predicted scenario of rising atmospheric CO 2 , P. haitanensis is capable to adjust its physiology by increasing its carbon and nitrogen metabolism to acclimate the acidified seawater, at the background of global climate change and simultaneously increased iron concentration due to decreased pH levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Understanding the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets in activated carbon using a quantum mechanics/molecular mechanics computational approach.

    PubMed

    Ha, Nguyen Ngoc; Cam, Le Minh; Ha, Nguyen Thi Thu; Goh, Bee-Min; Saunders, Martin; Jiang, Zhong-Tao; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z; El-Harbawi, Mohanad; Yin, Chun-Yang

    2017-06-07

    The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO 4 2- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO 4 2- . Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.

  7. [Effects of Chinese prickly ash orchard on soil organic carbon mineralization and labile organic carbon in karst rocky desertification region of Guizhou province].

    PubMed

    Zhang, Wen-Juan; Liao, Hong-Kai; Long, Jian; Li, Juan; Liu, Ling-Fei

    2015-03-01

    Taking 5-year-old Chinese prickly ash orchard (PO-5), 17-year-old Chinese prickly ash orchard (PO- 17), 30-year-old Chinese prickly ash orchard (PO-30) and the forest land (FL, about 60 years) in typical demonstration area of desertification control test in southwestern Guizhou as our research objects, the aim of this study using a batch incubation experiment was to research the mineralization characteristics of soil organic carbon and changes of the labile soil organic carbon contents at different depths (0-15 cm, 15-30 cm, and 30-50 cm). The results showed that: the cumulative mineralization amounts of soil organic carbon were in the order of 30-year-old Chinese prickly ash orchard, the forest land, 5-year-old Chinese prickly ash orchard and 17-year-old Chinese prickly ash orchard at corresponding depth. Distribution ratios of CO2-C cumulative mineralization amount to SOC contents were higher in Chinese prickly ash orchards than in forest land at each depth. Cultivation of Chinese prickly ash in long-term enhanced the mineralization of soil organic carbon, and decreased the stability of soil organic carbon. Readily oxidized carbon and particulate organic carbon in forest land soils were significantly more than those in Chinese prickly ash orchards at each depth (P < 0.05). With the increasing times of cultivation of Chinese prickly ash, the contents of readily oxidized carbon and particulate organic carbon first increased and then declined at 0-15 cm and 15-30 cm depth, respectively, but an opposite trend was found at 30-50 cm depth. At 0-15 cm and 15-30 cm, cultivation of Chinese prickly ash could be good for improving the contents of labile soil organic carbon in short term, but it was not conducive in long-term. In this study, we found that cultivation of Chinese prickly ash was beneficial for the accumulation of labile organic carbon at the 30-50 cm depth.

  8. Land Use Change and Soil Organic Carbon Dynamics in China

    NASA Astrophysics Data System (ADS)

    Peng, C.; Wu, H.; Guo, Z.

    2004-05-01

    The changes of soil organic carbon depend not only on biogeochemical and climatological processes, but also on human activities and their interaction with carbon cycle. A long history of agricultural exploitation, forest management practice, rapid change in land use, forestry policies, and economic growth suggest that Chinese terrestrial ecosystems play an important role in the global carbon cycles. Using the data compiled from China's second national soil survey and an improved method of soil carbon bulk density, we have estimated the changes of soil organic carbon due to land use, and compared the spatial distribution and storage of soil organic carbon (SOC) in cultivated soils and non-cultivated soils in China. The results reveal that ~57% of the cultivated soil subgroups (~31% of the total soil surface) have experienced a significant carbon loss, ranging from 40% to 10% relative to their non-cultivated counterparts. The most significant carbon loss is observed for the non-irrigated soils (dry farmland) within a semi-arid/semi-humid belt from northeastern to southwestern China, with the maximum loss occurring in northeast China. Our results suggest that total organic carbon storage in soils in China is estimated to be about 70.31 Pg, representing 4.7% of the world storage. The results also indicated that a soil organic carbon loss of 7.1 Pg was primarily due to human activity, in which the loss in organic horizons has contributed to 77%. This total loss of soil organic carbon in China induced by land use represents 9.5% of the world's soil organic carbon decrease.

  9. Method for reducing iron losses in an iron smelting process

    DOEpatents

    Sarma, B.; Downing, K.B.

    1999-03-23

    A process of smelting iron that comprises the steps of: (a) introducing a source of iron oxide, oxygen, nitrogen, and a source of carbonaceous fuel to a smelting reactor, at least some of said oxygen being continuously introduced through an overhead lance; (b) maintaining conditions in said reactor to cause (1) at least some of the iron oxide to be chemically reduced, (2) a bath of molten iron to be created and stirred in the bottom of the reactor, surmounted by a layer of slag, and (3) carbon monoxide gas to rise through the slag; (c) causing at least some of said carbon monoxide to react in the reactor with the incoming oxygen, thereby generating heat for reactions taking place in the reactor; and (d) releasing from the reactor an offgas effluent, is run in a way that keeps iron losses in the offgas relatively low. After start-up of the process is complete, steps (a) and (b) are controlled so as to: (1) keep the temperature of the molten iron at or below about 1550 C and (2) keep the slag weight at or above about 0.8 ton per square meter. 13 figs.

  10. Method for reducing iron losses in an iron smelting process

    DOEpatents

    Sarma, Balu; Downing, Kenneth B.

    1999-01-01

    A process of smelting iron that comprises the steps of: a) introducing a source of iron oxide, oxygen, nitrogen, and a source of carbonaceous fuel to a smelting reactor, at least some of said oxygen being continuously introduced through an overhead lance; b) maintaining conditions in said reactor to cause (i) at least some of the iron oxide to be chemically reduced, (ii) a bath of molten iron to be created and stirred in the bottom of the reactor, surmounted by a layer of slag, and (iii) carbon monoxide gas to rise through the slag; c) causing at least some of said carbon monoxide to react in the reactor with the incoming oxygen, thereby generating heat for reactions taking place in the reactor; and d) releasing from the reactor an offgas effluent, is run in a way that keeps iron losses in the offgas relatively low. After start-up of the process is complete, steps (a) and (b) are controlled so as to: e) keep the temperature of the molten iron at or below about 1550.degree. C. and f) keep the slag weight at or above about 0.8 tonne per square meter.

  11. Dynamics of maize carbon contribution to soil organic carbon in association with soil type and fertility level.

    PubMed

    Pei, Jiubo; Li, Hui; Li, Shuangyi; An, Tingting; Farmer, John; Fu, Shifeng; Wang, Jingkuan

    2015-01-01

    Soil type and fertility level influence straw carbon dynamics in the agroecosystems. However, there is a limited understanding of the dynamic processes of straw-derived and soil-derived carbon and the influence of the addition of straw carbon on soil-derived organic carbon in different soils associated with different fertility levels. In this study, we applied the in-situ carborundum tube method and 13C-labeled maize straw (with and without maize straw) at two cropland (Phaeozem and Luvisol soils) experimental sites in northeast China to quantify the dynamics of maize-derived and soil-derived carbon in soils associated with high and low fertility, and to examine how the addition of maize carbon influences soil-derived organic carbon and the interactions of soil type and fertility level with maize-derived and soil-derived carbon. We found that, on average, the contributions of maize-derived carbon to total organic carbon in maize-soil systems during the experimental period were differentiated among low fertility Luvisol (from 62.82% to 42.90), high fertility Luvisol (from 53.15% to 30.00%), low fertility Phaeozem (from 58.69% to 36.29%) and high fertility Phaeozem (from 41.06% to 16.60%). Furthermore, the addition of maize carbon significantly decreased the remaining soil-derived organic carbon in low and high fertility Luvisols and low fertility Phaeozem before two months. However, the increasing differences in soil-derived organic carbon between both soils with and without maize straw after two months suggested that maize-derived carbon was incorporated into soil-derived organic carbon, thereby potentially offsetting the loss of soil-derived organic carbon. These results suggested that Phaeozem and high fertility level soils would fix more maize carbon over time and thus were more beneficial for protecting soil-derived organic carbon from maize carbon decomposition.

  12. Dynamics of Maize Carbon Contribution to Soil Organic Carbon in Association with Soil Type and Fertility Level

    PubMed Central

    Pei, Jiubo; Li, Hui; Li, Shuangyi; An, Tingting; Farmer, John; Fu, Shifeng; Wang, Jingkuan

    2015-01-01

    Soil type and fertility level influence straw carbon dynamics in the agroecosystems. However, there is a limited understanding of the dynamic processes of straw-derived and soil-derived carbon and the influence of the addition of straw carbon on soil-derived organic carbon in different soils associated with different fertility levels. In this study, we applied the in-situ carborundum tube method and 13C-labeled maize straw (with and without maize straw) at two cropland (Phaeozem and Luvisol soils) experimental sites in northeast China to quantify the dynamics of maize-derived and soil-derived carbon in soils associated with high and low fertility, and to examine how the addition of maize carbon influences soil-derived organic carbon and the interactions of soil type and fertility level with maize-derived and soil-derived carbon. We found that, on average, the contributions of maize-derived carbon to total organic carbon in maize-soil systems during the experimental period were differentiated among low fertility Luvisol (from 62.82% to 42.90), high fertility Luvisol (from 53.15% to 30.00%), low fertility Phaeozem (from 58.69% to 36.29%) and high fertility Phaeozem (from 41.06% to 16.60%). Furthermore, the addition of maize carbon significantly decreased the remaining soil-derived organic carbon in low and high fertility Luvisols and low fertility Phaeozem before two months. However, the increasing differences in soil-derived organic carbon between both soils with and without maize straw after two months suggested that maize-derived carbon was incorporated into soil-derived organic carbon, thereby potentially offsetting the loss of soil-derived organic carbon. These results suggested that Phaeozem and high fertility level soils would fix more maize carbon over time and thus were more beneficial for protecting soil-derived organic carbon from maize carbon decomposition. PMID:25774529

  13. Dispersion and separation of nanostructured carbon in organic solvents

    NASA Technical Reports Server (NTRS)

    Evans, Christopher M. (Inventor); Ruf, Herbert J. (Inventor); Landi, Brian J. (Inventor); Raffaelle, Ryne P. (Inventor)

    2011-01-01

    The present invention relates to dispersions of nanostructured carbon in organic solvents containing alkyl amide compounds and/or diamide compounds. The invention also relates to methods of dispersing nanostructured carbon in organic solvents and methods of mobilizing nanostructured carbon. Also disclosed are methods of determining the purity of nanostructured carbon.

  14. Iron Hydroxide Minerals Drive Organic and Phosphorus Chemistry in Subsurface Redox / pH Gradients

    NASA Astrophysics Data System (ADS)

    Flores, E.; Barge, L. M.; VanderVelde, D.; Baum, M.

    2017-12-01

    Iron minerals, particularly iron oxides and oxyhydroxides, are prevalent on Mars and may exist in mixed valence or even reduced states beneath the oxidized surface. Iron (II,III) hydroxides, including green rust, are reactive and potentially catalytic minerals that can absorb and concentrate charged species, while also driving chemical reactions. These minerals are highly redox-sensitive and the presence of organics and/or phosphorus species could affect their mineralogy and/or stability. Conversely, the minerals might be able to drive chemical processes such as amino acid formation, phosphorus oxyanion reactions, or could simply selectively preserve organic species via surface adsorption. In an open aqueous sediment column, soluble products of mineral-driven reactions could also diffuse to sites of different chemical conditions to react even further. We synthesized Fe-hydroxide minerals under various conditions relevant to early Earth and ancient Mars (>3.0 Gyr), anoxically and in the presence of salts likely to have been present in surface or ground waters. Using these minerals we conducted experiments to test whether iron hydroxides could promote amino acid formation, and how the reaction is affected by subsurface gradients of redox, pH, and temperature. We also tested the adsorption of organic and phosphorus species onto Fe-hydroxide minerals at different conditions within the gradients. The suite of organic or phosphorus signatures that may be found in a particular mineral system is a combination of what is synthesized there, what is preferentially concentrated / retained there, and what is preserved against degradation. Further work is needed to determine how these processes could have proceeded on Mars and what mineral-organic signatures, abiotic or otherwise, would be produced from such processes.

  15. Organic acids influence iron uptake in the human epithelial cell line Caco-2.

    PubMed

    Salovaara, Susan; Sandberg, Ann-Sofie; Andlid, Thomas

    2002-10-09

    It has previously been suggested that organic acids enhance iron absorption. We have studied the effect of nine organic acids on the absorption of Fe(II) and Fe(III) in the human epithelial cell line Caco-2. The effect obtained was dose-dependent, and the greatest increase (43-fold) was observed for tartaric acid (4 mmol/L) on Fe(III) (10 micromol/L). Tartaric, malic, succinic, and fumaric acids enhanced Fe(II) and Fe(III) uptake. Citric and oxalic acid, on the other hand, inhibited Fe(II) uptake but enhanced Fe(III) uptake. Propionic and acetic acid increased the Fe(II) uptake, but had no effect on Fe(III) uptake. Our results show a correlation between absorption pattern and chemical structure; e.g. hydroxyl groups, in addition to carboxyls, were connected with a positive influence. The results may be important for elucidating factors affecting iron bioavailability in the small intestine and for the development of foods with improved iron bioavailability.

  16. Sorptive Uptake Studies of an Aryl-Arsenical with Iron Oxide Composites on an Activated Carbon Support

    PubMed Central

    Kwon, Jae H.; Wilson, Lee D.; Sammynaiken, Ramaswami

    2014-01-01

    Sorption uptake kinetics and equilibrium studies for 4-hydroxy-3-nitrobenzene arsonic acid (roxarsone) was evaluated with synthetic magnetite (Mag-P), commercial magnetite (Mag-C), magnetite 10%, 19%, and 32% composite material (CM-10, -19, -32) that contains granular activated carbon (GAC), and synthetic goethite at pH 7.00 in water at 21 °C for 24 h. GAC showed the highest sorptive removal of roxarsone and the relative uptake for each sorbent material with roxarsone are listed in descending order as follows: GAC (471 mg/g) > goethite (418 mg/g) > CM-10 (377 mg/g) CM-19 (254 mg/g) > CM-32 (227 mg/g) > Mag-P (132 mg/g) > Mag-C (29.5 mg/g). The As (V) moiety of roxarsone is adsorbed onto the surface of the iron oxide/oxyhydrate and is inferred as inner-sphere surface complexes; monodentate-mononuclear, bidentate-mononuclear, and bidentate-binuclear depending on the protolytic speciation of roxarsone. The phenyl ring of roxarsone provides the primary driving force for the sorptive interaction with the graphene surface of GAC and its composites. Thus, magnetite composites are proposed as multi-purpose adsorbents for the co-removal of inorganic and organic arsenicals due to the presence of graphenic and iron oxide active adsorption sites. PMID:28788545

  17. Characteristics of organic carbon accumulation in subtropical seagrass meadows

    NASA Astrophysics Data System (ADS)

    Tanaya, T.; Watanabe, K.; Yamamoto, S.; Hongo, C.; Kayanne, H.; Kuwae, T.

    2016-02-01

    The carbon sequestrated in marine ecosystems has been termed "blue carbon", and seagrass meadows are one of the most dominant blue carbon stocks. Globally, the major distribution sites of seagrass meadows are coral reef flats, where it is technically difficult to quantify organic carbon in carbonate sediments. Since blue carbon stocks have been estimated to date based on seagrass biomass and fine sediments (<1 mm), no studies have measured total carbon stocks, including coarse sediments (1> mm) in seagrass meadows. To solve this problem, we developed a new box corer which can facilitate to obtain the intact cores structured by both sediments and seagrass bodies. Using the core samples taken in subtropical seagrass meadows, located off Ishigaki Island, Japan, we measured total organic carbon mass (TOCmass) and stable isotope ratios (δ13C) of total sedimentary organic matter (SOM) and estimated their sources and controlling factors. The averaged TOCmass of top 15 cm SOM including living seagrasses was 940±480 gC/m2. The live seagrass biomass accounted for only 14±14wt%, whereas the dead biomass (>2 mm), coarse sediments (>1 mm except for dead plant structures >2 mm) and fine sediments (<1 mm) accounted for 3±4wt%, 19±13wt%, and 63±14wt%, respectively. The dead biomass and coarse sediments, which have not yet been included in the past estimations, accounted for about 22wt% of the averaged TOCmass. Total organic carbon content (TOC%) of mixture of the dead biomass, coarse sediments and fine sediments increased with increasing the live seagrass biomass (R = 0.66, n = 13, p = 0.014). The live seagrass biomass was one of the controlling factors of blue carbon stocks at the sites. Using a Bayesian isotopic mixing model, we estimated that the contribution of seagrass-derived carbon to total sedimentary organic carbon was about 70%. The enrichment of sediment organic carbon with increasing the live seagrass biomass was mainly due to the increase of seagrass

  18. Acetone Sensing Properties of a Gas Sensor Composed of Carbon Nanotubes Doped With Iron Oxide Nanopowder.

    PubMed

    Tan, Qiulin; Fang, Jiahua; Liu, Wenyi; Xiong, Jijun; Zhang, Wendong

    2015-11-11

    Iron oxide (Fe₂O₃) nanopowder was prepared by a precipitation method and then mixed with different proportions of carbon nanotubes. The composite materials were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. A fabricated heater-type gas sensor was compared with a pure Fe₂O₃ gas sensor under the influence of acetone. The effects of the amount of doping, the sintering temperature, and the operating temperature on the response of the sensor and the response recovery time were analyzed. Experiments show that doping of carbon nanotubes with iron oxide effectively improves the response of the resulting gas sensors to acetone gas. It also reduces the operating temperature and shortens the response recovery time of the sensor. The response of the sensor in an acetone gas concentration of 80 ppm was enhanced, with good repeatability.

  19. Greenhouse Gas Mitigation Options in ISEEM Global Energy Model: 2010-2050 Scenario Analysis for Least-Cost Carbon Reduction in Iron and Steel Sector

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

    Karali, Nihan; Xu, Tengfang; Sathaye, Jayant

    The goal of the modeling work carried out in this project was to quantify long-term scenarios for the future emission reduction potentials in the iron and steel sector. The main focus of the project is to examine the impacts of carbon reduction options in the U.S. iron and steel sector under a set of selected scenarios. In order to advance the understanding of carbon emission reduction potential on the national and global scales, and to evaluate the regional impacts of potential U.S. mitigation strategies (e.g., commodity and carbon trading), we also included and examined the carbon reduction scenarios in China’smore » and India’s iron and steel sectors in this project. For this purpose, a new bottom-up energy modeling framework, the Industrial Sector Energy Efficiency Modeling (ISEEM), (Karali et al. 2012) was used to provide detailed annual projections starting from 2010 through 2050. We used the ISEEM modeling framework to carry out detailed analysis, on a country-by-country basis, for the U.S., China’s, and India’s iron and steel sectors. The ISEEM model applicable to iron and steel section, called ISEEM-IS, is developed to estimate and evaluate carbon emissions scenarios under several alternative mitigation options - including policies (e.g., carbon caps), commodity trading, and carbon trading. The projections will help us to better understand emission reduction potentials with technological and economic implications. The database for input of ISEEM-IS model consists of data and information compiled from various resources such as World Steel Association (WSA), the U.S. Geological Survey (USGS), China Steel Year Books, India Bureau of Mines (IBM), Energy Information Administration (EIA), and recent LBNL studies on bottom-up techno-economic analysis of energy efficiency measures in the iron and steel sector of the U.S., China, and India, including long-term steel production in China. In the ISEEM-IS model, production technology and manufacturing

  20. Edaphic controls on soil organic carbon stocks in restored grasslands

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

    O'Brien, Sarah L.; Jastrow, Julie D.; Grimley, David A.

    Cultivation of undisturbed soils dramatically depletes organic carbon stocks at shallow depths, releasing a substantial quantity of stored carbon to the atmosphere. Restoration of native ecosystems can help degraded soils rebuild a portion of the depleted soil organic matter. However, the rate and magnitude of soil carbon accrual can be highly variable from site to site. Thus, a better understanding of the mechanisms controlling soil organic carbon stocks is necessary to improve predictions of soil carbon recovery. We measured soil organic carbon stocks and a suite of edaphic factors in the upper 10 cm of a series of restored tallgrassmore » prairies representing a range of drainage conditions. Our findings suggest that factors related to soil organic matter stabilization mechanisms (texture, polyvalent cations) were key predictors of soil organic carbon, along with variables that influence plant and microbial biomass (available phosphorus, pH) and soil moisture. Exchangeable soil calcium was the strongest single predictor, explaining 74% of the variation in soil organic carbon, followed by clay content,which explained 52% of the variation. Our results demonstrate that the cumulative effects of even relatively small differences in these edaphic properties can have a large impact on soil carbon stocks when integrated over several decades.« less

  1. Impact of Nanoparticles and Natural Organic Matter on the Removal of Organic Pollutants by Activated Carbon Adsorption

    EPA Science Inventory

    Isotherm experiments evaluating trichloroethylene (TCE) adsorption onto powdered activated carbon (PAC) were conducted in the presence and absence of three commercially available nanomaterials— iron oxide (Fe2O3), titanium dioxide (TiO2), and silicon dioxide (SiO2). Isotherm exp...

  2. Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon

    NASA Astrophysics Data System (ADS)

    Xiong, Ying; Tong, Qiang; Shan, Weijun; Xing, Zhiqiang; Wang, Yuejiao; Wen, Siqi; Lou, Zhenning

    2017-09-01

    Iron hydroxide/manganese dioxide doped straw activated carbon was synthesized for As(III) adsorption. The Fe-Mn-SAc adsorbent has two advantages, on the one hand, the straw active carbon has a large surface area (1360.99 m2 g-1) for FeOOH and MnO2 deposition, on the other hand, the manganese dioxide has oxidative property as a redox potential of (MnO2 + H+)/Mn2+, which could convert As(III) into As(V). Combined with the arsenic species after reacting with Fe-Mn-SAc, the As(III) transformation and adsorption mechanism was discussed. H2AsO4-oxidized from As(III) reacts with the Fe-Mn-SAc by electrostatic interaction, and unoxidized As(III) as H3AsO3 reacts with SAc and/or iron oxide surface by chelation effect. The adsorption was well-described by Langmuir isotherms model, and the adsorption capacity of As(III) was 75.82 mg g-1 at pH 3. Therefore, considering the straw as waste biomass material, the biosorbent (Fe-Mn-SAc) is promising to be exploited for applications in the treatment of industrial wastewaters containing a certain ratio of arsenic and germanium.

  3. Preservation of organic matter in nontronite against iron redox cycling.

    NASA Astrophysics Data System (ADS)

    Zeng, Q.

    2015-12-01

    It is generally believed that clay minerals can protect organic matter from degradation in redox active environments, but both biotic and abiotic factors can influence the redox process and thus potentially change the clay-organic associations. However, the specific mechanisms involved in this process remain poorly understood. In this study, a model organic compound, 12-Aminolauric acid (ALA) was selected to intercalate into the structural interlayer of nontronite (an iron-rich smectite, NAu-2) to form an ALA-intercalated NAu-2 composite (ALA-NAu-2). Shawanella putrefaciens CN32 and sodium dithionite were used to reduce structural Fe(III) to Fe(II) in NAu-2 and ALA-NAu-2. The bioreduced ALA-NAu-2 was subsequently re-oxidized by air. The rates and extents of bioreduction and air re-oxidation were determined with wet chemistry methods. ALA release from ALA-NAu-2 via redox process was monitored. Mineralogical changes after iron redox cycle were investigated with X-ray diffraction, infrared spectroscopy, and scanning and transmission electron microscopy. At the beginning stage of bioreduction, S. putrefaciens CN32 reduced Fe(III) from the edges of nontronite and preferentially reduced and dissolved small and poorly crystalline particles, and released ALA, resulting a positive correlation between ALA release and iron reduction extent (<12%). The subsequent bioreduction (reduction extent ranged from 12~30%) and complete air re-oxidation showed no effect on ALA release. These results suggest that released ALA was largely from small and poorly crystalline NAu-2 particles. In contrast to bioreduction, chemical reduction did not exhibit any selectivity in reducing ALA-NAu-2 particles, and a considerable amount of reductive dissolution was responsible for a large amount of ALA release (>80%). Because bacteria are the principal agent for mediating redox process in natural environments, our results demonstrated that the structural interlayer of smectite can serve as a potential

  4. The role of microbial iron reduction in the formation of Proterozoic molar tooth structures

    NASA Astrophysics Data System (ADS)

    Hodgskiss, Malcolm S. W.; Kunzmann, Marcus; Poirier, André; Halverson, Galen P.

    2018-01-01

    Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger, with the exception of two isolated Ediacaran occurrences. Despite being locally volumetrically significant in carbonate rocks of this age, their formation and disappearance in the geological record remain enigmatic. Here we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and sulphur contents for 87 samples from units in ten different basins spanning ca. 1900-635 Ma. The iron isotope composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or residue components in the host sediment. We interpret the isotopically light iron in molar tooth structures to have been produced by dissimilatory iron reduction utilising Fe-rich smectites and Fe-oxyhydroxides in the upper sediment column. The microbial conversion of smectite to illite results in a volume reduction of clay minerals (∼30%) while simultaneously increasing pore water alkalinity. When coupled with wave loading, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures in the mid-Neoproterozoic is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and an increase in the concentration of O2 in shallow seawater.

  5. First-principles calculations of high-pressure iron-bearing monoclinic dolomite and single-cation carbonates with internally-consistent Hubbard U

    NASA Astrophysics Data System (ADS)

    Solomatova, N. V.; Asimow, P. D.

    2017-12-01

    It has been proposed that iron has a significant effect on the relative stability of carbonate phases at high pressures, possibly even stabilizing double-cation carbonates (e.g., dolomite) with respect to single-cation carbonates (e.g., magnesite, aragonite and siderite). X-ray diffraction experiments have shown that dolomite transforms at 35 GPa to a high-pressure polymorph that is stable to decomposition; however, there has been disagreement on the structure of the high-pressure phase [1,2]. Ab initio calculations interfaced with an evolutionary structure prediction algorithm demonstrated that a C2/c polymorph of pure CaMg(CO3)2 dolomite is more stable than previously reported structures [3]. In this study, we calculate the relative enthalpies up to 80 GPa for a set of carbonate phases including Fe-bearing solutions and endmembers, using the generalized gradient approximation and a Hubbard U parameter calculated through linear response theory to accurately characterize the electronic structure of Fe. When calculated with a constant U of 4 eV, the spin transition pressure of (Mg,Fe)CO3 agrees well with experiments, whereas an internally-consistent U overestimates the spin transition pressure by 50 GPa. However, whether we use constant or internally-consistent U values, a higher iron concentration increases the stability field of dolomite C2/c with respect to single-cation carbonate assemblages, but iron-free dolomite is not stable with respect to single-cation carbonates at any pressure. Thus, high-pressure polymorphs of Fe-bearing dolomite could in fact represent an important reservoir for carbon storage within oxidized sections of Earth's mantle. [1] Mao, Z. et al. (2011) Geophysical Research Letters, 38. [2] Merlini, M. et al. (2012) Proceedings of the National Academy of Sciences, 109, 13509-13514. [3] Solomatova, N. V. and Asimow, P. D. (2017) American Mineralogist, 102, 210-215.

  6. Soil Carbon Cycling - More than Changes in Soil Organic Carbon Stocks

    NASA Astrophysics Data System (ADS)

    Lorenz, K.

    2015-12-01

    Discussions about soil carbon (C) sequestration generally focus on changes in soil organic carbon (SOC) stocks. Global SOC mass in the top 1 m was estimated at about 1325 Pg C, and at about 3000 Pg C when deeper soil layers were included. However, both inorganically and organically bound carbon forms are found in soil but estimates on global soil inorganic carbon (SIC) mass are even more uncertain than those for SOC. Globally, about 947 Pg SIC may be stored in the top 1 m, and especially in arid and semi-arid regions SIC stocks can be many times great than SOC stocks. Both SIC and SOC stocks are vulnerable to management practices, and stocks may be enhanced, for example, by optimizing net primary production (NPP) by fertilization and irrigation (especially optimizing belowground NPP for enhancing SOC stocks), adding organic matter (including black C for enhancing SOC stocks), and reducing soil disturbance. Thus, studies on soil C stocks, fluxes, and vulnerability must look at both SIC and SOC stocks in soil profiles to address large scale soil C cycling.

  7. Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits

    NASA Astrophysics Data System (ADS)

    Baumann, Lydia; Birgel, Daniel; Wagreich, Michael; Peckmann, Jörn

    2015-04-01

    Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope

  8. Out of Balance—Systemic Iron Homeostasis in Iron-Related Disorders

    PubMed Central

    Steinbicker, Andrea U.; Muckenthaler, Martina U.

    2013-01-01

    Iron is an essential element in our daily diet. Most iron is required for the de novo synthesis of red blood cells, where it plays a critical role in oxygen binding to hemoglobin. Thus, iron deficiency causes anemia, a major public health burden worldwide. On the other extreme, iron accumulation in critical organs such as liver, heart, and pancreas causes organ dysfunction due to the generation of oxidative stress. Therefore, systemic iron levels must be tightly balanced. Here we focus on the regulatory role of the hepcidin/ferroportin circuitry as the major regulator of systemic iron homeostasis. We discuss how regulatory cues (e.g., iron, inflammation, or hypoxia) affect the hepcidin response and how impairment of the hepcidin/ferroportin regulatory system causes disorders of iron metabolism. PMID:23917168

  9. Adsorption and photodegradation of methylene blue by iron oxide impregnated on granular activated carbons in an oxalate solution

    NASA Astrophysics Data System (ADS)

    Kadirova, Zukhra C.; Katsumata, Ken-ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Okada, Kiyoshi

    2013-11-01

    The photocatalytic adsorbents BAU-OA, BAU-CL and BAU-HA with varying iron oxide content (9-10 mass%) were prepared by heat treatment at 250 °C from commercial activated carbon (BAU) impregnated with iron oxalate, chloride, tris-benzohydroxamate, respectively. The XRD patterns showed amorphous structure in the BAU-CL sample (SBET 50 m2/g) and low crystallinity (as FeOOH and Fe2O3 phases) in the BAU-HA and BAU-OA samples (SBET 4 and 111 m2/g, respectively). The methylene blue adsorption capacities was decreased in order of BAU-OA < BAU-CL < BAU-HA sample and the adsorption followed Langmuir model. The apparent MB photodegradation rate constant (kapp) was increased in same order BAU-HA < BAU-CL < BAU-OA under the standard experimental conditions (initial MB concentrations 0.015-0.025 mM; sample content - 10 mg/l; initial oxalic acid concentration - 0.43 mM; pH 3-4; UV illumination). The process included high efficiency combination of adsorption, heterogeneous and homogeneous catalysis under UV and solar lights illumination without addition of hydrogen peroxide. The detoxification of water sample containing organic dyes was confirmed after combined sorption-photocatalytic treatment.

  10. Coal desulfurization. [using iron pentacarbonyl

    NASA Technical Reports Server (NTRS)

    Hsu, G. C. (Inventor)

    1979-01-01

    Organic sulfur is removed from coal by treatment with an organic solution of iron pentacarbonyl. Organic sulfur compounds can be removed by reaction of the iron pentacarbonyl with coal to generate CO and COS off-gases. The CO gas separated from COS can be passed over hot iron fillings to generate iron pentacarbonyl.

  11. Variations of iron flux and organic carbon remineralization in a subterranean estuary caused by inter-annual variations in recharge

    NASA Astrophysics Data System (ADS)

    Roy, Moutusi; Martin, Jonathan B.; Cable, Jaye E.; Smith, Christopher G.

    2013-02-01

    We determine the inter-annual variations in diagenetic reaction rates of sedimentary iron (Fe) in an east Florida subterranean estuary and evaluate the connection between metal fluxes and recharge to the coastal aquifer. Over the three years study period (from 2004 to 2007), the amount of Fe-oxides reduced at the study site decreased from 192 to 153 g/yr and associated organic carbon (OC) remineralization decreased from 48 to 38 g/yr. These reductions occurred although the Fe-oxide reduction rates remained constant around 1 mg/cm2/yr. These results suggest that changes in flow rates of submarine groundwater discharge (SGD) related to changes in precipitation may be important to fluxes of the diagenetic reaction products. Rainfall at a weather station approximately 5 km from the field area decreased from 12.6 to 8.4 cm/month from 2004 to 2007. Monthly potential evapotranspiration (PET) calculated from Thornthwaite's method indicated potential evapotranspiration cycled from about 3 cm/month in the winter to about 15 cm/month in the summer so that net annual recharge to the aquifer decreased from 40 cm in 2004 to -10 cm in 2007. Simultaneously with the decrease in recharge of groundwater, freshwater SGD decreased by around 20% and caused the originally 25 m wide freshwater seepage face to decrease in width by about 5 m. The smaller seepage face reduced the area under which Fe-oxides were undergoing reductive dissolution. Consequently, the observed decrease in Fe flux is controlled by hydrology of the subterranean estuary. These results point out the need to better understand linkages between temporal variations in diagenetic reactions and changes in flow within subterranean estuaries in order to accurately constrain their contribution to oceanic fluxes of solutes from subterranean estuaries.

  12. Soil Organic Carbon Degradation during Incubation, Barrow, Alaska, 2012

    DOE Data Explorer

    Elizabeth Herndon; Ziming Yang; Baohua Gu

    2017-01-05

    This dataset provides information about soil organic carbon decomposition in Barrow soil incubation studies. The soil cores were collected from low-center polygon (Area A) and were incubated in the laboratory at different temperatures for up to 60 days. Transformations of soil organic carbon were characterized by UV and FT-IR, and small organic acids in water-soluble carbons were quantified by ion chromatography during the incubation (Herndon et al., 2015).

  13. Acetone Sensing Properties of a Gas Sensor Composed of Carbon Nanotubes Doped With Iron Oxide Nanopowder

    PubMed Central

    Tan, Qiulin; Fang, Jiahua; Liu, Wenyi; Xiong, Jijun; Zhang, Wendong

    2015-01-01

    Iron oxide (Fe2O3) nanopowder was prepared by a precipitation method and then mixed with different proportions of carbon nanotubes. The composite materials were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. A fabricated heater-type gas sensor was compared with a pure Fe2O3 gas sensor under the influence of acetone. The effects of the amount of doping, the sintering temperature, and the operating temperature on the response of the sensor and the response recovery time were analyzed. Experiments show that doping of carbon nanotubes with iron oxide effectively improves the response of the resulting gas sensors to acetone gas. It also reduces the operating temperature and shortens the response recovery time of the sensor. The response of the sensor in an acetone gas concentration of 80 ppm was enhanced, with good repeatability. PMID:26569253

  14. Degradation mechanism of Direct Pink 12B treated by iron-carbon micro-electrolysis and Fenton reaction.

    PubMed

    Wang, Xiquan; Gong, Xiaokang; Zhang, Qiuxia; Du, Haijuan

    2013-12-01

    The Direct Pink 12B dye was treated by iron-carbon micro-electrolysis (ICME) and Fenton oxidation. The degradation pathway of Direct Pink 12B dye was inferred by ultraviolet visible (UV-Vis), infrared absorption spectrum (IR) and high performance liquid chromatography-mass spectrometry (HPLC-MS). The major reason of decolorization was that the conjugate structure was disrupted in the iron-carbon micro-electrolysis (ICME) process. However, the dye was not degraded completely because benzene rings and naphthalene rings were not broken. In the Fenton oxidation process, the azo bond groups surrounded by higher electron cloud density were first attacked by hydroxyl radicals to decolorize the dye molecule. Finally benzene rings and naphthalene rings were mineralized to H2O and CO2 under the oxidation of hydroxyl radicals. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

  15. A Description of an Acidophilic, Iron Reducer, Geobacter sp. FeAm09 Isolated from Tropical Soils

    NASA Astrophysics Data System (ADS)

    Healy, O.; Souchek, J.; Heithoff, A.; LaMere, B.; Pan, D.; Hollis, G.; Yang, W. H.; Silver, W. L.; Weber, K. A.

    2014-12-01

    Iron (Fe) is the fourth most abundant element in the Earth's crust and plays a significant role controlling the geochemistry in soils, sediments, and aquatic systems. As part of a study to understand microbially-catalysed iron biogeochemical cycling in tropical soils, an iron reducing isolate, strain FeAm09, was obtained. Strain FeAm09 was isolated from acidic, Fe-rich soils collected from a tropical forest (Luquillo Experimental Forest, Puerto Rico). Strain FeAm09 is a rod-shaped, motile, Gram-negative bacterium. Taxonomic analysis of the near complete 16S rRNA gene sequence revealed that strain FeAm09 is 94.7% similar to Geobacter lovleyi, placing it in the genus Geobacter within the Family Geobacteraceae in the Deltaproteobacteria. Characterization of the optimal growth conditions revealed that strain FeAm09 is a moderate acidophile with an optimal growth pH of 5.0. The optimal growth temperature was 37°C. Growth of FeAm09 was coupled to the reduction of soluble Fe(III), Fe(III)-NTA, with H2, fumarate, ethanol, and various organic acids and sugars serving as the electron donor. Insoluble Fe(III), in the form of synthetic ferrihydrite, was reduced by strain FeAm09 using acetate or H2 as the electron donor. The use of H2 as an electron donor in the presence of CO2 and absence of organic carbon and assimilation of 14C-labelled CO2 into biomass indicate that strain FeAm09 is an autotrophic Fe(III)-reducing bacterium. Together, these data describe the first acidophilic, autotrophic Geobacter species. Iron reducing bacteria were previously shown to be as abundant in tropical soils as in saturated sediments (lake-bottoms) and saturated soils (wetlands) where Fe(III) reduction is more commonly recognized as a dominant mode of microbial respiration. Furthermore, Fe(III) reduction was identified as a primary driver of carbon mineralization in these tropical soils (Dubinsky et al. 2010). In addition to mineralizing organic carbon, Geobacter sp. FeAm09 is likely to also

  16. Changes in coal sulfur during carbonization

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

    Anderson, R.A.; Polansky, T.S.

    1960-08-01

    Changes in the sulfur forms during carbonization of a High Volatile A rank, high sulfur, Pittsburgh Seam coal were investigated. Possible effects of mineral matter content were investigated by use of a float fraction of the whole coal. The coals were carbonized in a vertical, static bed unit designed to study the effects of primary and secondary reactions of the sulfur forms. Pyrite was completely decomposed at about 700/sup 0/C and sulfate sulfur was not observed above 650/sup 0/C. Formation of inorganic sulfides, excluding iron sulfide, was noted by the nonstoichiometric relationship of sulfide sulfur and non-pyritic iron. Iron, uncombinedmore » with sulfur, was observed in cokes carbonized at temperatures between 350/sup 0/ and 650/sup 0/C. Organic sulfur began to decompose at about 366/sup 0/C, and it amounted to approximately 11 percent of the total coke sulfur at 885/sup 0/C. Elmental sulfur was qualitatively detected in cokes produced above 700/sup 0/C by benzoin, and a method for determining it quantitatively was investigated.« less

  17. PHOTOCHEICAL PRODUCTION OF HYDROXYL RADICAL IN NATURAL WATER - THE ROLE OF IRON AND DISSOLVED ORGANIC MATTER

    EPA Science Inventory

    Photochemical hydroxyl radical (OH) production was measured in several natural waters to investigate the importance of colored dissolved organic matter (CDOM) and iron-CDOM complexes as sources of OH. High rates of OH photoproduction in highly colored, iron-rich, acidic waters a...

  18. Soil organic carbon response to shrub encroachment regulated by soil aggregates

    NASA Astrophysics Data System (ADS)

    Zhu, Y.; Li, H.; Shen, H.; Feng, Y.; Fang, J.

    2017-12-01

    Shrub encroachment leads to change in soil organic carbon content, but there still exists a lot of uncertainty in its mechanism as it relates to deep soil research. Soil organic carbon is usually associated with stable aggregate quantity. In this study, we conducted a field investigation for typical steppe and desert steppe in Inner Mongolia with the view to examining the impact of shrub encroachment on soil organic carbon with soil aggregate at a depth of 0-500 cm. The results show that in the desert steppe, the particle size of soil aggregate content level in different depth are presented the trend of shrub patches is lower than the herb matrix, organic carbon content of soil aggregate under 50 cm deeper presents the trend of shrub patches is higher than herb matrix, eventually leading to shrub patches whole soil organic carbon in the 0 to 50 cm depth lower than the herb matrix, and in deeper soil below 50 cm higher than the herb matrix. In the typical steppe, there is no significant difference between soil aggregate structure of shrub patches and herb matrix, but organic carbon content of soil aggregate, especially large aggregate organic carbon content in the shrub patches is significantly higher than the herb matrix, so that the whole soil organic carbon content in the shrub patches is significantly higher than herb matrix. The rate of soil organic carbon content change (0-100 cm) by shrub encroachment showed significant negative correlation with the mean weight diameter of soil aggregate of herb matrix. We also found that the variations of soil organic carbon in desert steppe is not dominant by aggregates of some size, but the change of the typical steppe soil organic carbon mainly contributed by > 0.25 mm and 0.053-0.25 mm aggregates. The results suggested that the effects of shrub encroachment on soil organic carbon is regulated by soil aggregate, but it is varied for different type of grassland, which should provide some insights into our understanding on

  19. Insights in groundwater organic matter from Liquid Chromatography-Organic Carbon Detection

    NASA Astrophysics Data System (ADS)

    Rutlidge, H.; Oudone, P.; McDonough, L.; Andersen, M. S.; Baker, A.; Meredith, K.; O'Carroll, D. M.

    2017-12-01

    Understanding the processes that control the concentration and characteristics of organic matter in groundwater has important implications for the terrestrial global carbon budget. Liquid Chromatography - Organic Carbon Detection (LC-OCD) is a size-exclusion based chromatography technique that separates the organic carbon into molecular weight size fractions of biopolymers, humic substances, building blocks (degradation products of humic substances), low molecular weight acids and low molecular weight neutrals. Groundwater and surface water samples were collected from a range of locations in Australia representing different surface soil, land cover, recharge type and hydrological properties. At one site hyporheic zone samples were also collected from beneath a stream. The results showed a general decrease in the aromaticity and molecular weight indices going from surface water, hyporheic downwelling and groundwater samples. The aquifer substrate also affected the organic composition. For example, groundwater samples collected from a zone of fractured rock showed a relative decrease in the proportion of humic substances, suggestive of sorption or degradation of humic substances. This work demonstrates the potential for using LC-OCD in elucidating the processes that control the concentration and characteristics of organic matter in groundwater.

  20. Net carbon flux in organic and conventional olive production systems

    NASA Astrophysics Data System (ADS)

    Saeid Mohamad, Ramez; Verrastro, Vincenzo; Bitar, Lina Al; Roma, Rocco; Moretti, Michele; Chami, Ziad Al

    2014-05-01

    Agricultural systems are considered as one of the most relevant sources of atmospheric carbon. However, agriculture has the potentiality to mitigate carbon dioxide mainly through soil carbon sequestration. Some agricultural practices, particularly fertilization and soil management, can play a dual role in the agricultural systems regarding the carbon cycle contributing to the emissions and to the sequestration process in the soil. Good soil and input managements affect positively Soil Organic Carbon (SOC) changes and consequently the carbon cycle. The present study aimed at comparing the carbon footprint of organic and conventional olive systems and to link it to the efficiency of both systems on carbon sequestration by calculating the net carbon flux. Data were collected at farm level through a specific and detailed questionnaire based on one hectare as a functional unit and a system boundary limited to olive production. Using LCA databases particularly ecoinvent one, IPCC GWP 100a impact assessment method was used to calculate carbon emissions from agricultural practices of both systems. Soil organic carbon has been measured, at 0-30 cm depth, based on soil analyses done at the IAMB laboratory and based on reference value of SOC, the annual change of SOC has been calculated. Substracting sequestrated carbon in the soil from the emitted on resulted in net carbon flux calculation. Results showed higher environmental impact of the organic system on Global Warming Potential (1.07 t CO2 eq. yr-1) comparing to 0.76 t CO2 eq. yr-1 in the conventional system due to the higher GHG emissions caused by manure fertilizers compared to the use of synthetic foliar fertilizers in the conventional system. However, manure was the main reason behind the higher SOC content and sequestration in the organic system. As a resultant, the organic system showed higher net carbon flux (-1.7 t C ha-1 yr-1 than -0.52 t C ha-1 yr-1 in the conventional system reflecting higher efficiency as a

  1. A reduced organic carbon component in martian basalts.

    PubMed

    Steele, A; McCubbin, F M; Fries, M; Kater, L; Boctor, N Z; Fogel, M L; Conrad, P G; Glamoclija, M; Spencer, M; Morrow, A L; Hammond, M R; Zare, R N; Vicenzi, E P; Siljeström, S; Bowden, R; Herd, C D K; Mysen, B O; Shirey, S B; Amundsen, H E F; Treiman, A H; Bullock, E S; Jull, A J T

    2012-07-13

    The source and nature of carbon on Mars have been a subject of intense speculation. We report the results of confocal Raman imaging spectroscopy on 11 martian meteorites, spanning about 4.2 billion years of martian history. Ten of the meteorites contain abiotic macromolecular carbon (MMC) phases detected in association with small oxide grains included within high-temperature minerals. Polycyclic aromatic hydrocarbons were detected along with MMC phases in Dar al Gani 476. The association of organic carbon within magmatic minerals indicates that martian magmas favored precipitation of reduced carbon species during crystallization. The ubiquitous distribution of abiotic organic carbon in martian igneous rocks is important for understanding the martian carbon cycle and has implications for future missions to detect possible past martian life.

  2. Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines.

    PubMed

    Modin, Hanna; Persson, Kenneth M; Andersson, Anna; van Praagh, Martijn

    2011-05-30

    Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. The transformation of inorganic sulfur compounds and the assimilation of organic and inorganic carbon by the sulfur disproportionating bacterium Desulfocapsa sulfoexigens.

    PubMed

    Frederiksen, Trine-Maria; Finster, Kai

    2004-02-01

    The physiology of the sulfur disproportionator Desulfocapsa sulfoexigens was investigated in batch cultures and in a pH-regulated continuously flushed fermentor system. It was shown that a sulphide scavanger in the form of ferric iron was not obligatory and that the control of pH allowed production of more biomass than was possible in carbonate buffered but unregulated batch cultures. Small amounts of sulphite were produced during disproportionation of elemental sulfur and thiosulphate. In addition, it was shown that in the presence of hydrogen, a respiratory type of process is favored before the disproportionation of sulphite, thiosulphate and elemental sulfur. Sulphate reduction was not observed. D. sulfoexigens assimilated inorganic carbon even in the presence of organic carbon sources. Inorganic carbon assimilation was probably catalyzed by the reverse CO-dehydrogenase pathway, which was supported by the constitutive expression of the gene encoding CO-dehydrogenase in cultures grown in the presence of acetate and by the high carbon fractionation values that are indicative of this pathway.

  4. Fertilization increases paddy soil organic carbon density.

    PubMed

    Wang, Shao-xian; Liang, Xin-qiang; Luo, Qi-xiang; Fan, Fang; Chen, Ying-xu; Li, Zu-zhang; Sun, Huo-xi; Dai, Tian-fang; Wan, Jun-nan; Li, Xiao-jun

    2012-04-01

    Field experiments provide an opportunity to study the effects of fertilization on soil organic carbon (SOC) sequestration. We sampled soils from a long-term (25 years) paddy experiment in subtropical China. The experiment included eight treatments: (1) check, (2) PK, (3) NP, (4) NK, (5) NPK, (6) 7F:3M (N, P, K inorganic fertilizers+30% organic N), (7) 5F:5M (N, P, K inorganic fertilizers+50% organic N), (8) 3F:7M (N, P, K inorganic fertilizers+70% organic N). Fertilization increased SOC content in the plow layers compared to the non-fertilized check treatment. The SOC density in the top 100 cm of soil ranged from 73.12 to 91.36 Mg/ha. The SOC densities of all fertilizer treatments were greater than that of the check. Those treatments that combined inorganic fertilizers and organic amendments had greater SOC densities than those receiving only inorganic fertilizers. The SOC density was closely correlated to the sum of the soil carbon converted from organic amendments and rice residues. Carbon sequestration in paddy soils could be achieved by balanced and combined fertilization. Fertilization combining both inorganic fertilizers and organic amendments is an effective sustainable practice to sequestrate SOC.

  5. Fertilization increases paddy soil organic carbon density*

    PubMed Central

    Wang, Shao-xian; Liang, Xin-qiang; Luo, Qi-xiang; Fan, Fang; Chen, Ying-xu; Li, Zu-zhang; Sun, Huo-xi; Dai, Tian-fang; Wan, Jun-nan; Li, Xiao-jun

    2012-01-01

    Field experiments provide an opportunity to study the effects of fertilization on soil organic carbon (SOC) sequestration. We sampled soils from a long-term (25 years) paddy experiment in subtropical China. The experiment included eight treatments: (1) check, (2) PK, (3) NP, (4) NK, (5) NPK, (6) 7F:3M (N, P, K inorganic fertilizers+30% organic N), (7) 5F:5M (N, P, K inorganic fertilizers+50% organic N), (8) 3F:7M (N, P, K inorganic fertilizers+70% organic N). Fertilization increased SOC content in the plow layers compared to the non-fertilized check treatment. The SOC density in the top 100 cm of soil ranged from 73.12 to 91.36 Mg/ha. The SOC densities of all fertilizer treatments were greater than that of the check. Those treatments that combined inorganic fertilizers and organic amendments had greater SOC densities than those receiving only inorganic fertilizers. The SOC density was closely correlated to the sum of the soil carbon converted from organic amendments and rice residues. Carbon sequestration in paddy soils could be achieved by balanced and combined fertilization. Fertilization combining both inorganic fertilizers and organic amendments is an effective sustainable practice to sequestrate SOC. PMID:22467369

  6. Effects of dissolved low molecular weight organic acids on oxidation of ferrous iron by Acidithiobacillus ferrooxidans.

    PubMed

    Ren, Wan-Xia; Li, Pei-Jun; Zheng, Le; Fan, Shu-Xiu; Verhozina, V A

    2009-02-15

    A few researchers have reported on work concerning bioleaching of heavy-metal-contaminated soil using Acidithiobacillus ferrooxidans, since this acidophile is sensitive to dissolved low molecular weight (LMW) organic acids. Iron oxidation by A. ferrooxidans R2 as well as growth on ferrous iron was inhibited by a variety of dissolved LMW organic acids. Growth experiments with ferrous iron as an oxidant showed that the inhibition capability sequence was formic acid>acetic acid>propionic acid>oxalic acid>malic acid>citric acid. The concentrations that R2 might tolerate were formic acid 0.1mmolL(-1) (2mmolkg(-1)soil), acetic and propionic acids 0.4mmolL(-1) (8mmolkg(-1)soil), oxalic acid 2.0mmolL(-1) (40mmolkg(-1)soil), malic acid 20mmolL(-1) (400mmolkg(-1)soil), citric acid 40mmolL(-1) (800mmolkg(-1)soil), respectively. Although R2 was sensitive to organic acids, the concentrations of LMW organic acids in the contaminated soils were rather lower than the tolerable levels. Hence, it is feasible that R2 might be used for bioleaching of soils contaminated with metals or metals coupled with organic compounds because of the higher concentrations of LMW organic acids to which R2 is tolerant.

  7. Magnetite impregnation effects on the sorbent properties of activated carbons and biochars.

    PubMed

    Han, Zhantao; Sani, Badruddeen; Mrozik, Wojciech; Obst, Martin; Beckingham, Barbara; Karapanagioti, Hrissi K; Werner, David

    2015-03-01

    This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Decoupling of Iron and Phosphate in the Global Ocean

    NASA Technical Reports Server (NTRS)

    Parekh, Payal

    2003-01-01

    Iron is an essential micronutrient for marine phytoplankton, limiting their growth in high nutrient, low chlorophyll regions of the ocean. I use a hierarchy of ocean circulation and biogeochemistry models to understand controls on global iron distribution. I formulate a mechanistic model of iron cycling which includes scavenging onto sinking particles and complexation with an organic ligand. The iron cycle is coupled to a phosphorus cycling model. Iron's aeolian source is prescribed. In the context of a highly idealized multi-box model scheme, the model can be brought into consistency with the relatively sparse ocean observations of iron in the oceans. This biogeochemical scheme is also implemented in a coarse resolution ocean general circulation model. This model also successfully reproduces the broad regional patterns of iron and phosphorus. In particular, the high macronutrient concentrations of the Southern Ocean result from iron limitation in the model. Due to the potential ability of iron to change the efficiency of the carbon pump in the remote Southern Ocean, I study Southern Ocean surface phosphate response to increased aeolian dust flux. My box model and GCM results suggest that a global ten fold increase in dust flux can support a phosphate drawdown of 0.25-0.5 micromolar.

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

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

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

    2012-04-04

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

  10. [Deposition and burial of organic carbon in coastal salt marsh: research progress].

    PubMed

    Cao, Lei; Song, Jin-Ming; Li, Xue-Gang; Yuan, Hua-Mao; Li, Ning; Duan, Li-Qin

    2013-07-01

    Coastal salt marsh has higher potential of carbon sequestration, playing an important role in mitigating global warming, while coastal saline soil is the largest organic carbon pool in the coastal salt marsh carbon budget. To study the carbon deposition and burial in this soil is of significance for clearly understanding the carbon budget of coastal salt marsh. This paper summarized the research progress on the deposition and burial of organic carbon in coastal salt marsh from the aspects of the sources of coastal salt marsh soil organic carbon, soil organic carbon storage and deposition rate, burial mechanisms of soil organic carbon, and the relationships between the carbon sequestration in coastal salt marsh and the global climate change. Some suggestions for the future related researches were put forward: 1) to further study the underlying factors that control the variability of carbon storage in coastal salt marsh, 2) to standardize the methods for measuring the carbon storage and the deposition and burial rates of organic carbon in coastal salt marsh, 3) to quantify the lateral exchange of carbon flux between coastal salt marsh and adjacent ecosystems under the effects of tide, and 4) to approach whether the effects of global warming and the increased productivity could compensate for the increase of the organic carbon decomposition rate resulted from sediment respiration. To make clear the driving factors determining the variability of carbon sequestration rate and how the organic carbon storage is affected by climate change and anthropogenic activities would be helpful to improve the carbon sequestration capacity of coastal salt marshes in China.

  11. [Effects of combined application of water retention agent and organic fertilizer on physico-chemical properties of iron tailings.

    PubMed

    Li, Xiang; Zhang, Bao Juan; Li, Ji Quan; Li, Yu Ling; Li, Chen Guang

    2017-02-01

    In order to analyze the effects of combined application of water retention agent and orga-nic fertilizer on physico-chemical properties of iron tailings and to find the optimal proportion of water retention agent and organic fertilizer for the improvement of iron tailings, the experimental plots of the combination trials with 2 factors in 4 levels were designed in the iron tailings of Qian'an Shougang through investigating some indexes of physico-chemical properties such as bulk density, moisture capacity, porosity, pH and the contents of organic matter, nitrogen, phosphorus and potas-sium. The biomasses of Medicago sativa and Amorpha fruticosa planted in the experimental plots were measured to verify the improvement effects. 4 levels of super absorbent polymers (L·m -3 ) used in treatments were 0 (B 0 ), 10 (B 1 ), 50 (B 2 ), 100 (B 3 ), and 4 levels of organic fertilizer (kg·m -2 ) were 0(N 0 ), 2.25 (N 1 ), 11.24 (N 2 ), 22.49 (N 3 ). The improving effects of different treatments on physico-chemical properties of iron tailings were mainly reflected in the surface layer of 0-20 cm. All the tested indexes were significantly different from control (CK) in the layer of 0-20 cm. The improvement effects of organic fertilizer on physical and chemical properties of iron tai-lings were better than that of water retention agent. In the 0-20 cm layer, the bulk density, non-capillary porosity, organic matter, rapidly available phosphorus, and available potassium under all treatments of adding water retention agent individually were not significantly different from the CK, while significant difference was observed when the organic fertilizer was solely applied in B 0 N 2 and B 0 N 3 treatments. The improvement synergy effect of organic fertilizer and water retention agent was better than that of organic fertilizer or water retention agent, respectively. In 0-20 cm layer, all the indexes obtained from treatment B 3 N 3 performed best and were significantly different from

  12. Statistics provide guidance for indigenous organic carbon detection on Mars missions.

    PubMed

    Sephton, Mark A; Carter, Jonathan N

    2014-08-01

    Data from the Viking and Mars Science Laboratory missions indicate the presence of organic compounds that are not definitively martian in origin. Both contamination and confounding mineralogies have been suggested as alternatives to indigenous organic carbon. Intuitive thought suggests that we are repeatedly obtaining data that confirms the same level of uncertainty. Bayesian statistics may suggest otherwise. If an organic detection method has a true positive to false positive ratio greater than one, then repeated organic matter detection progressively increases the probability of indigeneity. Bayesian statistics also reveal that methods with higher ratios of true positives to false positives give higher overall probabilities and that detection of organic matter in a sample with a higher prior probability of indigenous organic carbon produces greater confidence. Bayesian statistics, therefore, provide guidance for the planning and operation of organic carbon detection activities on Mars. Suggestions for future organic carbon detection missions and instruments are as follows: (i) On Earth, instruments should be tested with analog samples of known organic content to determine their true positive to false positive ratios. (ii) On the mission, for an instrument with a true positive to false positive ratio above one, it should be recognized that each positive detection of organic carbon will result in a progressive increase in the probability of indigenous organic carbon being present; repeated measurements, therefore, can overcome some of the deficiencies of a less-than-definitive test. (iii) For a fixed number of analyses, the highest true positive to false positive ratio method or instrument will provide the greatest probability that indigenous organic carbon is present. (iv) On Mars, analyses should concentrate on samples with highest prior probability of indigenous organic carbon; intuitive desires to contrast samples of high prior probability and low prior

  13. Modeling the effects of naturally occurring organic carbon on chlorinated ethene transport to a public supply well

    USGS Publications Warehouse

    Chapelle, Francis H.; Kauffman, Leon J.; Widdowson, Mark A.

    2013-01-01

    The vulnerability of public supply wells to chlorinated ethene (CE) contamination in part depends on the availability of naturally occurring organic carbon to consume dissolved oxygen (DO) and initiate reductive dechlorination. This was quantified by building a mass balance model of the Kirkwood-Cohansey aquifer, which is widely used for public water supply in New Jersey. This model was built by telescoping a calibrated regional three-dimensional (3D) MODFLOW model to the approximate capture zone of a single public supply well that has a history of CE contamination. This local model was then used to compute a mass balance between dissolved organic carbon (DOC), particulate organic carbon (POC), and adsorbed organic carbon (AOC) that act as electron donors and DO, CEs, ferric iron, and sulfate that act as electron acceptors (EAs) using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. SEAM3D was constrained by varying concentrations of DO and DOC entering the aquifer via recharge, varying the bioavailable fraction of POC in aquifer sediments, and comparing observed and simulated vertical concentration profiles of DO and DOC. This procedure suggests that approximately 15% of the POC present in aquifer materials is readily bioavailable. Model simulations indicate that transport of perchloroethene (PCE) and its daughter products trichloroethene (TCE), cis-dichloroethene (cis-DCE), and vinyl chloride (VC) to the public supply well is highly sensitive to the assumed bioavailable fraction of POC, concentrations of DO entering the aquifer with recharge, and the position of simulated PCE source areas in the flow field. The results are less sensitive to assumed concentrations of DOC in aquifer recharge. The mass balance approach used in this study also indicates that hydrodynamic processes such as advective mixing, dispersion, and sorption account for a significant amount of the observed natural attenuation in this system.

  14. Modeling the Effects of Naturally Occurring Organic Carbon on Chlorinated Ethene Transport to a Public Supply Well†

    PubMed Central

    Chapelle, Francis H; Kauffman, Leon J; Widdowson, Mark A

    2014-01-01

    The vulnerability of public supply wells to chlorinated ethene (CE) contamination in part depends on the availability of naturally occurring organic carbon to consume dissolved oxygen (DO) and initiate reductive dechlorination. This was quantified by building a mass balance model of the Kirkwood-Cohansey aquifer, which is widely used for public water supply in New Jersey. This model was built by telescoping a calibrated regional three-dimensional (3D) MODFLOW model to the approximate capture zone of a single public supply well that has a history of CE contamination. This local model was then used to compute a mass balance between dissolved organic carbon (DOC), particulate organic carbon (POC), and adsorbed organic carbon (AOC) that act as electron donors and DO, CEs, ferric iron, and sulfate that act as electron acceptors (EAs) using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. SEAM3D was constrained by varying concentrations of DO and DOC entering the aquifer via recharge, varying the bioavailable fraction of POC in aquifer sediments, and comparing observed and simulated vertical concentration profiles of DO and DOC. This procedure suggests that approximately 15% of the POC present in aquifer materials is readily bioavailable. Model simulations indicate that transport of perchloroethene (PCE) and its daughter products trichloroethene (TCE), cis-dichloroethene (cis-DCE), and vinyl chloride (VC) to the public supply well is highly sensitive to the assumed bioavailable fraction of POC, concentrations of DO entering the aquifer with recharge, and the position of simulated PCE source areas in the flow field. The results are less sensitive to assumed concentrations of DOC in aquifer recharge. The mass balance approach used in this study also indicates that hydrodynamic processes such as advective mixing, dispersion, and sorption account for a significant amount of the observed natural attenuation in this system. PMID:24372440

  15. Removal of Trace Arsenic to Meet Drinking Water Standards Using Iron Oxide Coated Multiwall Carbon Nanotubes.

    PubMed

    Ntim, Susana Addo; Mitra, Somenath

    2011-05-12

    This study presents the removal of trace level arsenic to meet drinking water standards using an iron oxide-multi-walled carbon nanotube (Fe-MWCNT) hybrid as a sorbent. The synthesis was facilitated by the high degree of nanotube functionalization using a microwave assisted process, and a controlled assembly of iron oxide was possible where the MWCNT served as an effective support for the oxide. In the final product, 11 % of the carbon atoms were attached to Fe. The Fe-MWCNT was effective in arsenic removal to below the drinking water standard levels of 10 µg L(-1). The absorption capacity of the composite was 1723 µg g(-1) and 189 µg g(-1) for As(III) and As(V) respectively. The adsorption of As(V) on Fe-MWCNT was faster than that of As(III). The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models.

  16. Process based modelling of soil organic carbon redistribution on landscape scale

    NASA Astrophysics Data System (ADS)

    Schindewolf, Marcus; Seher, Wiebke; Amorim, Amorim S. S.; Maeso, Daniel L.; Jürgen, Schmidt

    2014-05-01

    Recent studies have pointed out the great importance of erosion processes in global carbon cycling. Continuous erosion leads to a massive loss of top soils including the loss of organic carbon accumulated over long time in the soil humus fraction. Lal (2003) estimates that 20% of the organic carbon eroded with top soils is emitted into atmosphere, due to aggregate breakdown and carbon mineralization during transport by surface runoff. Furthermore soil erosion causes a progressive decrease of natural soil fertility, since cation exchange capacity is associated with organic colloids. As a consequence the ability of soils to accumulate organic carbon is reduced proportionately to the drop in soil productivity. The colluvial organic carbon might be protected from further degradation depending on the depth of the colluvial cover and local decomposing conditions. Some colluvial sites can act as long-term sinks for organic carbon. The erosional transport of organic carbon may have an effect on the global carbon budget, however, it is uncertain, whether erosion is a sink or a source for carbon in the atmosphere. Another part of eroded soils and organic carbon will enter surface water bodies and might be transported over long distances. These sediments might be deposited in the riparian zones of river networks. Erosional losses of organic carbon will not pass over into atmosphere for the most part. But soil erosion limits substantially the potential of soils to sequester atmospheric CO2 by generating humus. The present study refers to lateral carbon flux modelling on landscape scale using the process based EROSION 3D soil loss simulation model, using existing parameter values. The selective nature of soil erosion results in a preferentially transport of fine particles while less carbonic larger particles remain on site. Consequently organic carbon is enriched in the eroded sediment compared to the origin soil. For this reason it is essential that EROSION 3D provides the

  17. Rapid decolorization of textile wastewater by green synthesized iron nanoparticles.

    PubMed

    Ozkan, Z Y; Cakirgoz, M; Kaymak, E S; Erdim, E

    2018-01-01

    The effectiveness of green tea (Camellia sinensis) and pomegranate (Punica granatum) extracts for the production of iron nanoparticles and their application for color removal from a textile industry wastewater was investigated. Polyphenols in extracts act as reducing agents for iron ions in aqueous solutions, forming iron nanoparticles. Pomegranate extract was found to have almost a 10-fold higher polyphenolic content than the same amount of green tea extract on a mass basis. However, the size of the synthesized nanoparticles did not show a correlation with the polyphenolic content. 100 ppm and 300 ppm of iron nanoparticles were evaluated in terms of color removal efficiency from a real textile wastewater sample. 300 ppm of pomegranate nanoscale zero-valent iron particles showed more than 95% color removal and almost 80% dissolved organic carbon removal. The degradation mechanisms are is considered to be adsorption and precipitation to a major extent, and mineralization to a minor extent.

  18. Deep instability of deforested tropical peatlands revealed by fluvial organic carbon fluxes.

    PubMed

    Moore, Sam; Evans, Chris D; Page, Susan E; Garnett, Mark H; Jones, Tim G; Freeman, Chris; Hooijer, Aljosja; Wiltshire, Andrew J; Limin, Suwido H; Gauci, Vincent

    2013-01-31

    Tropical peatlands contain one of the largest pools of terrestrial organic carbon, amounting to about 89,000 teragrams (1 Tg is a billion kilograms). Approximately 65 per cent of this carbon store is in Indonesia, where extensive anthropogenic degradation in the form of deforestation, drainage and fire are converting it into a globally significant source of atmospheric carbon dioxide. Here we quantify the annual export of fluvial organic carbon from both intact peat swamp forest and peat swamp forest subject to past anthropogenic disturbance. We find that the total fluvial organic carbon flux from disturbed peat swamp forest is about 50 per cent larger than that from intact peat swamp forest. By carbon-14 dating of dissolved organic carbon (which makes up over 91 per cent of total organic carbon), we find that leaching of dissolved organic carbon from intact peat swamp forest is derived mainly from recent primary production (plant growth). In contrast, dissolved organic carbon from disturbed peat swamp forest consists mostly of much older (centuries to millennia) carbon from deep within the peat column. When we include the fluvial carbon loss term, which is often ignored, in the peatland carbon budget, we find that it increases the estimate of total carbon lost from the disturbed peatlands in our study by 22 per cent. We further estimate that since 1990 peatland disturbance has resulted in a 32 per cent increase in fluvial organic carbon flux from southeast Asia--an increase that is more than half of the entire annual fluvial organic carbon flux from all European peatlands. Our findings emphasize the need to quantify fluvial carbon losses in order to improve estimates of the impact of deforestation and drainage on tropical peatland carbon balances.

  19. Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

    PubMed

    Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Ward, Matthew; Pelletier, Mia

    2018-05-01

    The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

  20. Organic Complexation of Dissolved Copper and Iron from Shipboard Incubations in the Central California Current System: Investigating the Impacts of Light Conditions and Phytoplankton Growth on Iron- and Copper-Binding Ligand Characteristics

    NASA Astrophysics Data System (ADS)

    Mellett, T.; Parker, C.; Brown, M.; Coale, T.; Duckham, C.; Chappell, D.; Maldonado, M. T.; Bruland, K. W.; Buck, K. N.

    2016-02-01

    Two shipboard incubation experiments were carried out in July of 2014 to investigate potential sources and sinks of iron- and copper-binding organic ligands in the surface ocean. Seawater for the experiments was collected from the central California Current System (cCCS) and incubated under varying light conditions and in the presence and absence of natural phytoplankton communities. Incubation treatments were sampled over a period of up to 3 days for measurements of total dissolved copper and iron, and for the concentration and conditional stability constants of copper- and iron-binding organic ligands. Dissolved copper and iron were determined by inductively coupled plasma-mass spectrometry (ICP-MS) following preconcentration on a Nobias PA1 resin. Organic ligand characteristics for iron and copper were determined using a method of competitive ligand exchange-absorptive cathodic stripping voltammetry (CLE-ACSV) with the added competing ligand salicylaldoxime. Trends in ligand concentrations and conditional stability constants across the different treatments and over the course of the incubation experiments will be presented.

  1. Engineering of Iron-Based Magnetic Activated Carbon Fabrics for Environmental Remediation

    PubMed Central

    Haham, Hai; Grinblat, Judith; Sougrati, Moulay-Tahar; Stievano, Lorenzo; Margel, Shlomo

    2015-01-01

    Magnetic Fe3O4, Fe and Fe/Pd nanoparticles embedded within the pores of activated carbon fabrics (ACF) were prepared by impregnation of the ACF in iron acetylacetanoate (Fe(acac)3) ethanol solution, followed by thermal decomposition of the embedded iron precursor at 200, 400 and 600 °C in an inert atmosphere. The effect of the annealing temperature on the chemical composition, shape, crystallinity, surface area, pore volume, and magnetic properties of the various functionalized ACF was elucidated. The Fe nanoparticles within the ACF were also doped with tinier Pd nanoparticles, by impregnation of the Fe/ACF in palladium acetate ethanol solution. The potential use of the functionalized ACF for removal of a model azo-dye, orange II, was demonstrated. This study illustrated the enhanced removal of the dye from an aqueous solution according to the following order: Fe/Pd/ACF > Fe/ACF > ACF. In addition, the enhanced activity of Fe3O4/ACF in the presence of increasing concentrations of H2O2 (Fenton catalysts) was also illustrated. PMID:28793459

  2. Volatile organic compound constituents from an integrated iron and steel facility.

    PubMed

    Tsai, Jiun-Horng; Lin, Kuo-Hsiung; Chen, Chih-Yu; Lai, Nina; Ma, Sen-Yi; Chiang, Hung-Lung

    2008-09-15

    This study measured the volatile organic compound (VOC) constituents of four processes in an integrated iron and steel industry; cokemaking, sintering, hot forming, and cold forming. Toluene, 1,2,4-trimethylbenzene, isopentane, m,p-xylene, 1-butene, ethylbenzene, and benzene were the predominant VOC species in these processes. However, some of the chlorinated compounds were high (hundreds ppbv), i.e., trichloroethylene in all four processes, carbon tetrachloride in the hot forming process, chlorobenzene in the cold forming process, and bromomethane in the sintering process. In the sintering process, the emission factors of toluene, benzene, xylene, isopentane, 1,2,4-trimethylbenzene, and ethylbenzene were over 9 g/tonne-product. In the vicinity of the manufacturing plant, toluene, isopentane, 1,2,4-trimethylbenzene, xylene and ethylbenzene were high. Toluene, 1,2,4-trimethylbenzene, xylene, 1-butene and isopentane were the major ozone formation species. Aromatic compounds were the predominant VOC groups, constituting 45-70% of the VOC concentration and contributing >70% to the high ozone formation potential in the stack exhaust and workplace air. The sequence of VOC concentration and ozone formation potential was as follows: cold forming>sintering>hot forming>cokemaking. For the workplace air, cokemaking was the highest producer, which was attributed to the fugitive emissions of the coke oven and working process release.

  3. Reduction of Iron-Oxide-Carbon Composites: Part III. Shrinkage of Composite Pellets during Reduction

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

  4. Respiratory Effects of Inhaled Single-Walled Carbon Nanotubes: The Role of Particle Morphology and Iron Content

    NASA Astrophysics Data System (ADS)

    Madl, Amy Kathleen

    Nanotechnology provides promise for significant advancements in a number of different fields including imaging, electronics, and therapeutics. With worldwide production of carbon nanotubes (CNTs) exceeding over 500 metric tons annually and industry growth expecting to double over the next 5 yr, there are concerns our understanding of the hazards of these nanomaterials may not be keeping pace with market demand. The physicochemical properties of CNTs may delineate the key features that determine either toxicity or biocompatibility and assist in evaluating the potential health risks posed in industrial and consumer product settings. We hypothesized that the iron content and morphology of inhaled single-walled carbon nanotubes (SWCNTs) influences the extent of cellular injury and alters homeostasis in the lung. To address this hypothesis, (1) an aerosol system was developed to deliver carbon-based nanomaterials in a manner of exposure that is physiologically and environmentally relevant (e.g., inhalation), (2) acute (1 d) and subacute (10 d) nose-only inhalation studies to a well-characterized aerosol of iron-containing (FeSWCNT) versus cleaned (iron removed, cSWCNTs) SWCNTs were conducted to evaluate the time-course patterns of possible injury through measurement of markers of cytotoxicity, inflammation, and cellular remodeling/homeostasis, and (3) the effects of SWCNTs were compared to other well-studied materials (e.g. non-fibrous, low-iron content ultrafine carbon black and fibrous, high-iron content, highly persistent, durable and potent carcinogen crocidolite) to offer insights into the relative toxicity of these nanomaterials as well as the possible mechanisms by which the effects occur. Rats (SD) were exposed to either aerosolized SWCNTs (raw FeSWCNT or purified cSWCNT), carbon black (CB), crocidolite, or fresh air via nose-only inhalation. Markers of inflammation and cytotoxicity in lung lavage, mucin in different airway generations, and collagen in the

  5. Influence of AOM on iron-sulfur-carbon systematics in marine sediment: A study from Krishna-Godavari basin, Bay of Bengal

    NASA Astrophysics Data System (ADS)

    Carvalho, M. A.

    2017-12-01

    Sedimentary diagenetic processes play key role in global sulfur-iron-carbon cycle. Microbially driven organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) pathways are responsible for sulfate reduction in marine sediments. Concomitant H2S production and iron sulfide precipitation lead to Fe-sulfide burial in the sediments. Intra/intermolecular organic bound sulfur is also another major sink of global sulfur burial. In the present study, we have investigated the sulfidisation process in a core from Krishna-Godavari (K-G) basin, Bay of Bengal. K-G basin is well known for gas hydrate deposits and methane enrichment within 100-120 mbsf. Previous work from K-G basin has shown tell-tale evidence of paleo episodic- methane expulsion events and formation of authigenic carbonate crust at or above the sea floor1. Our study was carried out on a core MD-161-15 (water depth of 983 m and Lat. =16° 00.5700' N;Long. = 82° 03.4502' E) recovered on board R/V Marion Dufrense). The pyrite content in the core (measured as chromium reducible sulfur: CRS) range from 0.003 to 1.1 wt%. The reactive content (FeTR = FeOx + FeD + FeCRS) range from 0.9 to 3.5 wt%, where FeOX, FeD and FeCRS represents oxalate extractable (magnetite), buffered dithionite extractable (ferrihydrite, lepidocrocite, goethite, hematite) and boiling CrCl2 (in 6N HCl) extractable (Pyrite: FeS2) iron respectively. The δ34SCRS range from -49 to +16.7 ‰ VCDT and show good positive correlation with FeTR. Presence of highly 13C depleted authigenic carbonate in the sediments within 1600-3000 mbsf indicate influence of AOM and possible methane seepage2. The δ34SCRS profile show marked 34S depletion trend within the top 1012 mbsf. Below this depth, δ34SCRS values show steadily increasing trend superimposed by zones of sharp enrichment/ depletion of 34S. The 34S enrichment trend may attributed to late diagenetic pyritization from 34S enriched H2S produced from residual pore water sulfate via AOM

  6. Hyperspectral Analysis of Soil Nitrogen, Carbon, Carbonate, and Organic Matter Using Regression Trees

    PubMed Central

    Gmur, Stephan; Vogt, Daniel; Zabowski, Darlene; Moskal, L. Monika

    2012-01-01

    The characterization of soil attributes using hyperspectral sensors has revealed patterns in soil spectra that are known to respond to mineral composition, organic matter, soil moisture and particle size distribution. Soil samples from different soil horizons of replicated soil series from sites located within Washington and Oregon were analyzed with the FieldSpec Spectroradiometer to measure their spectral signatures across the electromagnetic range of 400 to 1,000 nm. Similarity rankings of individual soil samples reveal differences between replicate series as well as samples within the same replicate series. Using classification and regression tree statistical methods, regression trees were fitted to each spectral response using concentrations of nitrogen, carbon, carbonate and organic matter as the response variables. Statistics resulting from fitted trees were: nitrogen R2 0.91 (p < 0.01) at 403, 470, 687, and 846 nm spectral band widths, carbonate R2 0.95 (p < 0.01) at 531 and 898 nm band widths, total carbon R2 0.93 (p < 0.01) at 400, 409, 441 and 907 nm band widths, and organic matter R2 0.98 (p < 0.01) at 300, 400, 441, 832 and 907 nm band widths. Use of the 400 to 1,000 nm electromagnetic range utilizing regression trees provided a powerful, rapid and inexpensive method for assessing nitrogen, carbon, carbonate and organic matter for upper soil horizons in a nondestructive method. PMID:23112620

  7. Factors influencing organic carbon preservation in marine sediments

    NASA Technical Reports Server (NTRS)

    Canfield, D. E.

    1994-01-01

    The organic matter that escapes decomposition is buried and preserved in marine sediments, with much debate as to whether the amount depends on bottom-water O2 concentration. One group argues that decomposition is more efficient with O2, and hence, organic carbon will be preferentially oxidized in its presence, and preserved in its absence. Another group argues that the kinetics of organic matter decomposition are similar in the presence and absence of O2, and there should be no influence of O2 on preservation. A compilation of carbon preservation shows that both groups are right, depending on the circumstances of deposition. At high rates of deposition, such as near continental margins, little difference in preservation is found with varying bottom-water O2. It is important that most carbon in these sediments decomposes by anaerobic pathways regardless of bottom-water O2. Hence, little influence of bottom-water O2 on preservation would, in fact, be expected. As sedimentation rate drops, sediments deposited under oxygenated bottom water become progressively more aerobic, while euxinic sediments remain anaerobic. Under these circumstances, the relative efficiencies of aerobic and anaerobic decomposition could affect preservation. Indeed, enhanced preservation is observed in low-O2 and euxinic environments. To explore in detail the factors contributing to this enhanced carbon preservation, aspects of the biochemistries of the aerobic and anaerobic process are reviewed. Other potential influences on preservation are also explored. Finally, a new model for organic carbon decomposition, the "pseudo-G" model, is developed. This model couples the degradation of refractory organic matter to the overall metabolic activity of the sediment, and has consequences for carbon preservation due to the mixing together of labile and refractory organic matter by bioturbation.

  8. [Roles of soil dissolved organic carbon in carbon cycling of terrestrial ecosystems: a review].

    PubMed

    Li, Ling; Qiu, Shao-Jun; Liu, Jing-Tao; Liu, Qing; Lu, Zhao-Hua

    2012-05-01

    Soil dissolved organic carbon (DOC) is an active fraction of soil organic carbon pool, playing an important role in the carbon cycling of terrestrial ecosystems. In view of the importance of the carbon cycling, this paper summarized the roles of soil DOC in the soil carbon sequestration and greenhouse gases emission, and in considering of our present ecological and environmental problems such as soil acidification and climate warming, discussed the effects of soil properties, environmental factors, and human activities on the soil DOC as well as the response mechanisms of the DOC. This review could be helpful to the further understanding of the importance of soil DOC in the carbon cycling of terrestrial ecosystems and the reduction of greenhouse gases emission.

  9. The next generation of iron fertilization experiments in the Southern Ocean.

    PubMed

    Smetacek, V; Naqvi, S W A

    2008-11-13

    Of the various macro-engineering schemes proposed to mitigate global warming, ocean iron fertilization (OIF) is one that could be started at short notice on relevant scales. It is based on the reasoning that adding trace amounts of iron to iron-limited phytoplankton of the Southern Ocean will lead to blooms, mass sinking of organic matter and ultimately sequestration of significant amounts of atmospheric carbon dioxide (CO2) in the deep sea and sediments. This iron hypothesis, proposed by John Martin in 1990 (Martin 1990 Paleoceanography 5, 1-13), has been tested by five mesoscale experiments that provided strong support for its first condition: stimulation of a diatom bloom accompanied by significant CO2 drawdown. Nevertheless, a number of arguments pertaining to the fate of bloom biomass, the ratio of iron added to carbon sequestered and various side effects of fertilization, continue to cast doubt on its efficacy. The idea is also unpopular with the public because it is perceived as meddling with nature. However, this apparent consensus against OIF is premature because none of the published experiments were specifically designed to test its second condition pertaining to the fate of iron-induced organic carbon. Furthermore, the arguments on side effects are based on worst-case scenarios. These doubts, formulated as hypotheses, need to be tested in the next generation of OIF experiments. We argue that such experiments, if carried out at appropriate scales and localities, will not only show whether the technique will work, but will also reveal a wealth of insights on the structure and functioning of pelagic ecosystems in general and the krill-based Southern Ocean ecosystem, in particular. The outcomes of current models on the efficacy and side effects of OIF differ widely, so data from adequately designed experiments are urgently needed for realistic parametrization. OIF is likely to boost zooplankton stocks, including krill, which could have a positive effect on

  10. [Effects of different cultivation patterns on soil aggregates and organic carbon fractions].

    PubMed

    Qiu, Xiao-Lei; Zong, Liang-Gang; Liu, Yi-Fan; Du, Xia-Fei; Luo, Min; Wang, Run-Chi

    2015-03-01

    Combined with the research in an organic farm in the past 10 years, differences of soil aggregates composition, distribution and organic carbon fractions between organic and conventional cultivation were studied by simultaneous sampling analysis. The results showed that the percentages of aggregates (> 1 mm, 1-0.5 mm, 0.5-0.25 mm and < 0.25 mm) in the conventional cultivation were 23.75%, 15.15%, 19.98% and 38.09%, while those in organic cultivation were 9.73%, 18.41%, 24.46% and 43.90%, respectively. The percentage of < 0.25 mm micro-aggregates was significantly higher in organic cultivation than that in conventional cultivation. Organic cultivation increased soil organic carbon (average of 17.95 g x kg(-1)) and total nitrogen contents (average of 1.51 g x kg(-1)). Among the same aggregates in organic cultivation, the average content of heavy organic carbon fraction was significantly higher than that in conventional cultivation. This fraction accumulated in < 0. 25 mm micro-aggregates, which were main storage sites of stable organic carbon. In organic cultivation, the content of labile organic carbon in > 1 mm macro-aggregates was significantly higher than that in conventional cultivation, while no significant difference was found among the other aggregates, indicating that the labile organic carbon was enriched in > 1 mm macro-aggregates. Organic cultivation increased the amounts of organic carbon and its fractions, reduced tillage damage to aggregates, and enhanced the stability of organic carbon. Organic cultivation was therefore beneficial for soil carbon sequestration. The findings of this research may provide theoretical basis for further acceleration of the organic agriculture development.

  11. Selection criteria for oxidation method in total organic carbon measurement.

    PubMed

    Yoon, GeunSeok; Park, Sang-Min; Yang, Heuiwon; Tsang, Daniel C W; Alessi, Daniel S; Baek, Kitae

    2018-05-01

    During the measurement of total organic carbon (TOC), dissolved organic carbon is converted into CO 2 by using high temperature combustion (HTC) or wet chemical oxidation (WCO). However, the criteria for selecting the oxidation methods are not clear. In this study, the chemical structures of organic material were considered as a key factor to select the oxidation method used. Most non-degradable organic compounds showed a similar oxidation efficiency in both methods, including natural organic compounds, dyes, and pharmaceuticals, and thus both methods are appropriate to measure TOC in waters containing these compounds. However, only a fraction of the carbon in the halogenated compounds (perfluorooctanoic acid and trifluoroacetic acid) were oxidized using WCO, resulting in measured TOC values that are considerably lower than those determined by HTC. This result is likely due to the electronegativity of halogen elements which inhibits the approach of electron-rich sulfate radicals in the WCO, and the higher bond strength of carbon-halogen pairs as compared to carbon-hydrogen bonds, which results in a lower degree of oxidation of the compounds. Our results indicate that WCO could be used to oxidize most organic compounds, but may not be appropriate to quantify TOC in organic carbon pools that contain certain halogenated compounds. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Microscopic insight into the bilateral formation of carbon spirals from a symmetric iron core

    PubMed Central

    Shiozawa, Hidetsugu; Bachmatiuk, Alicja; Stangl, Andreas; Cox, David C.; Silva, S. Ravi P.; Rümmeli, Mark H.; Pichler, Thomas

    2013-01-01

    Mirrored carbon-spirals have been produced from pressured ferrocene via the bilateral extrusion of the spiral pairs from an iron core. A parametric plot of the surface geometry displays the fractal growth of the conical helix made with the logarithmic spiral. Electron microscopy studies show the core is a crystalline cementite which grows and transforms its shape from spherical to biconical as it extrudes two spiralling carbon arms. In a cross section along the arms we observe graphitic flakes arranged in a herringbone structure, normal to which defects propagate. Local-wave-pattern analysis reveals nanoscale defect patterns of two-fold symmetry around the core. The data suggest that the bilateral growth originates from a globular cementite crystal with molten surfaces and the nano-defects shape emerging hexagonal carbon into a fractal structure. Understanding and knowledge obtained provide a basis for the controlled production of advanced carbon materials with designed geometries. PMID:23670649

  13. Fractionation between inorganic and organic carbon during the Lomagundi (2.22 2.1 Ga) carbon isotope excursion

    NASA Astrophysics Data System (ADS)

    Bekker, A.; Holmden, C.; Beukes, N. J.; Kenig, F.; Eglinton, B.; Patterson, W. P.

    2008-07-01

    The Lomagundi (2.22-2.1 Ga) positive carbon isotope excursion in shallow-marine sedimentary carbonates has been associated with the rise in atmospheric oxygen, but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen. The amount of oxygen released to the exosphere during the Lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon, which is poorly characterized. Because dissolved inorganic and organic carbon reservoirs were arguably larger in the Paleoproterozoic ocean, at a time of lower solar luminosity and lower ocean redox state, decoupling between these two variables might be expected. We determined carbon isotope values of carbonate and organic matter in carbonates and shales of the Silverton Formation, South Africa and in the correlative Sengoma Argillite Formation, near the border in Botswana. These units were deposited between 2.22 and 2.06 Ga along the margin of the Kaapvaal Craton in an open-marine deltaic setting and experienced lower greenschist facies metamorphism. The prodelta to offshore marine shales are overlain by a subtidal carbonate sequence. Carbonates exhibit elevated 13C values ranging from 8.3 to 11.2‰ vs. VPDB consistent with deposition during the Lomagundi positive excursion. The total organic carbon (TOC) contents range from 0.01 to 0.6% and δ13C values range from - 24.8 to - 13.9‰. Thus, the isotopic fractionation between organic and carbonate carbon was on average 30.3 ± 2.8‰ ( n = 32) in the shallow-marine environment. The underlying Sengoma shales have highly variable TOC contents (0.14 to 21.94%) and δ13C values (- 33.7 to - 20.8‰) with an average of - 27.0 ± 3.0‰ ( n = 50). Considering that the shales were also deposited during the Lomagundi excursion, and taking δ13C values of the overlying carbonates as representative of the δ13C value of dissolved inorganic carbon during shale deposition, a carbon

  14. Inorganic carbon and fossil organic carbon are source of bias for quantification of sequestered carbon in mine spoil

    NASA Astrophysics Data System (ADS)

    Vindušková, Olga; Frouz, Jan

    2016-04-01

    Carbon sequestration in mine soils has been studied as a possibility to mitigate the rising atmospheric CO2 levels and to improve mine soil quality (Vindu\\vsková and Frouz, 2013). Moreover, these soils offer an unique opportunity to study soil carbon dynamics using the chronosequence approach (using a set of sites of different age on similar parent material). However, quantification of sequestered carbon in mine soils is often complicated by fossil organic carbon (e.g., from coal or kerogen) or inorganic carbon present in the spoil. We present a methodology for quantification of both of these common constituents of mine soils. Our recommendations are based on experiments done on post-mining soils in Sokolov basin, Czech Republic. Here, fossil organic carbon is present mainly as kerogen Type I and II and represents 2-6 wt.% C in these soils. Inorganic carbon in these soils is present mainly as siderite (FeCO3), calcite (CaCO3), and dolomite (CaMg(CO3)2). All of these carbonates are often found in the overburden of coal seams thus being a common constituent of post-mining soils in the world. Vindu\\vsková O, Frouz J, 2013. Soil carbon accumulation after open-cast coal and oil shale mining in Northern Hemisphere: a quantitative review. ENVIRONMENTAL EARTH SCIENCES, 69: 1685-1698. Vindu\\vsková O, Dvořáček V, Prohasková A, Frouz J. 2014. Distinguishing recent and fossil organic matter - A critical step in evaluation of post-mining soil development - using near infrared spectroscopy. ECOLOGICAL ENGINEERING. 73: 643-648. Vindu\\vsková O, Sebag D, Cailleau G, Brus J, Frouz J. 2015. Methodological comparison for quantitative analysis of fossil and recently derived carbon in mine soils with high content of aliphatic kerogen. ORGANIC GEOCHEMISTRY, 89-90:14-22.

  15. Advection of surface-derived organic carbon fuels microbial reduction in Bangladesh groundwater

    PubMed Central

    Mailloux, Brian J.; Trembath-Reichert, Elizabeth; Cheung, Jennifer; Watson, Marlena; Stute, Martin; Freyer, Greg A.; Ferguson, Andrew S.; Ahmed, Kazi Matin; Alam, Md. Jahangir; Buchholz, Bruce A.; Thomas, James; Layton, Alice C.; Zheng, Yan; Bostick, Benjamin C.; van Geen, Alexander

    2013-01-01

    Chronic exposure to arsenic (As) by drinking shallow groundwater causes widespread disease in Bangladesh and neighboring countries. The release of As naturally present in sediment to groundwater has been linked to the reductive dissolution of iron oxides coupled to the microbial respiration of organic carbon (OC). The source of OC driving this microbial reduction—carbon deposited with the sediments or exogenous carbon transported by groundwater—is still debated despite its importance in regulating aquifer redox status and groundwater As levels. Here, we used the radiocarbon (14C) signature of microbial DNA isolated from groundwater samples to determine the relative importance of surface and sediment-derived OC. Three DNA samples collected from the shallow, high-As aquifer and one sample from the underlying, low-As aquifer were consistently younger than the total sediment carbon, by as much as several thousand years. This difference and the dominance of heterotrophic microorganisms implies that younger, surface-derived OC is advected within the aquifer, albeit more slowly than groundwater, and represents a critical pool of OC for aquifer microbial communities. The vertical profile shows that downward transport of dissolved OC is occurring on anthropogenic timescales, but bomb 14C-labeled dissolved OC has not yet accumulated in DNA and is not fueling reduction. These results indicate that advected OC controls aquifer redox status and confirm that As release is a natural process that predates human perturbations to groundwater flow. Anthropogenic perturbations, however, could affect groundwater redox conditions and As levels in the future. PMID:23487743

  16. [Soil organic carbon fractionation methods and their applications in farmland ecosystem research: a review].

    PubMed

    Zhang, Guo; Cao, Zhi-ping; Hu, Chan-juan

    2011-07-01

    Soil organic carbon is of heterogeneity in components. The active components are sensitive to agricultural management, while the inert components play an important role in carbon fixation. Soil organic carbon fractionation mainly includes physical, chemical, and biological fractionations. Physical fractionation is to separate the organic carbon into active and inert components based on the density, particle size, and its spatial distribution; chemical fractionation is to separate the organic carbon into various components based on the solubility, hydrolizability, and chemical reactivity of organic carbon in a variety of extracting agents. In chemical fractionation, the dissolved organic carbon is bio-available, including organic acids, phenols, and carbohydrates, and the acid-hydrolyzed organic carbon can be divided into active and inert organic carbons. Simulated enzymatic oxidation by using KMnO4 can separate organic carbon into active and non-active carbon. Biological fractionation can differentiate microbial biomass carbon and potential mineralizable carbon. Under different farmland management practices, the chemical composition and pool capacity of soil organic carbon fractions will have different variations, giving different effects on soil quality. To identify the qualitative or quantitative relationships between soil organic carbon components and carbon deposition, we should strengthen the standardization study of various fractionation methods, explore the integrated application of different fractionation methods, and sum up the most appropriate organic carbon fractionation method or the appropriate combined fractionation methods for different farmland management practices.

  17. METHOD 415.3 - MEASUREMENT OF TOTAL ORGANIC CARBON, DISSOLVED ORGANIC CARBON AND SPECIFIC UV ABSORBANCE AT 254 NM IN SOURCE WATER AND DRINKING WATER

    EPA Science Inventory

    2.0 SUMMARY OF METHOD

    2.1 In both TOC and DOC determinations, organic carbon in the water sample is oxidized to form carbon dioxide (CO2), which is then measured by a detection system. There are two different approaches for the oxidation of organic carbon in water sample...

  18. Comparing carbon to carbon: Organic and inorganic carbon balances across nitrogen fertilization gradients in rainfed vs. irrigated Midwest US cropland

    NASA Astrophysics Data System (ADS)

    Hamilton, S. K.; McGill, B.

    2017-12-01

    The top meter of the earth's soil contains about twice the amount of carbon than the atmosphere. Agricultural management practices influence whether a cropland soil is a net carbon source or sink. These practices affect both organic and inorganic carbon cycling although the vast majority of studies examine the former. We will present results from several rarely-compared carbon fluxes: carbon dioxide emissions and sequestration from lime (calcium carbonate) weathering, dissolved gases emitted from groundwater-fed irrigation, dissolved organic carbon (DOC) leaching to groundwater, and soil organic matter storage. These were compared in a corn-soybean-wheat rotation under no-till management across a nitrogen fertilizer gradient where half of the replicated blocks are irrigated with groundwater. DOC and liming fluxes are also estimated from a complementary study in neighboring plots comparing a gradient of management practices from conventional to biologically-based annuals and perennials. These studies were conducted at the Kellogg Biological Station Long Term Ecological Research site in Michigan where previous work estimated that carbon dioxide emissions from liming accounted for about one quarter of the total global warming impact (GWI) from no-till systems—our work refines that figure. We will present a first time look at the GWI of gases dissolved in groundwater that are emitted when the water equilibrates with the atmosphere. We will explore whether nitrogen fertilizer and irrigation increase soil organic carbon sequestration by producing greater crop biomass and residues or if they enhance microbial activity, increasing decomposition of organic matter. These results are critical for more accurately estimating how intensive agricultural practices affect the carbon balance of cropping systems.

  19. Variability in organic carbon reactivity across lake residence time and trophic gradients

    NASA Astrophysics Data System (ADS)

    Evans, Chris D.; Futter, Martyn N.; Moldan, Filip; Valinia, Salar; Frogbrook, Zoe; Kothawala, Dolly N.

    2017-11-01

    The transport of dissolved organic carbon from land to ocean is a large dynamic component of the global carbon cycle. Inland waters are hotspots for organic matter turnover, via both biological and photochemical processes, and mediate carbon transfer between land, oceans and atmosphere. However, predicting dissolved organic carbon reactivity remains problematic. Here we present in situ dissolved organic carbon budget data from 82 predominantly European and North American water bodies with varying nutrient concentrations and water residence times ranging from one week to 700 years. We find that trophic status strongly regulates whether water bodies act as net dissolved organic carbon sources or sinks, and that rates of both dissolved organic carbon production and consumption can be predicted from water residence time. Our results suggest a dominant role of rapid light-driven removal in water bodies with a short water residence time, whereas in water bodies with longer residence times, slower biotic production and consumption processes are dominant and counterbalance one another. Eutrophication caused lakes to transition from sinks to sources of dissolved organic carbon. We conclude that rates and locations of dissolved organic carbon processing and associated CO2 emissions in inland waters may be misrepresented in global carbon budgets if temporal and spatial reactivity gradients are not accounted for.

  20. Effects Of Aging And Oxidation Of Palladized Iron Embedded In Activated Carbon On The Dechlorination Of 2-Chlorobiphenyl

    EPA Science Inventory

    Reactive activated carbon (RAC) impregnated with palladized iron has been developed to effectively treat polychlorinated biphenyls (PCBs) in the environment by coupling adsorption and dechlorination of PCBs. In this study, we addressed the dechlorination reactivity and capacity ...

  1. Effect Of Reaction Environments On The Reactivity Of PCB (2-Chlorobiphenyl) Over Activated Carbon Impregnated With Palladized Iron

    EPA Science Inventory

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-...

  2. Nitrogen activation of carbon-encapsulated zero-valent iron nanoparticles and influence of the activation temperature on heavy metals removal

    NASA Astrophysics Data System (ADS)

    Bonaiti, Stefania; Calderon, Blanca; Collina, Elena; Lasagni, Marina; Mezzanotte, Valeria; Aracil, Ignacio; Fullana, Andrés

    2017-05-01

    Nanoparticles of zero-valent iron (nZVI) represent a promising agent for environmental remediation. This is due to their core-shell structure which presents the characteristics of both metallic and oxidised iron, leading to sorption and reductive precipitation of metal ions. Nevertheless, nZVI application presents some limitations regarding their rapid oxidation and aggregation in the media which leads to the delivery of the ions after some hours (the “aging effect”). To address these issues, modifications of nZVI structure and synthesis methods have been developed in the last years. The aging problem was solved by using nZVI encapsulated inside carbon spheres (CE-nZVI), synthetized through Hydrothermal Carbonization (HTC). Results showed high heavy metals removal percentage. Furthermore, CE-nZVI were activated with nitrogen in order to increase the metallic iron content. The aim of this study was to test CE-nZVI post-treated with nitrogen at different temperatures in heavy metals removal, demonstrating that the influence of the temperature was negligible in nanoparticles removal efficiency.

  3. Carbonate concretions as a significant component of ancient marine carbon cycles: Insights from paired organic and inorganic carbon isotope analyses of a Cretaceous shale

    NASA Astrophysics Data System (ADS)

    Loyd, S. J.

    2014-12-01

    Carbonate concretions often occur within fine-grained, organic-rich sedimentary rocks. This association reflects the common production of diagenetic minerals through biologic cycling of organic matter. Chemical analysis of carbonate concretions provides the rare opportunity to explore ancient shallow diagenetic environments, which are inherently transient due to progressive burial but are an integral component of the marine carbon cycle. The late Cretaceous Holz Shale (~80 Ma) contains abundant calcite concretions that exhibit textural and geochemical characteristics indicative of relatively shallow formation (i.e., near the sediment-water interface). Sampled concretions contain between 5.4 and 9.8 wt.% total inorganic carbon (TIC), or ~45 and 82 wt.% CaCO3, compared to host shale values which average ~1.5 wt.% TIC. Organic carbon isotope compositions (δ13Corg) are relatively constant in host and concretion samples ranging from ­-26.3 to -24.0‰ (VPDB). Carbonate carbon isotope compositions (δ13Ccarb) range from -22.5 to -3.4‰, indicating a significant but not entirely organic source of carbon. Concretions of the lower Holz Shale exhibit considerably elevated δ13Ccarb values averaging -4.8‰, whereas upper Holz Shale concretions express an average δ13Ccarb value of -17.0‰. If the remaining carbonate for lower Holz Shale concretions is sourced from marine fluids and/or dissolved marine carbonate minerals (e.g., shells), a simple mass balance indicates that ~28% of concretion carbon was sourced from organic matter and ~72% from late Cretaceous marine inorganic carbon (with δ13C ~ +2.5‰). Upper Holz Shale calculations indicate a ~73% contribution from organic matter and a ~27% contribution from inorganic carbon. When normalized for carbonate, organic contents within the concretions are ~2-13 wt.% enriched compared to host contents. This potentially reflects the protective nature of cementation that acts to limit permeability and chemical destruction of

  4. High mobilization of arsenic, metals and rare earth elements in seepage waters driven by respiration of old allochthonous organic carbon.

    PubMed

    Weiske, Arndt; Schaller, Jörg; Hegewald, Tilo; Machill, Susanne; Werner, Ingo; Dudel, E Gert

    2013-12-01

    Metal and metalloid mobilization processes within seepage water are of major concern in a range of water reservoir systems. The mobilization process of arsenic and heavy metals within a dam and sediments of a drinking water reservoir was investigated. Principle component analysis (PCA) on time series data of seepage water showed a clear positive correlation of arsenic with iron and DOC (dissolved organic carbon), and a negative correlation with nitrate due to respiratory processes. A relationship of reductive metal and metalloid mobilization with respiration of old carbon was shown. The system is influenced by sediment layers as well as a recent DOC input from degraded ombrotrophic peatbogs in the catchment area. The isotopic composition ((12)C, (13)C and (14)C) of DOC is altered along the path from basin to seepage water, but no significant changes in structural parameters (LC-OCD-OND, FT-IR) could be seen. DIC (dissolved inorganic carbon) in seepage water partly originates from respiratory processes, and a higher relationship of it with sediment carbon than with the DOC inventory of infiltrating water was found. This study revealed the interaction of respiratory processes with metal and metalloid mobilization in sediment water flows. In contrast to the presumption that emerging DOC via respiratory processes mainly controls arsenic and metal mobilization it could be shown that the presence of aged carbon compounds is essential. The findings emphasize the importance of aged organic carbon for DOC, DIC, arsenic and metal turnover.

  5. Thermal conversion of an Fe₃O₄@metal-organic framework: a new method for an efficient Fe-Co/nanoporous carbon microwave absorbing material.

    PubMed

    Zhang, Xingmiao; Ji, Guangbin; Liu, Wei; Quan, Bin; Liang, Xiaohui; Shang, Chaomei; Cheng, Yan; Du, Youwei

    2015-08-14

    A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks.

  6. Limitation of Bacterial Growth by Dissolved Organic Matter and Iron in the Southern Ocean†

    PubMed Central

    Church, Matthew J.; Hutchins, David A.; Ducklow, Hugh W.

    2000-01-01

    The importance of resource limitation in controlling bacterial growth in the high-nutrient, low-chlorophyll (HNLC) region of the Southern Ocean was experimentally determined during February and March 1998. Organic- and inorganic-nutrient enrichment experiments were performed between 42°S and 55°S along 141°E. Bacterial abundance, mean cell volume, and [3H]thymidine and [3H]leucine incorporation were measured during 4- to 5-day incubations. Bacterial biomass, production, and rates of growth all responded to organic enrichments in three of the four experiments. These results indicate that bacterial growth was constrained primarily by the availability of dissolved organic matter. Bacterial growth in the subtropical front, subantarctic zone, and subantarctic front responded most favorably to additions of dissolved free amino acids or glucose plus ammonium. Bacterial growth in these regions may be limited by input of both organic matter and reduced nitrogen. Unlike similar experimental results in other HNLC regions (subarctic and equatorial Pacific), growth stimulation of bacteria in the Southern Ocean resulted in significant biomass accumulation, apparently by stimulating bacterial growth in excess of removal processes. Bacterial growth was relatively unchanged by additions of iron alone; however, additions of glucose plus iron resulted in substantial increases in rates of bacterial growth and biomass accumulation. These results imply that bacterial growth efficiency and nitrogen utilization may be partly constrained by iron availability in the HNLC Southern Ocean. PMID:10653704

  7. A linear solvation energy relationship model of organic chemical partitioning to dissolved organic carbon.

    PubMed

    Kipka, Undine; Di Toro, Dominic M

    2011-09-01

    Predicting the association of contaminants with both particulate and dissolved organic matter is critical in determining the fate and bioavailability of chemicals in environmental risk assessment. To date, the association of a contaminant to particulate organic matter is considered in many multimedia transport models, but the effect of dissolved organic matter is typically ignored due to a lack of either reliable models or experimental data. The partition coefficient to dissolved organic carbon (K(DOC)) may be used to estimate the fraction of a contaminant that is associated with dissolved organic matter. Models relating K(DOC) to the octanol-water partition coefficient (K(OW)) have not been successful for many types of dissolved organic carbon in the environment. Instead, linear solvation energy relationships are proposed to model the association of chemicals with dissolved organic matter. However, more chemically diverse K(DOC) data are needed to produce a more robust model. For humic acid dissolved organic carbon, the linear solvation energy relationship predicts log K(DOC) with a root mean square error of 0.43. Copyright © 2011 SETAC.

  8. Carbon mineralization in Laptev and East Siberian sea shelf and slope sediment

    NASA Astrophysics Data System (ADS)

    Brüchert, Volker; Bröder, Lisa; Sawicka, Joanna E.; Tesi, Tommaso; Joye, Samantha P.; Sun, Xiaole; Semiletov, Igor P.; Samarkin, Vladimir A.

    2018-01-01

    The Siberian Arctic Sea shelf and slope is a key region for the degradation of terrestrial organic material transported from the organic-carbon-rich permafrost regions of Siberia. We report on sediment carbon mineralization rates based on O2 microelectrode profiling; intact sediment core incubations; 35S-sulfate tracer experiments; pore-water dissolved inorganic carbon (DIC); δ13CDIC; and iron, manganese, and ammonium concentrations from 20 shelf and slope stations. This data set provides a spatial overview of sediment carbon mineralization rates and pathways over large parts of the outer Laptev and East Siberian Arctic shelf and slope and allows us to assess degradation rates and efficiency of carbon burial in these sediments. Rates of oxygen uptake and iron and manganese reduction were comparable to temperate shelf and slope environments, but bacterial sulfate reduction rates were comparatively low. In the topmost 50 cm of sediment, aerobic carbon mineralization dominated degradation and comprised on average 84 % of the depth-integrated carbon mineralization. Oxygen uptake rates and anaerobic carbon mineralization rates were higher in the eastern East Siberian Sea shelf compared to the Laptev Sea shelf. DIC / NH4+ ratios in pore waters and the stable carbon isotope composition of remineralized DIC indicated that the degraded organic matter on the Siberian shelf and slope was a mixture of marine and terrestrial organic matter. Based on dual end-member calculations, the terrestrial organic carbon contribution varied between 32 and 36 %, with a higher contribution in the Laptev Sea than in the East Siberian Sea. Extrapolation of the measured degradation rates using isotope end-member apportionment over the outer shelf of the Laptev and East Siberian seas suggests that about 16 Tg C yr-1 is respired in the outer shelf seafloor sediment. Of the organic matter buried below the oxygen penetration depth, between 0.6 and 1.3 Tg C yr-1 is degraded by anaerobic processes

  9. Effect of Reduced Flux Iron Ore Pellets on Removal of Impurities from Pig Iron During Induction Melting: A New Phenomenon

    NASA Astrophysics Data System (ADS)

    Dishwar, Raj Kumar; Agrawal, Shavi; Mandal, A. K.; Mahobia, G. S.; Sinha, O. P.

    2018-06-01

    The present work represents a comparative study of impurity removal (sulfur, phosphorus, and carbon) from pig iron melt by the addition of lime powder and reduced fluxed iron ore pellets separately in a 5-kg-capacity induction melting furnace. Two types of reduced flux pellets (80% and 50%) of similar basicity ( 3.06) were charged separately into the pool to obtain the different oxidizing atmospheres of the bath. Results showed that the rate of impurity removal increases up to 6 min of exposure time and decreases afterward. Only lime powder charging, sulfur ( 77%), and a small fraction of carbon were removed from pig iron. Phosphorous ( 41%), sulfur ( 53%), and carbon ( 96%) were removed simultaneously when 80% reduced fluxed pellets were used. The present study indicates that the optimum removal of impurities is possible by charging 80% reduced flux iron ore pellets from the pig iron melt.

  10. [Effects of climate change on forest soil organic carbon storage: a review].

    PubMed

    Zhou, Xiao-yu; Zhang, Cheng-yi; Guo, Guang-fen

    2010-07-01

    Forest soil organic carbon is an important component of global carbon cycle, and the changes of its accumulation and decomposition directly affect terrestrial ecosystem carbon storage and global carbon balance. Climate change would affect the photosynthesis of forest vegetation and the decomposition and transformation of forest soil organic carbon, and further, affect the storage and dynamics of organic carbon in forest soils. Temperature, precipitation, atmospheric CO2 concentration, and other climatic factors all have important influences on the forest soil organic carbon storage. Understanding the effects of climate change on this storage is helpful to the scientific management of forest carbon sink, and to the feasible options for climate change mitigation. This paper summarized the research progress about the distribution of organic carbon storage in forest soils, and the effects of elevated temperature, precipitation change, and elevated atmospheric CO2 concentration on this storage, with the further research subjects discussed.

  11. Rise of Earth's atmospheric oxygen controlled by efficient subduction of organic carbon

    NASA Astrophysics Data System (ADS)

    Duncan, Megan S.; Dasgupta, Rajdeep

    2017-04-01

    The net flux of carbon between the Earth's interior and exterior, which is critical for redox evolution and planetary habitability, relies heavily on the extent of carbon subduction. While the fate of carbonates during subduction has been studied, little is known about how organic carbon is transferred from the Earth's surface to the interior, although organic carbon sequestration is related to sources of oxygen in the surface environment. Here we use high pressure-temperature experiments to determine the capacity of rhyolitic melts to carry carbon under graphite-saturated conditions in a subducting slab, and thus to constrain the subduction efficiency of organic carbon, the remnants of life, through time. We use our experimental data and a thermodynamic model of CO2 dissolution in slab melts to quantify organic carbon mobility as a function of slab parameters. We show that the subduction of graphitized organic carbon, and the graphite and diamond formed by reduction of carbonates with depth, remained efficient even in ancient, hotter subduction zones where oxidized carbon subduction probably remained limited. We suggest that immobilization of organic carbon in subduction zones and deep sequestration in the mantle facilitated the rise (~103-5 fold) and maintenance of atmospheric oxygen since the Palaeoproterozoic and is causally linked to the Great Oxidation Event. Our modelling shows that episodic recycling of organic carbon before the Great Oxidation Event may also explain occasional whiffs of atmospheric oxygen observed in the Archaean.

  12. The chemistry of iron, aluminum, and dissolved organic material in three acidic, metal-enriched, mountain streams, as controlled by watershed and in-stream processes

    USGS Publications Warehouse

    McKnight, Diane M.; Bencala, Kenneth E.

    1990-01-01

    Several studies were conducted in three acidic, metal-enriched, mountain streams, and the results are discussed together in this paper to provide a synthesis of watershed and in-stream processes controlling Fe, Al, and DOC (dissolved organic carbon) concentrations. One of the streams, the Snake River, is naturally acidic; the other two, Peru Creek and St. Kevin Gulch, receive acid mine drainage. Analysis of stream water chemistry data for the acidic headwaters of the Snake River shows that some trace metal solutes (Al, Mn, Zn) are correlated with major ions, indicating that watershed processes control their concentrations. Once in the stream, biogeochemical processes can control transport if they occur over time scales comparable to those for hydrologic transport. Examples of the following in-stream reactions are presented: (1) photoreduction and dissolution of hydrous iron oxides in response to an experimental decrease in stream pH, (2) precipitation of Al at three stream confluences, and (3) sorption of dissolved organic material by hydrous iron and aluminum oxides in a stream confluence. The extent of these reactions is evaluated using conservative tracers and a transport model that includes storage in the substream zone.

  13. New developments and controversies in iron metabolism and iron chelation therapy

    PubMed Central

    Kontoghiorghe, Christina N; Kontoghiorghes, George J

    2016-01-01

    Iron is essential for all organisms including microbial, cancer and human cells. More than a quarter of the human population is affected by abnormalities of iron metabolism, mainly from iron deficiency and iron overload. Iron also plays an important role in free radical pathology and oxidative damage which is observed in almost all major diseases, cancer and ageing. New developments include the complete treatment of iron overload and reduction of morbidity and mortality in thalassaemia using deferiprone and selected deferiprone/deferoxamine combinations and also the use of the maltol iron complex in the treatment of iron deficiency anaemia. There is also a prospect of using deferiprone as a universal antioxidant in non iron overloaded diseases such as neurodegenerative, cardiovascular, renal, infectious diseases and cancer. New regulatory molecules of iron metabolism such as endogenous and dietary chelating molecules, hepcidin, mitochondrial ferritin and their role in health and disease is under evaluation. Similarly, new mechanisms of iron deposition, removal, distribution and toxicity have been identified using new techniques such as magnetic resonance imaging increasing our understanding of iron metabolic processes and the targeted treatment of related diseases. The uniform distribution of iron in iron overload between organs and within each organ is no longer valid. Several other controversies such as the toxicity impact of non transferrin bound iron vs injected iron, the excess levels of iron in tissues causing toxicity and the role of chelation on iron absorption need further investigation. Commercial interests of pharmaceutical companies and connections to leading journals are playing a crucial role in shaping worldwide medical opinion on drug sales and use but also patients’ therapeutic outcome and safety. Major controversies include the selection criteria and risk/benefit assessment in the use of deferasirox in thalassaemia and more so in idiopathic

  14. VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

    EPA Science Inventory

    Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  16. The placenta: the forgotten essential organ of iron transport

    PubMed Central

    Cao, Chang

    2016-01-01

    Optimal iron nutrition in utero is essential for development of the fetus and helps establish birth iron stores adequate to sustain growth in early infancy. In species with hemochorial placentas, such as humans and rodents, iron in the maternal circulation is transferred to the fetus by directly contacting placental syncytiotrophoblasts. Early kinetic studies provided valuable data on the initial uptake of maternal transferrin, an iron-binding protein, by the placenta. However, the remaining steps of iron trafficking across syncytiotrophoblasts and through the fetal endothelium into the fetal blood remain poorly characterized. Over the last 20 years, identification of transmembrane iron transporters and the iron regulatory hormone hepcidin has greatly expanded the knowledge of cellular iron transport and its regulation by systemic iron status. In addition, emerging human and animal data demonstrating comprised fetal iron stores in severe maternal iron deficiency challenge the classic dogma of exclusive fetal control over the transfer process and indicate that maternal and local signals may play a role in regulating this process. This review compiles current data on the kinetic, molecular, and regulatory aspects of placental iron transport and considers new questions and knowledge gaps raised by these advances. PMID:27261274

  17. Insights into nutrient assimilation and export in naturally iron-fertilized waters of the Southern Ocean from nitrogen, carbon and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Trull, Thomas W.; Davies, Diana; Casciotti, Karen

    2008-03-01

    The KErguelen Ocean and Plateau compared Study (KEOPS) documented enhanced iron input and phytoplankton biomass over the deep Kerguelen plateau in comparison to surrounding high-nutrient low-chlorophyll (HNLC) waters in late summer 2005. We examined the influence of this iron on nitrogen and carbon metabolism by the microbial food-web, by comparing samples from on-plateau and off-plateau. Suspended particulate organic carbon (POC) was ˜5 times more abundant on-plateau and exhibited greater POC/PON (˜6.5 vs. ˜5.5), δ13C-POC (˜-21.5 vs. ˜-24.5‰) and δ15N-PON (˜+2 vs. ˜0‰) than off-plateau. These differences arose in part from changes in ecosystem structure as demonstrated by size-fractionation (1, 5, 20, 55, 210, and 335-μm filters in series), which revealed large isotopic variations with size ( δ13C-POC ranged from -28 to -19‰ and δ15N-PON from -3 to +5‰) and greater abundances of 13C- and 15N-enriched large phytoplankton over the plateau. The 13C enrichment in POC reflected faster growth rates and greater draw-down of dissolved inorganic carbon over the plateau. Quantitative comparison to the δ15N of dissolved nitrate indicates that the δ15N-PON enrichment derived from increased assimilation of nitrate, corresponding to new production f-ratios of 0.7-0.9 on-plateau vs. 0.4-0.6 off-plateau. Results from a sparse set of free-drifting sediment trap samples suggest control of export by zooplankton grazing. The 15N and 18O enrichments in dissolved nitrate exhibited a 1:1 correlation, indicating that phytoplankton assimilation controls nitrate availability and only a relatively small amount of nitrate was regenerated by nitrification. The δ15N-NO 3 values yield indistinguishable isotopic fractionation factors on and off the plateau ( 15ɛ of 4-5‰). This suggests that variations in iron availability may not bias the interpretation of paleo-environmental 15N records, and leaves intact the view that higher sedimentary δ15N-PON values during the

  18. Research on dispose of wastewater from printing and dyeing by CWF combined with Iron-carbon Microelectrolysis

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Ye, Tingjin; Xu, Zizhen; Chen, Xiaogang; Shi, Liang; He, Lingfeng; Zhang, Yongli

    2018-03-01

    The carboxymethylchitosan cladding coal ash (CWF) was oxidized by the high temperature using coal ash and sodium carboxymethyl chitosan as raw and processed material for treatment of simulated and actual printing and dyeing wastewater over iron-carbon micro-electrolysis. The results on pH and CWF dosage for effluent dispose were evaluated by the decolorization rate, COD removal efficiency and turbidity removal rate. The experimental results indicated that the decolorization rate was first augmented and then declined with the increase of pH, and attained a peak value when pH was at 5-6. The COD removal efficiency augmented with the augmented of pH, and attained a peak value when pH was 6-7. The turbidity removal rate was first increases and afterwards decreases with the augment of pH, and attained a peak value when pH was at 5-6. Furthermore, the optimum pH for the treatment of simulated dyeing wastewater was 6 over iron-carbon micro-electrolysis, which indicated that the appropriate pH can promote the degradation of wastewater.

  19. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions.

    PubMed

    Zhang, Rui; Taddei, Phillip J; Fitzek, Markus M; Newhauser, Wayne D

    2010-05-07

    Heavy charged particle beam radiotherapy for cancer is of increasing interest because it delivers a highly conformal radiation dose to the target volume. Accurate knowledge of the range of a heavy charged particle beam after it penetrates a patient's body or other materials in the beam line is very important and is usually stated in terms of the water equivalent thickness (WET). However, methods of calculating WET for heavy charged particle beams are lacking. Our objective was to test several simple analytical formulas previously developed for proton beams for their ability to calculate WET values for materials exposed to beams of protons, helium, carbon and iron ions. Experimentally measured heavy charged particle beam ranges and WET values from an iterative numerical method were compared with the WET values calculated by the analytical formulas. In most cases, the deviations were within 1 mm. We conclude that the analytical formulas originally developed for proton beams can also be used to calculate WET values for helium, carbon and iron ion beams with good accuracy.

  20. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions

    PubMed Central

    Zhang, Rui; Taddei, Phillip J; Fitzek, Markus M; Newhauser, Wayne D

    2010-01-01

    Heavy charged particle beam radiotherapy for cancer is of increasing interest because it delivers a highly conformal radiation dose to the target volume. Accurate knowledge of the range of a heavy charged particle beam after it penetrates a patient’s body or other materials in the beam line is very important and is usually stated in terms of the water equivalent thickness (WET). However, methods of calculating WET for heavy charged particle beams are lacking. Our objective was to test several simple analytical formulas previously developed for proton beams for their ability to calculate WET values for materials exposed to beams of protons, helium, carbon and iron ions. Experimentally measured heavy charged particle beam ranges and WET values from an iterative numerical method were compared with the WET values calculated by the analytical formulas. Inmost cases, the deviations were within 1 mm. We conclude that the analytical formulas originally developed for proton beams can also be used to calculate WET values for helium, carbon and iron ion beams with good accuracy. PMID:20371908

  1. Removal of Trace Arsenic to Meet Drinking Water Standards Using Iron Oxide Coated Multiwall Carbon Nanotubes

    PubMed Central

    Ntim, Susana Addo; Mitra, Somenath

    2011-01-01

    This study presents the removal of trace level arsenic to meet drinking water standards using an iron oxide-multi-walled carbon nanotube (Fe-MWCNT) hybrid as a sorbent. The synthesis was facilitated by the high degree of nanotube functionalization using a microwave assisted process, and a controlled assembly of iron oxide was possible where the MWCNT served as an effective support for the oxide. In the final product, 11 % of the carbon atoms were attached to Fe. The Fe-MWCNT was effective in arsenic removal to below the drinking water standard levels of 10 µg L−1. The absorption capacity of the composite was 1723 µg g−1 and 189 µg g−1 for As(III) and As(V) respectively. The adsorption of As(V) on Fe-MWCNT was faster than that of As(III). The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models. PMID:21625394

  2. Toxicity of Nano-Zero Valent Iron to Freshwater and Marine Organisms

    PubMed Central

    Keller, Arturo A.; Garner, Kendra; Miller, Robert J.; Lenihan, Hunter S.

    2012-01-01

    We tested whether three commercial forms (uncoated, organic coating, and iron oxide coating) of nano zero-valent iron (nZVI) are toxic to freshwater and marine organisms, specifically three species of marine phytoplankton, one species of freshwater phytoplankton, and a freshwater zooplankton species (Daphnia magna), because these organisms may be exposed downstream of where nZVI is applied to remediate polluted soil. The aggregation and reactivity of the three types of nZVI varied considerably, which was reflected in their toxicity. Since levels of Fe2+ and Fe3+ increase as the nZVI react, we also evaluated their toxicity independently. All four phytoplankton species displayed decreasing population growth rates, and Daphnia magna showed increasing mortality, in response to increasing levels of nZVI, and to a lesser degree with increasing Fe2+ and Fe3+. All forms of nZVI aggregated in soil and water, especially in the presence of a high concentration of calcium ions in groundwater, thus reducing their transports through the environment. However, uncoated nZVI aggregated extremely rapidly, thus vastly reducing the probability of environmental transport and potential for toxicity. This information can be used to design a risk management strategy to arrest the transport of injected nZVI beyond the intended remediation area, by injecting inert calcium salts as a barrier to transport. PMID:22952836

  3. An improved method for quantitatively measuring the sequences of total organic carbon and black carbon in marine sediment cores

    NASA Astrophysics Data System (ADS)

    Xu, Xiaoming; Zhu, Qing; Zhou, Qianzhi; Liu, Jinzhong; Yuan, Jianping; Wang, Jianghai

    2018-01-01

    Understanding global carbon cycle is critical to uncover the mechanisms of global warming and remediate its adverse effects on human activities. Organic carbon in marine sediments is an indispensable part of the global carbon reservoir in global carbon cycling. Evaluating such a reservoir calls for quantitative studies of marine carbon burial, which closely depend on quantifying total organic carbon and black carbon in marine sediment cores and subsequently on obtaining their high-resolution temporal sequences. However, the conventional methods for detecting the contents of total organic carbon or black carbon cannot resolve the following specific difficulties, i.e., (1) a very limited amount of each subsample versus the diverse analytical items, (2) a low and fluctuating recovery rate of total organic carbon or black carbon versus the reproducibility of carbon data, and (3) a large number of subsamples versus the rapid batch measurements. In this work, (i) adopting the customized disposable ceramic crucibles with the microporecontrolled ability, (ii) developing self-made or customized facilities for the procedures of acidification and chemothermal oxidization, and (iii) optimizing procedures and carbon-sulfur analyzer, we have built a novel Wang-Xu-Yuan method (the WXY method) for measuring the contents of total organic carbon or black carbon in marine sediment cores, which includes the procedures of pretreatment, weighing, acidification, chemothermal oxidation and quantification; and can fully meet the requirements of establishing their highresolution temporal sequences, whatever in the recovery, experimental efficiency, accuracy and reliability of the measurements, and homogeneity of samples. In particular, the usage of disposable ceramic crucibles leads to evidently simplify the experimental scenario, which further results in the very high recovery rates for total organic carbon and black carbon. This new technique may provide a significant support for

  4. Iron-carbide cluster thermal dynamics for catalyzed carbon nanotube growth

    NASA Astrophysics Data System (ADS)

    Ding, Feng; Bolton, Kim; Rosén, Arne

    2004-07-01

    Molecular dynamics simulations have been used to study the thermal behavior of FeN-mCm clusters where N, the total number of atoms, extends up to 2400. Comparison of the computed results with experimental data shows that the simulations yield the correct trends for the liquid-solid region of the iron-carbide phase diagram as well as the correct dependence of cluster melting point as a function of cluster size. The calculation indicates that, when carbon nanotubes (CNTs) are grown on large (>3-4 nm) catalyst particles at low temperatures (<1200 K), the catalyst particles are not completely molten. It is argued that the mechanism of CNT growth under these conditions may be governed by the surface melting of the cluster. .

  5. Redox-controlled carbon and phosphorus burial: A mechanism for enhanced organic carbon sequestration during the PETM

    NASA Astrophysics Data System (ADS)

    Komar, Nemanja; Zeebe, Richard E.

    2017-12-01

    Geological records reveal a major perturbation in carbon cycling during the Paleocene-Eocene Thermal Maximum (PETM, ∼56 Ma), marked by global warming of more than 5 °C and a prominent negative carbon isotope excursion of at least 2.5‰ within the marine realm. The entire event lasted about 200,000 yr and was associated with a massive release of light carbon into the ocean-atmosphere system over several thousands of years. Here we focus on the terminal stage of the PETM, during which the ocean-atmosphere system rapidly recovered from the carbon cycle perturbation. We employ a carbon-cycle box model to examine the feedbacks between surface ocean biological production, carbon, oxygen, phosphorus, and carbonate chemistry during massive CO2 release events, such as the PETM. The model results indicate that the redox-controlled carbon-phosphorus feedback is capable of producing enhanced organic carbon sequestration during large carbon emission events. The locale of carbon oxidation (ocean vs. atmosphere) does not affect the amount of carbon sequestered. However, even though the model produces trends consistent with oxygen, excess accumulation rates of organic carbon (∼1700 Pg C during the recovery stage), export production and δ13 C data, it fails to reproduce the magnitude of change of sediment carbonate content and the CCD over-deepening during the recovery stage. The CCD and sediment carbonate content overshoot during the recovery stage is muted by a predicted increase in CaCO3 rain. Nonetheless, there are indications that the CaCO3 export remained relatively constant during the PETM. If this was indeed true, then an initial pulse of 3,000 Pg C followed by an additional, slow leak of 2,500 Pg C could have triggered an accelerated nutrient supply to the surface ocean instigating enhanced organic carbon export, consequently increasing organic carbon sequestration, resulting in an accelerated restoration of ocean-atmosphere biogeochemistry during the termination

  6. Young organic matter as a source of carbon dioxide outgassing from Amazonian rivers

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

    Mayorga, E; Aufdenkampe, A K; Masiello, C A

    2005-06-23

    Rivers are generally supersaturated with respect to carbon dioxide, resulting in large gas evasion fluxes that can be a significant component of regional net carbon budgets. Amazonian rivers were recently shown to outgas more than ten times the amount of carbon exported to the ocean in the form of total organic carbon or dissolved inorganic carbon. High carbon dioxide concentrations in rivers originate largely from in situ respiration of organic carbon, but little agreement exists about the sources or turnover times of this carbon. Here we present results of an extensive survey of the carbon isotope composition ({sup 13}C andmore » {sup 14}C) of dissolved inorganic carbon and three size-fractions of organic carbon across the Amazonian river system. We find that respiration of contemporary organic matter (less than 5 years old) originating on land and near rivers is the dominant source of excess carbon dioxide that drives outgassing in mid-size to large rivers, although we find that bulk organic carbon fractions transported by these rivers range from tens to thousands of years in age. We therefore suggest that a small, rapidly cycling pool of organic carbon is responsible for the large carbon fluxes from land to water to atmosphere in the humid tropics.« less

  7. Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides

    USGS Publications Warehouse

    Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian

    2013-01-01

    Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

  8. Examining organic carbon transport by the Orinoco River using SeaWiFS imagery

    NASA Astrophysics Data System (ADS)

    López, Ramón; Del Castillo, Carlos E.; Miller, Richard L.; Salisbury, Joseph; Wisser, Dominik

    2012-09-01

    The Orinoco River is the fourth largest in the world in terms of water discharge and organic carbon export to the ocean. River export of organic carbon is a key component of the carbon cycle and the global carbon budget. Here, we examined the seasonal transport of organic carbon by the Orinoco River into the eastern Caribbean using the conservative relationship of colored dissolved organic matter (CDOM) and dissolved organic carbon (DOC) in low salinity coastal waters influenced by river plumes. In situ measurements of CDOM absorption, DOC, and salinity were used to develop an empirical model for DOC concentration at the Orinoco River Plume. Satellite remote sensing reflectances were used with empirical models to determine DOC and Particulate organic carbon (POC) river transport. Our estimates of CDOM and DOC significantly correlated with in situ measurements and were within the expected ranges for the river. Total organic carbon transport by the Orinoco River during the period of 1998 to 2010 was 7.10 ×1012 g C y-1, from 5.29 × 1012 g C y-1 of DOC and 1.81 × 1012 g C y-1 of POC, representing ˜6% increase to previous published estimates. The variability in organic carbon transport responded to the seasonality in river flow more than to changes in organic carbon concentration in the river. Our results corroborate that is possible to estimate organic carbon transport using ocean color data at global scales. This is needed to reduce the uncertainties of land-ocean carbon fluxes.

  9. Iron-catalyzed synthesis of secondary amines: on the way to green reductive aminations.

    PubMed

    Stemmler, Tobias; Surkus, Annette-Enrika; Pohl, Marga-Martina; Junge, Kathrin; Beller, Matthias

    2014-11-01

    Amines represent important intermediates in chemical and biological processes. Herein, we describe the use of a nanostructured iron-based catalyst for the tandem reductive amination between nitroarenes and aldehydes using hydrogen as reductant. The nanostructured iron-catalyst is prepared by immobilization of an iron-phenanthroline complex onto a commercially available carbon support. In the reaction sequence a primary amine is formed in situ from the corresponding nitro compound. Reversible condensation with aldehydes forms the respective imines, which are finally reduced to the desired secondary amine. This synthesis of secondary amines is atom-economical and environmentally attractive using cheap and readily available organic compounds as starting materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Dehalogenation of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated, and Nanoscale Zerovalent Iron

    PubMed Central

    Zhuang, Yuan; Ahn, Sungwoo; Seyfferth, Angelia L.; Masue-Slowey, Yoko; Fendorf, Scott; Luthy, Richard G.

    2011-01-01

    Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zero-valent, which shows the difficulty with in-situ synthesis of a significant fraction of zero-valent iron in the micro-porous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogenous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI. PMID:21557574

  11. Iron Impregnated Activated Carbon as an Efficient Adsorbent for the Removal of Methylene Blue: Regeneration and Kinetics Studies

    PubMed Central

    Shah, Irfan; Adnan, Rohana; Wan Ngah, Wan Saime; Mohamed, Norita

    2015-01-01

    In this study, iron impregnated activated carbon (FeAC) was synthesized following an oxidation and iron impregnation of activated carbon (AC). Both the AC and FeAC were characterized by pHZPC and FTIR spectroscopy. The removal of Methylene Blue (MB) by AC and FeAC was examined under various experimental conditions. The FeAC showed up to 95% (higher than AC) MB removal in the pH range of 7–10. Although the reaction kinetics was pseudo–second order, the overall rate was controlled by a number of processes such as film diffusion, pore diffusion and intraparticle diffusion. The activation energy values for the MB uptake by AC and FeAC (21.79 and 14.82 kJ/mol, respectively) revealed a physisorption process. In the regeneration study, FeAC has shown consistently ≥ 90% MB removal even up to 10 repeated cycles. The reusable characteristic of the spent FeAC improved the practical use of activated carbon and can be a breakthrough for continuous flow system applications where it can work effectively without any significant reduction in its performance. PMID:25849291

  12. Controls on the molecular and carbon isotopic composition of organic matter deposited in a Kimmeridgian euxinic shelf sea: evidence for preservation of carbohydrates through sulfurisation

    NASA Astrophysics Data System (ADS)

    Van Kaam-Peters, Heidy M. E.; Schouten, Stefan; Köster, Jörgen; Sinninghe Damstè, Jaap S.

    1998-10-01

    , represented by so-called condensed sections, the flux of reactive iron was relatively small compared to the flux of reactive organic matter, which resulted in the formation of relatively small amounts of pyrite and an excess of hydrogen sulfide capable of reacting with fresh organic matter. Within the condensed sections, variations in the degree of sulfurisation of organic matter are probably due to both differences in primary production and differences in the supply of reactive iron. These findings demonstrate that climatic changes, probably driven by Milankovitch cycles, can have a large impact on the molecular and carbon isotopic compositions of the sedimentary organic matter in an otherwise relatively stable stratified basin. They also show that large amounts of labile carbohydrate carbon may be preserved through sulfurisation.

  13. Universal HPLC Detector for Hydrophilic Organic Compounds by Means of Total Organic Carbon Detection.

    PubMed

    Ohira, Shin-Ichi; Kaneda, Kyosuke; Matsuzaki, Toru; Mori, Shuta; Mori, Masanobu; Toda, Kei

    2018-06-05

    Most quantifications are achieved by comparison of the signals obtained with the sample to those from a standard. Thus, the purity and stability of the standard are key in chemical analysis. Furthermore, if an analyte standard cannot be obtained, quantification cannot be achieved, even if the chemical structures are identified by a qualification method (e.g., high-resolution mass spectrometry). Herein, we describe a universal and analyte standard-free detector for aqueous-eluent-based high-performance liquid chromatography. This universal carbon detector (UCD) was developed based on total organic carbon detection. Separated analytes were oxidized in-line and converted to carbon dioxide (CO 2 ). Generated CO 2 was transferred into the gas phase and collected into ultrapure water, which was followed by conductivity detection. The system can be applied as a HPLC detector that does not use an organic solvent as an eluent. The system can be calibrated with a primary standard of sodium bicarbonate for organic compounds. The universality and quantification were evaluated with organic compounds, including organic acids, sugars, and amino acids. Furthermore, the system was successfully applied to evaluation of the purity of formaldehyde in formalin solution, and determination of sugars in juices. The results show the universal carbon detector has good universality and can quantify many kinds of organic compounds with a single standard such as sodium bicarbonate.

  14. Energy of the Isolated Metastable Iron-Nickel FCC Nanocluster with a Carbon Atom in the Tetragonal Interstice.

    PubMed

    Bondarenko, Natalya V; Nedolya, Anatoliy V

    2017-12-01

    The energy of the isolated iron-nickel nanocluster was calculated by molecular mechanics method using Lennard-Jones potential. The cluster included a carbon atom that drifted from an inside octahedral interstice to a tetrahedral interstice in [Formula: see text] direction and after that in <222> direction to the surface. In addition, one of 14 iron atoms was replaced by a nickel atom, the position of which was changing during simulation.The energy of the nanocluster was estimated at the different interatomic distances. As a result of simulation, the optimal interatomic distances of Fe-Ni-C nanocluster was chosen for the simulation, in which height of the potential barrier was maximal and face-centered cubic (FCC) nanocluster was the most stable.It is shown that there were three main positions of a nickel atom that significantly affected nanocluster's energy.The calculation results indicated that position of the carbon atom in the octahedral interstice was more energetically favorable than tetrahedral interstice in the case of FCC nanocluster. On the other side, the potential barrier was smaller in the direction [Formula: see text] than in the direction <022>.This indicates that there are two ways for carbon atom to drift to the surface of the nanocluster.

  15. Assimilation of aged organic carbon in a glacial river food web

    NASA Astrophysics Data System (ADS)

    Fellman, J.; Hood, E. W.; Raymond, P. A.; Bozeman, M.; Hudson, J.; Arimitsu, M.

    2013-12-01

    Identifying the key sources of organic carbon supporting fish and invertebrate consumers is fundamental to our understanding of stream ecosystems. Recent laboratory bioassays highlight that aged organic carbon from glacier environments is highly bioavailable to stream bacteria relative to carbon originating from ice-free areas. However, there is little evidence suggesting that this aged, bioavailable organic carbon is also a key basal carbon source for stream metazoa. We used natural abundance of Δ14C, δ13C, and δ15N to determine if fish and invertebrate consumers are subsidized by aged organic carbon in a glacial river in southeast Alaska. We collected biofilm, leaf litter, three different species of macroinvertebrates, and resident juvenile salmonids from a reference stream and two sites (one site is directly downstream of the glacial outflow and one site is upstream of the tidal estuary) on the heavily glaciated Herbert River. Key producers, fish, and invertebrate consumers in the reference stream had carbon isotope values that ranged from -26 to -30‰ for δ13C and from -12 to 53‰ for Δ14C, reflecting a food web sustained mainly on contemporary primary production. In contrast, biofilm in the two glacial sites was highly Δ14C depleted (-203 to -215‰) relative to the reference site. Although biofilm may consist of both bacteria and benthic algae utilizing carbon depleted in Δ14C, δ13C values for biofilm (-24.1‰), dissolved inorganic carbon (-5.9‰), and dissolved organic carbon (-24.0‰) suggest that biofilm consist of bacteria sustained in part by glacier-derived, aged organic carbon. Invertebrate consumers (mean Δ14C of -80.5, mean δ13C of -26.5) and fish (mean Δ14C of -63.3, mean δ13C of -25.7) in the two glacial sites had carbon isotope values similar to biofilm. These results similarly show that aged organic carbon is incorporated into the metazoan food web. Overall, our findings indicate that continued watershed deglaciation and

  16. Isotopic, petrologic and biogeochemical investigations of banded iron-formations

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.; Kaufman, A. J.; Klein, C.; Studley, S. A.; Baur, M. E.; Walter, M. R.

    1986-01-01

    It is recognized that the first occurrence of banded iron-formations (BIFs) clearly predates biological oxygenation of the atmosphere-hydrosphere system and that their last occurrences extend beyond plausible dates of pervasive biological oxygenation. For this reason, and because enormous quantities of oxidizing power have been sequestered in them, it is widely thought that these massive, but enigmatic, sediments must encode information about the mechanism and timing of the rise of atmospheric O2. By coupling isotopic analyses of iron-formation carbonates with biogeochemical and petrologic investigations, we are studying (1) the mechanism of initial sedimentation of iron; (2) the role of iron in microbially mediated diagenetic processes in fresh iron-formation sediments; and (3) the logical integration of mechanisms of deposition with observed levels of banding. Thus far, it has been shown that (1) carbonates in BIFs of the Hamersley Group of Western Australia are isotopically inhomogenous; (2) the nature and pattern of isotopic ordering is not consistent with a metamorphic origin for the overall depletion of C-13 observed in the carbonates; (3) if biological, the origin of the C-13 depleted carbonate could be either respiratory or fermentative; (4) iron may have been precipitate d as Fe(3+), then reduced to Fe(2+) within the sediment; and (5) sedimentary biogeochemical systems may have been at least partially closed to mass transport of carbonate species.

  17. Alteration of the Copper-Binding Capacity of Iron-Rich Humic Colloids during Transport from Peatland to Marine Waters.

    PubMed

    Muller, François L L; Cuscov, Marco

    2017-03-21

    Blanket bogs contain vast amounts of Sphagnum-derived organic substances which can act as powerful chelators for dissolved iron and thus enhance its export to the coastal ocean. To investigate the variations in quantity and quality of these exports, adsorptive cathodic stripping voltammetry (CSV) was used to characterize the metal binding properties of molecular weight-fractionated dissolved organic matter (MW-fractionated DOM) in the catchment and coastal plume of a small peat-draining river over a seasonal cycle. Within the plume, both iron- and copper-binding organic ligands showed a linear, conservative distribution with increasing salinity, illustrating the high stability of peatland-derived humic substances (HS). Within the catchment, humic colloids lost up to 50% of their copper-binding capacity, expressed as a molar ratio to organic carbon, after residing for 1 week or more in the main reservoir of the catchment. Immediately downstream of the reservoir, the molar ratio [L 2 ]/[C org ], where L 2 was the second strongest copper-binding ligand, was 0.75 × 10 -4 when the reservoir residence time was 5 h but 0.34 × 10 -4 when it was 25 days. Residence time did not affect the carbon specific iron-binding capacity of the humic substances which was [L]/[C org ] = (0.80 ± 0.20) × 10 -2 . Our results suggest that the loss of copper-binding capacity with increasing residence time is caused by intracolloidal interactions between iron and HS during transit from peat soil to river mouth.

  18. Reducing iron deficiency anemia in Bolivian school children: calcium and iron combined versus iron supplementation alone.

    PubMed

    Miranda, Melissa; Olivares, Manuel; Brito, Alex; Pizarro, Fernando

    2014-01-01

    The aim of this study was to determine the effect of combined calcium and iron versus single iron supplementation on iron status in Bolivian schoolchildren. Children ages 6 to 10 y old (N = 195), were randomly assigned to receive either 700 mg Ca (as calcium carbonate) plus 30 mg Fe (as ferrous sulfate) (Ca + Fe group) or 30 mg Fe (as ferrous sulfate) (Fe group). The doses were administered daily, from Monday to Friday, between meals at school over 3 mo. Iron status was assessed at baseline and after intervention. Additionally, overall nutritional status was assessed by anthropometry and an estimation of dietary intake. At baseline, the prevalence of anemia in the Ca + Fe group and the Fe group were 15% and 21.5%, respectively. After 3 mo follow-up, the prevalence of iron deficiency anemia dropped significantly (P < 0.001) to 3% in both groups (χ(2) = NS). Iron dietary intake was within recommended levels, but calcium intake only covered 39% of the Recommended Daily Intake. Combined calcium and iron supplementation is equally as effective as single iron supplementation in reducing the prevalence of iron deficiency anemia in Bolivian school children. Copyright © 2014 Elsevier Inc. All rights reserved.

  19. Reductive transformation of 2,4-dinitrotoluene: roles of iron and natural organic matter

    USDA-ARS?s Scientific Manuscript database

    This study investigated the effects of redox-active and iron-coordinating functional groups within natural organic matter (NOM) on the electron transfer interactions between Fe(II) and 2,4-dinitrotoluene (2,4-DNT), an energetic residue often encountered in aqueous environments as a propellant compon...

  20. Preservation of overmature, ancient, sedimentary organic matter in carbonate concretions during outcrop weathering.

    PubMed

    Loyd, S J

    2017-01-01

    Concretions are preferentially cemented zones within sediments and sedimentary rocks. Cementation can result from relatively early diagenetic processes that include degradation of sedimentary organic compounds or methane as indicated by significantly 13 C-depleted or enriched carbon isotope compositions. As minerals fill pore space, reduced permeability may promote preservation of sediment components from degradation during subsequent diagenesis, burial heating and outcrop weathering. Discrete and macroscopic organic remains, macro and microfossils, magnetic grains, and sedimentary structures can be preferentially preserved within concretions. Here, Cretaceous carbonate concretions of the Holz Shale are shown to contain relatively high carbonate-free total organic carbon (TOC) contents (up to ~18.5 wt%) compared to the surrounding host rock (with <2.1 wt%). TOC increases with total inorganic carbon (TIC) content, a metric of the degree of cementation. Pyrite contents within concretions generally correlate with organic carbon contents. Concretion carbonate carbon isotope compositions (δ 13 C carb ) range from -22.5 to -3.4‰ (VPDB) and do not correlate strongly with TOC. Organic carbon isotope compositions (δ 13 C org ) of concretions and host rock are similar. Thermal maturity data indicate that both host and concretion organic matter are overmature and have evolved beyond the oil window maturity stage. Although the organic matter in general has experienced significant oxidative weathering, concretion interiors exhibit lower oxygen indices relative to the host. These results suggest that carbonate concretions can preferentially preserve overmature, ancient, sedimentary organic matter during outcrop weathering, despite evidence for organic matter degradation genetic mechanisms. As a result, concretions may provide an optimal proxy target for characterization of more primary organic carbon concentrations and chemical compositions. In addition, these findings

  1. Elevated pCO2 enhances bacterioplankton removal of organic carbon

    PubMed Central

    James, Anna K.; Passow, Uta; Brzezinski, Mark A.; Parsons, Rachel J.; Trapani, Jennifer N.; Carlson, Craig A.

    2017-01-01

    Factors that affect the removal of organic carbon by heterotrophic bacterioplankton can impact the rate and magnitude of organic carbon loss in the ocean through the conversion of a portion of consumed organic carbon to CO2. Through enhanced rates of consumption, surface bacterioplankton communities can also reduce the amount of dissolved organic carbon (DOC) available for export from the surface ocean. The present study investigated the direct effects of elevated pCO2 on bacterioplankton removal of several forms of DOC ranging from glucose to complex phytoplankton exudate and lysate, and naturally occurring DOC. Elevated pCO2 (1000–1500 ppm) enhanced both the rate and magnitude of organic carbon removal by bacterioplankton communities compared to low (pre-industrial and ambient) pCO2 (250 –~400 ppm). The increased removal was largely due to enhanced respiration, rather than enhanced production of bacterioplankton biomass. The results suggest that elevated pCO2 can increase DOC consumption and decrease bacterioplankton growth efficiency, ultimately decreasing the amount of DOC available for vertical export and increasing the production of CO2 in the surface ocean. PMID:28257422

  2. Modeling the effects of naturally occurring organic carbon on chlorinated ethene transport to a public supply well.

    PubMed

    Chapelle, Francis H; Kauffman, Leon J; Widdowson, Mark A

    2014-09-01

    The vulnerability of public supply wells to chlorinated ethene (CE) contamination in part depends on the availability of naturally occurring organic carbon to consume dissolved oxygen (DO) and initiate reductive dechlorination. This was quantified by building a mass balance model of the Kirkwood-Cohansey aquifer, which is widely used for public water supply in New Jersey. This model was built by telescoping a calibrated regional three-dimensional (3D) MODFLOW model to the approximate capture zone of a single public supply well that has a history of CE contamination. This local model was then used to compute a mass balance between dissolved organic carbon (DOC), particulate organic carbon (POC), and adsorbed organic carbon (AOC) that act as electron donors and DO, CEs, ferric iron, and sulfate that act as electron acceptors (EAs) using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. SEAM3D was constrained by varying concentrations of DO and DOC entering the aquifer via recharge, varying the bioavailable fraction of POC in aquifer sediments, and comparing observed and simulated vertical concentration profiles of DO and DOC. This procedure suggests that approximately 15% of the POC present in aquifer materials is readily bioavailable. Model simulations indicate that transport of perchloroethene (PCE) and its daughter products trichloroethene (TCE), cis-dichloroethene (cis-DCE), and vinyl chloride (VC) to the public supply well is highly sensitive to the assumed bioavailable fraction of POC, concentrations of DO entering the aquifer with recharge, and the position of simulated PCE source areas in the flow field. The results are less sensitive to assumed concentrations of DOC in aquifer recharge. The mass balance approach used in this study also indicates that hydrodynamic processes such as advective mixing, dispersion, and sorption account for a significant amount of the observed natural attenuation in this system. Published 2013. This article

  3. [Effects of tree species fine root decomposition on soil active organic carbon].

    PubMed

    Liu, Yan; Wang, Si-Long; Wang, Xiao-Wei; Yu, Xiao-Jun; Yang, Yue-Jun

    2007-03-01

    With incubation test, this paper studied the effects of fine root decomposition of Alnus cremastogyne, Cunninghamia lanceolata and Michelia macclurei on the content of soil active organic carbon at 9 degrees C , 14 degrees C , 24 degrees C and 28 degrees C. The results showed that the decomposition rate of fine root differed significantly with test tree species, which was decreased in the order of M. macclurei > A. cremastogyne > C. lanceolata. The decomposition rate was increased with increasing temperature, but declined with prolonged incubation time. Fine root source, incubation temperature, and incubation time all affected the contents of soil microbial biomass carbon and water-soluble organic carbon. The decomposition of fine root increased soil microbial biomass carbon and water-soluble organic carbon significantly, and the effect decreased in the order of M. macclurei > A. cremastogyne > C. lanceolata. Higher contents of soil microbial biomass carbon and water-soluble organic carbon were observed at medium temperature and middle incubation stage. Fine root decomposition had less effect on the content of soil readily oxidized organic carbon.

  4. Biological iron oxidation by Gallionella spp. in drinking water production under fully aerated conditions.

    PubMed

    de Vet, W W J M; Dinkla, I J T; Rietveld, L C; van Loosdrecht, M C M

    2011-11-01

    Iron oxidation under neutral conditions (pH 6.5-8) may be a homo- or heterogeneous chemically- or a biologically-mediated process. The chemical oxidation is supposed to outpace the biological process under slightly alkaline conditions (pH 7-8). The iron oxidation kinetics and growth of Gallionella spp. - obligatory chemolithotrophic iron oxidizers - were assessed in natural, organic carbon-containing water, in continuous lab-scale reactors and full-scale groundwater trickling filters in the Netherlands. From Gallionella cell numbers determined by qPCR, balances were made for all systems. The homogeneous chemical iron oxidation occurred in accordance with the literature, but was retarded by a low water temperature (13 °C). The contribution of the heterogeneous chemical oxidation was, despite the presence of freshly formed iron oxyhydroxides, much lower than in previous studies in ultrapure water. This could be caused by the adsorption of natural organic matter (NOM) on the iron oxide surfaces. In the oxygen-saturated natural water with a pH ranging from 6.5 to 7.7, Gallionella spp. grew uninhibited and biological iron oxidation was an important, and probably the dominant, process. Gallionella growth was not even inhibited in a full-scale filter after plate aeration. From this we conclude that Gallionella spp. can grow under neutral pH and fully aerated conditions when the chemical iron oxidation is retarded by low water temperature and inhibition of the autocatalytic iron oxidation. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    Iron chemistry and mineralogy in the sedimentary rocks provide a valuable tool for studying paleoenvironmental conditions due to the fact that iron atoms can take on either the +II or +III valence state under geological redox conditions. One method utilizing this redox chemistry is `iron speciation', a bulk chemical sequential extraction technique that maps proportions of iron species to redox conditions empirically calibrated from modern sediments. However, all Precambrian and many Phanerozoic rocks have experienced post-depositional processes; it is vital to explore their effects on iron mineralogy and speciation. We combined light and electron microscopy, magnetic microscopy, (synchrotron-based) microprobe x-ray spectroscopy, and rock magnetic measurements in order to deconvolve secondary overprints from primary phases and provide quantitative measurement of iron minerals. These techniques were applied to excellently-preserved shale and siltstone samples of the 1.4 Ga lower Belt Supergroup, Montana and Idaho, USA, spanning a metamorphic gradient from sub-biotite to garnet zone. Previously measured Silurian-Devonian shales, sandstones, and carbonates in Maine and Vermont, USA spanning from the chlorite to kyanite zone provided additional well-constrained, quantitative data for comparison and to extend our analysis. In all of the studied samples, pyrrhotite formation occurred at the sub-biotite or sub-chlorite zone. Pyrrhotite was interpreted to form from pyrite and/or other iron phases based on lithology; these reactions can affect the paleoredox proxy. Iron carbonates can also severely influence iron speciation results since they often form in anoxic pore fluids during diagenesis; textural analyses of the Belt Supergroup samples highlighted that iron-bearing carbonates were early diagenetic cements or later diagenetic overprints. The inclusion of iron from diagenetic minerals during iron speciation analyses will skew results by providing a view of pore

  6. Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.

    PubMed

    Shih, Yang-hsin; Li, Mei-syue

    2008-06-15

    Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals.

  7. Impact of hydrothermalism on the ocean iron cycle

    PubMed Central

    Resing, Joseph

    2016-01-01

    As the iron supplied from hydrothermalism is ultimately ventilated in the iron-limited Southern Ocean, it plays an important role in the ocean biological carbon pump. We deploy a set of focused sensitivity experiments with a state of the art global model of the ocean to examine the processes that regulate the lifetime of hydrothermal iron and the role of different ridge systems in governing the hydrothermal impact on the Southern Ocean biological carbon pump. Using GEOTRACES section data, we find that stabilization of hydrothermal iron is important in some, but not all regions. The impact on the Southern Ocean biological carbon pump is dominated by poorly explored southern ridge systems, highlighting the need for future exploration in this region. We find inter-basin differences in the isopycnal layer onto which hydrothermal Fe is supplied between the Atlantic and Pacific basins, which when combined with the inter-basin contrasts in oxidation kinetics suggests a muted influence of Atlantic ridges on the Southern Ocean biological carbon pump. Ultimately, we present a range of processes, operating at distinct scales, that must be better constrained to improve our understanding of how hydrothermalism affects the ocean cycling of iron and carbon. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035256

  8. Impact of hydrothermalism on the ocean iron cycle.

    PubMed

    Tagliabue, Alessandro; Resing, Joseph

    2016-11-28

    As the iron supplied from hydrothermalism is ultimately ventilated in the iron-limited Southern Ocean, it plays an important role in the ocean biological carbon pump. We deploy a set of focused sensitivity experiments with a state of the art global model of the ocean to examine the processes that regulate the lifetime of hydrothermal iron and the role of different ridge systems in governing the hydrothermal impact on the Southern Ocean biological carbon pump. Using GEOTRACES section data, we find that stabilization of hydrothermal iron is important in some, but not all regions. The impact on the Southern Ocean biological carbon pump is dominated by poorly explored southern ridge systems, highlighting the need for future exploration in this region. We find inter-basin differences in the isopycnal layer onto which hydrothermal Fe is supplied between the Atlantic and Pacific basins, which when combined with the inter-basin contrasts in oxidation kinetics suggests a muted influence of Atlantic ridges on the Southern Ocean biological carbon pump. Ultimately, we present a range of processes, operating at distinct scales, that must be better constrained to improve our understanding of how hydrothermalism affects the ocean cycling of iron and carbon.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).

  9. Removal of arsenic and iron removal from drinking water using coagulation and biological treatment.

    PubMed

    Pramanik, Biplob Kumar; Pramanik, Sagor Kumar; Suja, Fatihah

    2016-02-01

    Effects of biological activated carbon (BAC), biological aerated filter (BAF), alum coagulation and Moringa oleifera coagulation were investigated to remove iron and arsenic contaminants from drinking water. At an initial dose of 5 mg/L, the removal efficiency for arsenic and iron was 63% and 58% respectively using alum, and 47% and 41% respectively using Moringa oleifera. The removal of both contaminants increased with the increase in coagulant dose and decrease in pH. Biological processes were more effective in removing these contaminants than coagulation. Compared to BAF, BAC gave greater removal of both arsenic and iron, removing 85% and 74%, respectively. Longer contact time for both processes could reduce the greater concentration of arsenic and iron contaminants. The addition of coagulation (at 5 mg/L dosage) and a biological process (with 15 or 60 min contact time) could significantly increase removal efficiency, and the maximum removal was observed for the combination of alum and BAC treatment (60 min contact time), with 100% and 98.56% for arsenic and iron respectively. The reduction efficiency of arsenic and iron reduced with the increase in the concentration of dissolved organics in the feedwater due to the adsorption competition between organic molecules and heavy metals.

  10. Worldwide organic soil carbon and nitrogen data

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

    Zinke, P.J.; Stangenberger, A.G.; Post, W.M.

    The objective of the research presented in this package was to identify data that could be used to estimate the size of the soil organic carbon pool under relatively undisturbed soil conditions. A subset of the data can be used to estimate amounts of soil carbon storage at equilibrium with natural soil-forming factors. The magnitude of soil properties so defined is a resulting nonequilibrium values for carbon storage. Variation in these values is due to differences in local and geographic soil-forming factors. Therefore, information is included on location, soil nitrogen content, climate, and vegetation along with carbon density and variation.

  11. Chemical evolution of atmospheric organic carbon over multiple generations of oxidation

    NASA Astrophysics Data System (ADS)

    Isaacman-VanWertz, Gabriel; Massoli, Paola; O'Brien, Rachel; Lim, Christopher; Franklin, Jonathan P.; Moss, Joshua A.; Hunter, James F.; Nowak, John B.; Canagaratna, Manjula R.; Misztal, Pawel K.; Arata, Caleb; Roscioli, Joseph R.; Herndon, Scott T.; Onasch, Timothy B.; Lambe, Andrew T.; Jayne, John T.; Su, Luping; Knopf, Daniel A.; Goldstein, Allen H.; Worsnop, Douglas R.; Kroll, Jesse H.

    2018-02-01

    The evolution of atmospheric organic carbon as it undergoes oxidation has a controlling influence on concentrations of key atmospheric species, including particulate matter, ozone and oxidants. However, full characterization of organic carbon over hours to days of atmospheric processing has been stymied by its extreme chemical complexity. Here we study the multigenerational oxidation of α-pinene in the laboratory, characterizing products with several state-of-the-art analytical techniques. Although quantification of some early generation products remains elusive, full carbon closure is achieved (within measurement uncertainty) by the end of the experiments. These results provide new insights into the effects of oxidation on organic carbon properties (volatility, oxidation state and reactivity) and the atmospheric lifecycle of organic carbon. Following an initial period characterized by functionalization reactions and particle growth, fragmentation reactions dominate, forming smaller species. After approximately one day of atmospheric aging, most carbon is sequestered in two long-lived reservoirs—volatile oxidized gases and low-volatility particulate matter.

  12. Chemical evolution of atmospheric organic carbon over multiple generations of oxidation.

    PubMed

    Isaacman-VanWertz, Gabriel; Massoli, Paola; O'Brien, Rachel; Lim, Christopher; Franklin, Jonathan P; Moss, Joshua A; Hunter, James F; Nowak, John B; Canagaratna, Manjula R; Misztal, Pawel K; Arata, Caleb; Roscioli, Joseph R; Herndon, Scott T; Onasch, Timothy B; Lambe, Andrew T; Jayne, John T; Su, Luping; Knopf, Daniel A; Goldstein, Allen H; Worsnop, Douglas R; Kroll, Jesse H

    2018-04-01

    The evolution of atmospheric organic carbon as it undergoes oxidation has a controlling influence on concentrations of key atmospheric species, including particulate matter, ozone and oxidants. However, full characterization of organic carbon over hours to days of atmospheric processing has been stymied by its extreme chemical complexity. Here we study the multigenerational oxidation of α-pinene in the laboratory, characterizing products with several state-of-the-art analytical techniques. Although quantification of some early generation products remains elusive, full carbon closure is achieved (within measurement uncertainty) by the end of the experiments. These results provide new insights into the effects of oxidation on organic carbon properties (volatility, oxidation state and reactivity) and the atmospheric lifecycle of organic carbon. Following an initial period characterized by functionalization reactions and particle growth, fragmentation reactions dominate, forming smaller species. After approximately one day of atmospheric aging, most carbon is sequestered in two long-lived reservoirs-volatile oxidized gases and low-volatility particulate matter.

  13. A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

    NASA Astrophysics Data System (ADS)

    Workman, Michael J., Jr.

    focused ion beam tomography is modified and optimized for platinum-group metal free catalyst layers, facilitating direct observation of catalyst integration into catalyst layers. I present evidence supporting the hypothesis that atomically dispersed iron coordinated with nitrogen are the dominant active sites in these catalysts. Further, that the concentration of surface oxides in the carbon structure, which can be directly influenced by synthesis parameters, correlates with both the concentration of active sites in the material and with fuel cell performance. Catalyst performance is hindered by the addition of carbon nanotubes and by the presence of metallic iron. Evidence consistent with the catalytic active sites residing in the graphitic plane is also presented.

  14. Concentrations, loads, and yields of organic carbon in streams of agricultural watersheds

    USGS Publications Warehouse

    Kronholm, Scott; Capel, Paul

    2012-01-01

    Carbon is cycled to and from large reservoirs in the atmosphere, on land, and in the ocean. Movement of organic carbon from the terrestrial reservoir to the ocean plays an important role in the global cycling of carbon. The transition from natural to agricultural vegetation can change the storage and movement of organic carbon in and from a watershed. Samples were collected from 13 streams located in hydrologically and agriculturally diverse watersheds, to better understand the variability in the concentrations and loads of dissolved organic carbon (DOC) and particulate organic carbon (POC) in the streams, and the variability in watershed yields. The overall annual median concentrations of DOC and POC were 4.9 (range: 2.1–6.8) and 1.1 (range: 0.4–3.8) mg C L−1, respectively. The mean DOC watershed yield (± SE) was 25 ± 6.8 kg C ha−1 yr−1. The yields of DOC from these agricultural watersheds were not substantially different than the DOC yield from naturally vegetated watersheds in equivalent biomes, but were at the low end of the range for most biomes. Total organic carbon (DOC + POC) annually exported from the agricultural watersheds was found to average 0.03% of the organic carbon that is contained in the labile plant matter and top 1 m of soil in the watershed. Since the total organic carbon exported from agricultural watersheds is a relatively small portion of the sequestered carbon within the watershed, there is the great potential to store additional carbon in plants and soils of the watershed, offsetting some anthropogenic CO2 emissions.

  15. Reactive Iron and Iron-Reducing Bacteria in Louisiana Continental Shelf Sediments

    EPA Science Inventory

    The Mississippi and Atchafalaya Rivers release sediments containing 15 x 106 t of iron onto the Louisiana continental shelf (LCS) each year. Iron oxides reaching the seafloor may be utilized as electron acceptors by iron-reducing bacteria for organic matter oxidation or become r...

  16. Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon.

    PubMed

    Lewis, Ariel S; Huntington, Thomas G; Marvin-DiPasquale, Mark C; Amirbahman, Aria

    2016-05-01

    Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon

    USGS Publications Warehouse

    Lewis, Ariel S.; Huntington, Thomas G.; Marvin-DiPasquale, Mark C.; Amirbahman, Aria

    2016-01-01

    Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment.

  18. The Quest for Organic Carbon on Mars

    NASA Technical Reports Server (NTRS)

    Eigenbrode, Jennifer

    2011-01-01

    We are entering an era of Mars exploration in which organic carbon detection, characterization, and structural identification will be key to addressing some of the outstanding science objectives of the Mars Exploration Program. Success of these missions will depend on technical, scientific, and strategic elements--all of which are strongly determined based on terrestrial experience and knowledge of organic matter formation, concentration, and preservation. Analog studies including Precambrian sediments, modern endolithic communities, and experiments help us fine-tune these approaches, but we also need to expect the unexpected. This presentation will provide perspective on the challenges of detecting organic carbon on Mars, how we may achieve such detections with the in situ instruments, such as the SAM (Science Analysis at Mars) instrument suite onboard Curiosity, the rover for the 2011 Mars Science Laboratory mission.

  19. Soil Organic Carbon Loss: An Overlooked Factor in the Carbon Sequestration Potential of Enhanced Mineral Weathering

    NASA Astrophysics Data System (ADS)

    Dietzen, Christiana; Harrison, Robert

    2016-04-01

    Weathering of silicate minerals regulates the global carbon cycle on geologic timescales. Several authors have proposed that applying finely ground silicate minerals to soils, where organic acids would enhance the rate of weathering, could increase carbon uptake and mitigate anthropogenic CO2 emissions. Silicate minerals such as olivine could replace lime, which is commonly used to remediate soil acidification, thereby sequestering CO2 while achieving the same increase in soil pH. However, the effect of adding this material on soil organic matter, the largest terrestrial pool of carbon, has yet to be considered. Microbial biomass and respiration have been observed to increase with decreasing acidity, but it is unclear how long the effect lasts. If the addition of silicate minerals promotes the loss of soil organic carbon through decomposition, it could significantly reduce the efficiency of this process or even create a net carbon source. However, it is possible that this initial flush of microbial activity may be compensated for by additional organic matter inputs to soil pools due to increases in plant productivity under less acidic conditions. This study aimed to examine the effects of olivine amendments on soil CO2 flux. A liming treatment representative of typical agricultural practices was also included for comparison. Samples from two highly acidic soils were split into groups amended with olivine or lime and a control group. These samples were incubated at 22°C and constant soil moisture in jars with airtight septa lids. Gas samples were extracted periodically over the course of 2 months and change in headspace CO2 concentration was determined. The effects of enhanced mineral weathering on soil organic matter have yet to be addressed by those promoting this method of carbon sequestration. This project provides the first data on the potential effects of enhanced mineral weathering in the soil environment on soil organic carbon pools.

  20. The Use of Flow-Injection Analysis with Chemiluminescence Detection of Aqueous Ferrous Iron in Waters Containing High Concentrations of Organic Compounds

    PubMed Central

    Borman, Christopher J.; Sullivan, B. Patrick; Eggleston, Carrick M.; Colberg, Patricia J. S.

    2009-01-01

    An evaluation of flow-injection analysis with chemiluminescence detection (FIA-CL) to quantify Fe2+(aq) in freshwaters was performed. Iron-coordinating and/or iron-reducing compounds, dissolved organic matter (DOM), and samples from two natural water systems were used to amend standard solutions of Fe2+(aq). Slopes of the response curves from ferrous iron standards (1 – 100 nM) were compared to the response curves of iron standards containing the amendments. Results suggest that FIA-CL is not suitable for systems containing ascorbate, hydroxylamine, cysteine or DOM. Little or no change in sensitivity occurred in solutions of oxalate and glycine or in natural waters with little organic matter. PMID:22408532

  1. Carbon with hierarchical pores from carbonized metal-organic frameworks for lithium sulphur batteries.

    PubMed

    Xi, Kai; Cao, Shuai; Peng, Xiaoyu; Ducati, Caterina; Kumar, R Vasant; Cheetham, Anthony K

    2013-03-18

    This paper presents a novel method and rationale for utilizing carbonized MOFs for sulphur loading to fabricate cathode structures for lithium-sulphur batteries. Unique carbon materials with differing hierarchical pore structures were synthesized from four types of zinc-containing metal-organic frameworks (MOFs). It is found that cathode materials made from MOFs-derived carbons with higher mesopore (2-50 nm) volumes exhibit increased initial discharge capacities, whereas carbons with higher micropore (<2 nm) volumes lead to cathode materials with better cycle stability.

  2. Soil Organic Carbon assessment on two different forest management

    NASA Astrophysics Data System (ADS)

    Fernández Minguillón, Alex; Sauras Yera, Teresa; Vallejo Calzada, Ramón

    2017-04-01

    Soil Organic Carbon assessment on two different forest management. A.F. Minguillón1, T. Sauras1, V.R: Vallejo1. 1 Departamento de Biología Evolutiva, Ecología y Ciencias Ambientales, Universidad de Barcelona, Avenida Diagonal 643, 03080 Barcelona, Spain. Soils from arid and semiarid zones are characterized by a low organic matter content from scarce plant biomass and it has been proposed that these soils have a big capacity to carbon sequestration. According to IPCC ARS WG2 (2014) report and WG3 draft, increase carbon storage in terrestrial ecosystems has been identified such a potential tool for mitigation and adaptation to climate change. In ecological restoration context improve carbon sequestration is considered a management option with multiple benefits (win-win-win). Our work aims to analyze how the recently developed restoration techniques contributed to increases in terrestial ecosystem carbon storage. Two restoration techniques carried out in the last years have been evaluated. The study was carried out in 6 localities in Valencian Community (E Spain) and organic horizons of two different restoration techniques were evaluated; slash brush and thinning Aleppo pine stands. For each technique, carbon stock and its physical and chemical stability has been analysed. Preliminary results point out restoration zones acts as carbon sink due to (1) the relevant necromass input produced by slash brush increases C stock on the topsoil ;(2) Thinning increase carbon accumulation in vegetation.

  3. Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

    PubMed

    Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

    2015-01-01

    Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.

  4. Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide-natural organic matter complexes.

    PubMed

    Yan, Jinlong; Jiang, Tao; Yao, Ying; Wang, Jun; Cai, Yuanli; Green, Nelson W; Wei, Shiqiang

    2017-05-01

    The phosphorus (P) fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid (HA) complexes were analyzed using the ultrafiltration method in this study. With an initial P concentration of 20mg/L (I=0.01mol/L and pH=7), it was shown that the colloid (1kDa-0.45μm) component of P accounted for 10.6%, 11.6%, 6.5%, and 4.0% of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite (FH), goethite (GE), ferrihydrite-humic acid complex (FH-HA), goethite-humic acid complex (GE-HA), respectively. The <1kDa component of P was still the predominant fraction in the supernatant, and underestimated colloidal P accounted for 2.2%, 55.1%, 45.5%, and 38.7% of P adsorption onto the solid surface of FH, FH-HA, GE and GE-HA, respectively. Thus, the colloid P could not be neglected. Notably, it could be interpreted that Fe 3+ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant. And colloidal adsorbent particles co-existing in the supernatant were another important reason for it. Additionally, dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant. Ultimately, we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P, even when considering other contaminants such as organic pollutants, heavy metal ions, and arsenate at the sediment/soil-water interface in the real environment. Copyright © 2016. Published by Elsevier B.V.

  5. Application of Polypyrrole Multi-Walled Carbon Nanotube Composite Layer for Detection of Mercury, Lead and Iron Ions Using Surface Plasmon Resonance Technique

    PubMed Central

    Sadrolhosseini, Amir Reza; Noor, A. S. M.; Bahrami, Afarin; Lim, H. N.; Talib, Zainal Abidin; Mahdi, Mohd. Adzir

    2014-01-01

    Polypyrrole multi-walled carbon nanotube composite layers were used to modify the gold layer to measure heavy metal ions using the surface plasmon resonance technique. The new sensor was fabricated to detect trace amounts of mercury (Hg), lead (Pb), and iron (Fe) ions. In the present research, the sensitivity of a polypyrrole multi-walled carbon nanotube composite layer and a polypyrrole layer were compared. The application of polypyrrole multi-walled carbon nanotubes enhanced the sensitivity and accuracy of the sensor for detecting ions in an aqueous solution due to the binding of mercury, lead, and iron ions to the sensing layer. The Hg ion bonded to the sensing layer more strongly than did the Pb and Fe ions. The limitation of the sensor was calculated to be about 0.1 ppm, which produced an angle shift in the region of 0.3° to 0.6°. PMID:24733263

  6. Transport and cycling of iron and hydrogen peroxide in a freshwater stream: Influence of organic acids

    USGS Publications Warehouse

    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.

  7. Effects of sulfur in flooded paddy soils: Implications for iron chemistry and arsenic mobilization

    NASA Astrophysics Data System (ADS)

    Avancha, S.; Boye, K.

    2013-12-01

    In the Mekong delta in Cambodia, naturally occurring arsenic (amplified by erosion in the Himalaya Mountains) in paddy soils is mobilized during the seasonal flooding. As a consequence, rice grown on the flooded soils may take up arsenic and expose people eating the rice to this carcinogenic substance. Iron and sulfur both interact strongly with arsenic in paddy soils: iron oxides are strong adsorbents for arsenic in oxic conditions, and sulfur (in the form of sulfide) is a strong adsorbent under anoxic conditions. In the process of reductive dissolution of iron oxides, arsenic, which had been adsorbed to the iron oxides, is released. Therefore, higher levels of reduced iron (ferrous iron) will likely correlate with higher levels of mobilized arsenic. However, the mobilized arsenic may then co-precipitate with or adsorb to iron sulfides, which form under sulfate-reducing conditions and with the aid of certain microbes already present in the soil. In a batch experiment, we investigated how these processes correlate and which has the greatest influence on arsenic mobilization and potential plant availability. The experiment was designed to measure the effects of various sources of sulfur (dried rice straw, charred rice straw, and gypsum) on the iron and arsenic release in an arsenic-contaminated paddy soil from Cambodia under flooded conditions. The two types of rice straw were designed to introduce the same amount of organic sulfur (7.7 μg/g of soil), but different levels of available carbon, since carbon stimulates microbial activity in the soil. In comparison, two different levels of gypsum (calcium sulfate) were used, 7.7 and 34.65 μg/g of soil, to test the effect of directly available inorganic sulfate without carbon addition. The soil was flooded with a buffer solution at pH 7.07 in airtight serum vials and kept as a slurry on a shaker at 25 °C. We measured pH, alkalinity, ferrous iron, ferric iron, sulfide, sulfate, total iron, sulfur, and arsenic in the

  8. Variations in Soil Microbial Biomass Carbon and Soil Dissolved Organic Carbon in the Re-Vegetation of Hilly Slopes with Purple Soil.

    PubMed

    Yang, Ning; Zou, Dongsheng; Yang, Manyuan; Lin, Zhonggui

    2016-01-01

    Crust restoration is increasingly being done but we lack quantitative information on soil improvements. The study aimed to elucidate the dynamics involving soil microbial biomass carbon and soil dissolved organic carbon in the re-vegetation chronosequences of a hillslope land with purple soil in Hengyang, Hunan Province. The soil can cause serious disasters with both soil erosion and seasonal drought, and also becomes a typical representative of ecological disaster area in South China. Using the space-for-time method, we selected six typical sampling plots, designated as follows: grassplot community, meadow thicket community, frutex community, frutex and arbor community, arbor community, and top-level vegetation community. These plots were established to analyze the changes in soil microbial biomass carbon, soil microbial quotien, dissolved organic carbon, dissolved organic carbon/soil organic carbon, and soil basal respiration in 0-10, 10-20, and 20-40 cm soil layers. The relationships of these parameters with soils physic-chemical properties were also determined. The ecological environment of the 6 plant communities is similar and typical; they denoted six different successive stages of restoration on hillslopes with purple soils in Hengyang, Hunan Province. The soil microbial biomass carbon and soil basal respiration contents decreased with increasing soil depth but increased with re-vegetation. By contrast, soil microbial quotient increased with increasing soil depth and re-vegetation. From 0-10 cm soil layer to 20-40 cm soil layer, the dissolved organic carbon content decreased in different re-vegetation stages. In the process of re-vegetation, the dissolved organic carbon content increased in the 0-10 and 10-20 cm soil layers, whereas the dissolved organic carbon content decreased after an initial increase in the 20-40 cm soil layers. Meanwhile, dissolved organic carbon/soil organic carbon increased with increasing soil depth but decreased with re

  9. Variations in Soil Microbial Biomass Carbon and Soil Dissolved Organic Carbon in the Re-Vegetation of Hilly Slopes with Purple Soil

    PubMed Central

    Yang, Ning; Zou, Dongsheng; Yang, Manyuan; Lin, Zhonggui

    2016-01-01

    Crust restoration is increasingly being done but we lack quantitative information on soil improvements. The study aimed to elucidate the dynamics involving soil microbial biomass carbon and soil dissolved organic carbon in the re-vegetation chronosequences of a hillslope land with purple soil in Hengyang, Hunan Province. The soil can cause serious disasters with both soil erosion and seasonal drought, and also becomes a typical representative of ecological disaster area in South China. Using the space-for-time method, we selected six typical sampling plots, designated as follows: grassplot community, meadow thicket community, frutex community, frutex and arbor community, arbor community, and top-level vegetation community. These plots were established to analyze the changes in soil microbial biomass carbon, soil microbial quotien, dissolved organic carbon, dissolved organic carbon/soil organic carbon, and soil basal respiration in 0–10, 10–20, and 20–40 cm soil layers. The relationships of these parameters with soils physic-chemical properties were also determined. The ecological environment of the 6 plant communities is similar and typical; they denoted six different successive stages of restoration on hillslopes with purple soils in Hengyang, Hunan Province. The soil microbial biomass carbon and soil basal respiration contents decreased with increasing soil depth but increased with re-vegetation. By contrast, soil microbial quotient increased with increasing soil depth and re-vegetation. From 0–10 cm soil layer to 20–40 cm soil layer, the dissolved organic carbon content decreased in different re-vegetation stages. In the process of re-vegetation, the dissolved organic carbon content increased in the 0–10 and 10–20 cm soil layers, whereas the dissolved organic carbon content decreased after an initial increase in the 20–40 cm soil layers. Meanwhile, dissolved organic carbon/soil organic carbon increased with increasing soil depth but decreased

  10. A Raman Study of Carbonates and Organic Contents in Five CM Chondrites

    NASA Technical Reports Server (NTRS)

    Chan, Q. H. S.; Zolensky, M. E.; Bodnar, R. J.; Farley, C.; Cheung, J. C. H.

    2016-01-01

    Carbonates comprise the second most abundant class of carbon-bearing phases in carbonaceous chondrites after organic matter (approximately 2 wt.%), followed by other C-bearing phases such as diamond, silicon carbide, and graphite. Therefore, understanding the abundances of carbonates and the associated organic matter provide critical insight into the genesis of major carbonaceous components in chondritic materials. Carbonates in CM chondrites mostly occur as calcite (of varying composition) and dolomite. Properly performed, Raman spectroscopy provides a non-destructive technique for characterizing meteorite mineralogy and organic chemistry. It is sensitive to many carbonaceous phases, allows the differentiation of organic from inorganic materials, and the interpretation of their spatial distribution. Here, with the use of Raman spectroscopy, we determine the structure of the insoluble organic matter (IOM) in the matrix and carbonate phases in five CM chondrites: Jbilet Winselwan, Murchison, Nogoya, Santa Cruz, and Wisconsin Range (WIS) 91600, and interpret the relative timing of carbonate precipitation and the extent of the associated alteration events.

  11. Degradation of nitrobenzene-containing wastewater by carbon nanotubes immobilized nanoscale zerovalent iron

    NASA Astrophysics Data System (ADS)

    Jiao, Weizhou; Feng, Zhirong; Liu, Youzhi; Jiang, Huihui

    2016-07-01

    Nanoscaled zerovalent iron (NZVI)-multiwalled carbon nanotubes (CNTs) composite materials were prepared by in situ reduction of Fe2+ onto CNTs for nitrobenzene (NB) degradation. The morphologies and the composites of the prepared materials were characterized by SEM, TEM, and XRD. The results showed that the agglomeration of NZVI decreased with NZVI dispersed well onto the surfaces of CNTs, the particle size of NZVI on CNTs was about 20-50 nm. The BET surface areas of NZVI-CNTs was about 95.8 m2/g, which was 39 % higher than that of bare NZVI. For storage, the prepared NZVI-CNTs were concentrated into slurry and stored in situ as fresh slurry without drying. Contrast experiment results showed that the removal efficiency of NB by NZVI-CNTs fresh slurry was 30 % higher than that of vacuum-dried NZVI-CNTs, which indicates that storing in situ as fresh slurry can be an alternative strategy for nanoparticle storage. Batch experiment results showed that NB could be degraded to aniline by NZVI-CNTs rapidly, and the appropriate pH can be conducted at a relatively wide range from 2.0 to 9.0. The optimum mass ratio of iron-carbon was 1:1, and removal efficiency of NB by NZVI-CNTs with this mass ratio can achieve 100 % within 1 min. The degradation process of NB to intermediates was accelerated significantly by NZVI-CNTs, however, there was still a long term for the intermediates to transfer completely into the final product of aniline. The existence of CNTs can improve the formation of aniline through accelerating the electron transfer by forming microscopic galvanic cells with NZVI.

  12. Dual-peak electrogenerated chemiluminescence of carbon dots for iron ions detection.

    PubMed

    Zhang, Pengjia; Xue, Zhenjie; Luo, Dan; Yu, Wei; Guo, Zhihui; Wang, Tie

    2014-06-17

    Carbon dots (CDs) have rigorously been investigated on their unique fluorescent properties but rarely their electrogenerated chemiluminescence (ECL) behavior. We are here to report a dual-peak ECL system of CDs, one at -2.84 V (ECL-1) and the other at -1.71 V (ECL-2) during the cyclic sweep between -3.0 and 3.0 V at scan rate of 0.2 V s(-1) in 0.1 M tetrabutyl ammonium bromide (TBAB) ethanol solution, which is more efficiency to distinguish metallic ions than single-peak ECL. The electron transfer reaction between individual electrochemically reduced nanocrystal species and coreactants led to ECL-1, in which the electron injected to the conduction band of CDs in the cathodic process. Ion annihilation reactions induced direct formation of exciplexes that produced another ECL signal, ECL-2. ECL-1 showed higher sensitivity to the surrounding environment than ECL-2 and thus was used for ECL detection of metallic ions. Herein, we can serve as an internal standard method to detect iron ions. A linear relationship of the intensity ratio R of ECL-1 and ECL-2 to iron ions was observed in the concentration extending from 5 × 10(-6) to 8 × 10(-5) M with a detection limit of 7 × 10(-7) M.

  13. Glutathione, Glutaredoxins, and Iron.

    PubMed

    Berndt, Carsten; Lillig, Christopher Horst

    2017-11-20

    Glutathione (GSH) is the most abundant cellular low-molecular-weight thiol in the majority of organisms in all kingdoms of life. Therefore, functions of GSH and disturbed regulation of its concentration are associated with numerous physiological and pathological situations. Recent Advances: The function of GSH as redox buffer or antioxidant is increasingly being questioned. New functions, especially functions connected to the cellular iron homeostasis, were elucidated. Via the formation of iron complexes, GSH is an important player in all aspects of iron metabolism: sensing and regulation of iron levels, iron trafficking, and biosynthesis of iron cofactors. The variety of GSH coordinated iron complexes and their functions with a special focus on FeS-glutaredoxins are summarized in this review. Interestingly, GSH analogues that function as major low-molecular-weight thiols in organisms lacking GSH resemble the functions in iron homeostasis. Since these iron-related functions are most likely also connected to thiol redox chemistry, it is difficult to distinguish between mechanisms related to either redox or iron metabolisms. The ability of GSH to coordinate iron in different complexes with or without proteins needs further investigation. The discovery of new Fe-GSH complexes and their physiological functions will significantly advance our understanding of cellular iron homeostasis. Antioxid. Redox Signal. 27, 1235-1251.

  14. Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

    NASA Technical Reports Server (NTRS)

    Mannino, Antonio; Harvey, H. Rodger

    2003-01-01

    Analysis of high-molecular-weight dissolved organic matter (DOM) from two estuaries in the northwest Atlantic Ocean reveals that black carbon (BC) is a significant component of previously uncharacterized DOM, suggesting that river-estuary systems are important exporters of recalcitrant dissolved organic carbon to the ocean.

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

    DOE Data Explorer

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

    2018-06-13

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

  16. Input related microbial carbon dynamic of soil organic matter in particle size fractions

    NASA Astrophysics Data System (ADS)

    Gude, A.; Kandeler, E.; Gleixner, G.

    2012-04-01

    This paper investigated the flow of carbon into different groups of soil microorganisms isolated from different particle size fractions. Two agricultural sites of contrasting organic matter input were compared. Both soils had been submitted to vegetation change from C3 (Rye/Wheat) to C4 (Maize) plants, 25 and 45 years ago. Soil carbon was separated into one fast-degrading particulate organic matter fraction (POM) and one slow-degrading organo-mineral fraction (OMF). The structure of the soil microbial community were investigated using phospholipid fatty acids (PLFA), and turnover of single PLFAs was calculated from the changes in their 13C content. Soil enzyme activities involved in the degradation of carbohydrates was determined using fluorogenic MUF (methyl-umbelliferryl phosphate) substrates. We found that fresh organic matter input drives soil organic matter dynamic. Higher annual input of fresh organic matter resulted in a higher amount of fungal biomass in the POM-fraction and shorter mean residence times. Fungal activity therefore seems essential for the decomposition and incorporation of organic matter input into the soil. As a consequence, limited litter input changed especially the fungal community favouring arbuscular mycorrhizal fungi. Altogether, supply and availability of fresh plant carbon changed the distribution of microbial biomass, the microbial community structure and enzyme activities and resulted in different priming of soil organic matter. Most interestingly we found that only at low input the OMF fraction had significantly higher calculated MRT for Gram-positive and Gram-negative bacteria suggesting high recycling of soil carbon or the use of other carbon sources. But on average all microbial groups had nearly similar carbon uptake rates in all fractions and both soils, which contrasted the turnover times of bulk carbon. Hereby the microbial carbon turnover was always faster than the soil organic carbon turnover and higher carbon input

  17. [Iron from soil to plant products].

    PubMed

    Briat, Jean-François

    2005-11-01

    As an essential mineral, iron plays an important role in fundamental biological processes such as photosynthesis, respiration, nitrogen fixation and assimilation, and DNA synthesis. Iron is also a co-factor of many enzymes involved in the synthesis of plant hormones. The latter are involved in many pathways controling plant development or adaptative responses to environmental conditions. Iron reactivity with oxygen leads to its insolubility (responsible for deficiency) and potential toxicity, and complicates iron use by aerobic organisms. If plants lacked an active root system with which to acquire iron from the soil, most would experience iron deficiency and show physiological changes. In contrast, an excess of soluble iron, which can occur in flooded acidic soils, can lead to ferrous iron toxicity due to iron reactivity with reduced forms of oxygen and subsequent free radical production. An optimal iron concentration is thus required for a plant to grow and develop normally. This concentration depends on multiple regulatory mechanisms controlling iron uptake from soil by the roots, as well as iron transport and distribution to the various plant organs. Optimized seed iron content is a major biotechnological challenge identified by the World Health Organization, and it is therefore crucial to understand the underlying mechanisms. Iron delivery to seeds is tightly controlled, and depends on the nature of iron speciation in specific chelates, and their transport.

  18. Organic carbon content of marine aerosols collected on Bermuda

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

    Hoffman, E.J.; Duce, R.A.

    1974-01-01

    The concentration of total organic carbon in marine aerosols collected from a 20-m tower on the Southwest Coast of Bermuda ranged from 0.15 to 0.47 microgram/M/sup 3/ STP under onshore wind conditions. The mass of the organic carbon ranged from 1 to 19% of the mass of sea salt in the particles in Bermuda, and the percentage decreased with increasing salt content.

  19. Fossil organic carbon in wastewater and its fate in treatment plants.

    PubMed

    Law, Yingyu; Jacobsen, Geraldine E; Smith, Andrew M; Yuan, Zhiguo; Lant, Paul

    2013-09-15

    This study reports the presence of fossil organic carbon in wastewater and its fate in wastewater treatment plants. The findings pinpoint the inaccuracy of current greenhouse gas accounting guidelines which defines all organic carbon in wastewater to be of biogenic origin. Stable and radiocarbon isotopes ((13)C and (14)C) were measured throughout the process train in four municipal wastewater treatment plants equipped with secondary activated sludge treatment. Isotopic mass balance analyses indicate that 4-14% of influent total organic carbon (TOC) is of fossil origin with concentrations between 6 and 35 mg/L; 88-98% of this is removed from the wastewater. The TOC mass balance analysis suggests that 39-65% of the fossil organic carbon from the influent is incorporated into the activated sludge through adsorption or from cell assimilation while 29-50% is likely transformed to carbon dioxide (CO2) during secondary treatment. The fossil organic carbon fraction in the sludge undergoes further biodegradation during anaerobic digestion with a 12% decrease in mass. 1.4-6.3% of the influent TOC consists of both biogenic and fossil carbon is estimated to be emitted as fossil CO2 from activated sludge treatment alone. The results suggest that current greenhouse gas accounting guidelines, which assume that all CO2 emission from wastewater is biogenic may lead to underestimation of emissions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

    PubMed Central

    Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

    2016-01-01

    Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications. PMID:27471193

  1. The effect of antacids on the absorption of simultaneously ingested iron.

    PubMed

    O'Neil-Cutting, M A; Crosby, W H

    1986-03-21

    Most discussions of iron therapy include a statement about the ineffectiveness of iron ingested simultaneously with antacids. This study was designed to determine whether or not antacids inhibit iron absorption. A small-dose iron tolerance test was used to compare absorption of iron with and without various antacids. Liquid antacid containing aluminum hydroxide and magnesium hydroxide did not significantly decrease iron absorption. Sodium bicarbonate and calcium carbonate caused the plasma iron increase to be 50% and 67% less than the control values, respectively. However, when calcium carbonate was present in a multivitamin-plus-minerals tablet, the plasma iron change was not significantly different from control trials. Presumably the competitive binding of iron by ascorbic acid in the vitamin pill allowed uninhibited absorption of the iron. Our results suggest that certain antacids may be combined with iron therapy without reducing the efficacy of the iron.

  2. Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

    NASA Technical Reports Server (NTRS)

    Williford, Kenneth H.; Ushikubo, Takayuki; Lepot, Kevin; Hallmann, Christian; Spicuzza, Michael J.; Eigenbrode, Jennifer L.; Summons, Roger E.; Valley, John W.

    2011-01-01

    Archean OM suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, approximately 2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, approximately 2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, approximately 2.6 Ga), and SV1 (n=1; Tumbiana Fm, approximately 2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, delta C-13 varies between -53.1 and -28.3 % and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for gradients of oxidation with depth in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of previously reported Archean OM will be discussed.

  3. Microbial iron oxidation in the Arctic tundra and its implications for biogeochemical cycling.

    PubMed

    Emerson, David; Scott, Jarrod J; Benes, Joshua; Bowden, William B

    2015-12-01

    The role that neutrophilic iron-oxidizing bacteria play in the Arctic tundra is unknown. This study surveyed chemosynthetic iron-oxidizing communities at the North Slope of Alaska near Toolik Field Station (TFS) at Toolik Lake (lat 68.63, long -149.60). Microbial iron mats were common in submerged habitats with stationary or slowly flowing water, and their greatest areal extent is in coating plant stems and sediments in wet sedge meadows. Some Fe-oxidizing bacteria (FeOB) produce easily recognized sheath or stalk morphotypes that were present and dominant in all the mats we observed. The cool water temperatures (9 to 11°C) and reduced pH (5.0 to 6.6) at all sites kinetically favor microbial iron oxidation. A microbial survey of five sites based on 16S rRNA genes found a predominance of Proteobacteria, with Betaproteobacteria and members of the family Comamonadaceae being the most prevalent operational taxonomic units (OTUs). In relative abundance, clades of lithotrophic FeOB composed 5 to 10% of the communities. OTUs related to cyanobacteria and chloroplasts accounted for 3 to 25% of the communities. Oxygen profiles showed evidence for oxygenic photosynthesis at the surface of some mats, indicating the coexistence of photosynthetic and FeOB populations. The relative abundance of OTUs belonging to putative Fe-reducing bacteria (FeRB) averaged around 11% in the sampled iron mats. Mats incubated anaerobically with 10 mM acetate rapidly initiated Fe reduction, indicating that active iron cycling is likely. The prevalence of iron mats on the tundra might impact the carbon cycle through lithoautotrophic chemosynthesis, anaerobic respiration of organic carbon coupled to iron reduction, and the suppression of methanogenesis, and it potentially influences phosphorus dynamics through the adsorption of phosphorus to iron oxides. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  4. Microbial Iron Oxidation in the Arctic Tundra and Its Implications for Biogeochemical Cycling

    PubMed Central

    Scott, Jarrod J.; Benes, Joshua; Bowden, William B.

    2015-01-01

    The role that neutrophilic iron-oxidizing bacteria play in the Arctic tundra is unknown. This study surveyed chemosynthetic iron-oxidizing communities at the North Slope of Alaska near Toolik Field Station (TFS) at Toolik Lake (lat 68.63, long −149.60). Microbial iron mats were common in submerged habitats with stationary or slowly flowing water, and their greatest areal extent is in coating plant stems and sediments in wet sedge meadows. Some Fe-oxidizing bacteria (FeOB) produce easily recognized sheath or stalk morphotypes that were present and dominant in all the mats we observed. The cool water temperatures (9 to 11°C) and reduced pH (5.0 to 6.6) at all sites kinetically favor microbial iron oxidation. A microbial survey of five sites based on 16S rRNA genes found a predominance of Proteobacteria, with Betaproteobacteria and members of the family Comamonadaceae being the most prevalent operational taxonomic units (OTUs). In relative abundance, clades of lithotrophic FeOB composed 5 to 10% of the communities. OTUs related to cyanobacteria and chloroplasts accounted for 3 to 25% of the communities. Oxygen profiles showed evidence for oxygenic photosynthesis at the surface of some mats, indicating the coexistence of photosynthetic and FeOB populations. The relative abundance of OTUs belonging to putative Fe-reducing bacteria (FeRB) averaged around 11% in the sampled iron mats. Mats incubated anaerobically with 10 mM acetate rapidly initiated Fe reduction, indicating that active iron cycling is likely. The prevalence of iron mats on the tundra might impact the carbon cycle through lithoautotrophic chemosynthesis, anaerobic respiration of organic carbon coupled to iron reduction, and the suppression of methanogenesis, and it potentially influences phosphorus dynamics through the adsorption of phosphorus to iron oxides. PMID:26386054

  5. Carbon isotopic studies of organic matter in Precambrian rocks.

    NASA Technical Reports Server (NTRS)

    Oehler, D. Z.; Schopf, J. W.; Kvenvolden, K. A.

    1972-01-01

    A survey has been undertaken of the carbon composition of the total organic fraction of a suite of Precambrian sediments to detect isotopic trends possibly correlative with early evolutionary events. Early Precambrian cherts of the Fig Tree and upper and middle Onverwacht groups of South Africa were examined for this purpose. Reduced carbon in these cherts was found to be isotopically similar to photosynthetically produced organic matter of younger geological age. Reduced carbon in lower Onverwacht cherts was found to be anomalously heavy; it is suggested that this discontinuity may reflect a major event in biological evolution.

  6. Effects of humus quality on the spatial iron distribution in hydromorphic topsoils

    NASA Astrophysics Data System (ADS)

    Ringer, Marianna; Jakab, Gergely; Sipos, Péter; Karlik, Máté; Balázs, Réka B.; Zihné Perényi, Katalin; Szalai, Zoltán

    2017-04-01

    Soil organic matter (SOM) has an effect on the fertility, nutrition and buffer function of the soils. As a reservoir of carbon SOM plays an important role in the global carbon cycle. Hydromorphic soils (generally located in low-land areas with a high groundwater table level) are characterized by accumulation of great amounts of humic substances due to inhibited decomposition of SOM. Long-term water saturation has a significant effect on the evolution of humic substances, causing particular traits in the SOM quality of waterlogged soils. In our study we investigated a wetland with a maximum of 1.5 m vertical difference in topography. This way the water-controlled processes of soil development, including the transformations of SOM, follow the patterns of the centimeter-scale variations of the micro-relief. Our aim was to find correlations between the effects of hydromorphy (driven by micro-relief) and the quantitative and qualitative characteristics of SOM. Considering iron distribution among the profile can unfold further interactions within the system of groundwater, SOM and iron. Samples were collected from the upper 20 cm and from the deepest part of the solum. Total soil organic carbon (SOC) and nitrogen content were determined by non-dispersive infrared spectroscopy. Humic substances were qualified by UV-Vis spectrometry, based on specific spectral absorbances (E4/E6, E2/E3). The determination of total iron content was carried out via X-ray fluorescence spectroscopy. Selective dissolution method and atomic absorption spectrometry were performed to measure free iron content. Particle size distribution was determined by laser diffraction. Our results show that intensive SOM accumulation has taken place in the studied area. High values of SOC were found even in the depth of 50-60 cm. The high proportion of C/N suggests that the aerobic decomposition of SOM is significantly inhibited. In the lower spots greater amount and higher polimerisation degree was measured

  7. Study the properties of activated carbon and oxyhydroxide aluminum as sorbents for removal humic substances from natural waters

    NASA Astrophysics Data System (ADS)

    Shiyan, L. N.; Machekhina, K. I.; Gryaznova, E. N.

    2016-02-01

    The present work relates to the problem of high-quality drinking water supply using processes of adsorption on activated carbon and aluminum oxyhydroxide for removal humic- type organic substances. Also the paper reports on sorbtion properties of the activeted carbon Norit SA UF and oxyhydroxide aluminum for removal humic substances. It was found out that the maximum adsorption capacity of activated carbon to organic substances is equal to 0.25 mg/mg and aluminum oxyhydroxide is equal to 0.3 mg/mg. It is shown that the maximum adsorption capacity of activated carbon Norit SA UF to iron (III) ions is equal to 0.0045 mg/mg and to silicon ions is equal to 0.024 mg/mg. Consequently, the aluminum oxyhydroxide has better adsorption characteristics in comparison with the activated carbon for removal of humic substances, iron and silicon ions. It is associated with the fact that activated carbon has a large adsorption surface, and this is due to its porous structure, but not all molecules can enter into these pores. Therefore, the fibrous structure of aluminum oxyhydroxide promotes better sorption capacity. The presented results suggest that activated carbon Norit SA UF and aluminum oxyhydroxide can be used as sorbents for removal humic substances or other organic substances from groundwater and natural waters.

  8. Nanophase Iron Oxides as an Ultraviolet Sunscreen for Ancient Photosynthetic Microbes: A Possible Link Between Early Organisms, Banded-Iron Formations, and the Oxygenation of the Atmosphere

    NASA Technical Reports Server (NTRS)

    Bishop, Janice L.; Rothschild, Lynn J.; Rothschild, Lynn J.; Rogoff, Dana A.

    2006-01-01

    We propose that nanophase iron oxide-bearing materials provided important niches for ancient photosynthetic microbes on the early Earth that ultimately led to the oxygenation of the Earth s atmosphere and the formation of iron oxide deposits. Atmospheric oxygen and ozone attenuate UV radiation on the Earth today providing substantial protection for photosynthetic organisms. With ultraviolet radiation fluxes likely to have been even higher on the early Earth than today, accessing solar radiation was particularly risky for early organisms. Yet, we know that photosynthesis arose then and played a critical role in subsequent evolution. Of primary importance was protection at approx.250-290 nm, where peak nucleic acid (approx.260 nm) and protein (approx.280 nm) absorptions occur. Nanophase ferric oxide/oxyhydroxide minerals absorb, and thus block, the lethal UV radiation, while transmitting light through much of the visible and near-infrared regions of interest to photosynthesis (400 to 1100 nm). Further, they were available in early environments, and are synthesized by many organisms. Based on ferric oxide/oxyhydroxide spectral properties, likely geologic processes, and the results of experiments with the photosynthetic organisms, Euglena sp. and Chlumydomonus reinhardtii, we propose a scenario where photosynthesis, and ultimately the oxygenation of the atmosphere, depended on the protection of early microbes by nanophase ferric oxides/oxyhydroxides. The results of this study are also applicable to other potentially habitable iron-bearing planetary bodies because of the evolutionary pressure to utilize solar radiation when available as an energy source.

  9. Impact of natural organic matter coatings on the microbial reduction of iron oxides

    NASA Astrophysics Data System (ADS)

    Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg

    2018-03-01

    Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L-1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that

  10. Changes in Soil Organic Carbon and Nitrogen as a Result of Cultivation

    DOE Data Explorer

    Post, Wilfred M [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mann, L. K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2005-01-01

    We assembed and analyzed a data base of soil organic carbon and nitrogen information from over 1100 profiles in order to explore factors related to the changes in storage of soil organic matter resulting from land conversion. The relationship between cultivated and uncultivated organic carbon and nitrogen storage in soils can be described by regression lines with uncultivated storage on the abscissa, and cultivated storage on the ordinate. The slope of the regression lines is less than 1 indicating that the amount of carbon or nitrogen lost is an increasing fraction of the intial amount stored in the soil. Average carbon loss for soils with high initial carbon is 23% for 1-meter depth. Average nitrogen loss for the same depth is 6%. In addition, for soils with very low uncultivated carbon or nitrogen storage, cultivation results in increases in storage. In soils with the same uncultivated carbon contents, profiles with higher C:N ratios lost more carbon than those with low C:N ratios, suggesting that decomposition of organic matter may, in general, be more limited by microbial ability to break carbon bonds than by nitrogen deficiency.

  11. Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

    PubMed

    Xiao, Dianne J; Bloch, Eric D; Mason, Jarad A; Queen, Wendy L; Hudson, Matthew R; Planas, Nora; Borycz, Joshua; Dzubak, Allison L; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G; Gagliardi, Laura; Brown, Craig M; Long, Jeffrey R

    2014-07-01

    Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.

  12. An enigmatic source of hematitic carbonate beds containing vast amounts of iron oxidizers in a paleozoic metamorphic complex, South Hungary, Geresd-Hills, Ófalu.

    NASA Astrophysics Data System (ADS)

    Jáger, Viktor; Dabi, Gergely; Menyhárt, Adrienn

    2013-04-01

    Near the village of Ófalu, in the Geresd Hills, South Hungary, within the "Mecsekalja tectonic belt", low and intermediate grade paleozoic metamorphic complex (phyllite, gneiss) contains vein-like hematitic carbonate beds, up to 30 cm in thickness. The carbonate mineral is calcite. These hematitic carbonate beds cross-cut the foliation of the phyllite, and show no signs of any metamorphic alteration. In the studied section the red carbonate beds are associated with a vein system filled with multiple generations of vein carbonates(Dabi et al., 2011). The red carbonate beds contain a vaste number of twisted stalks of the iron oxidizing taxon of Gallionella. Rarely in some siliceous parts, Leptothrix-like microbial fossils can be found and these beds also contain numerous unidentifiable, hematitic foraminifers. According to ICP-AES measurements, the hematitic carbonate beds contains 8 % Fe, 0.86 % Mn and 0.12 % Ba. XRD and Raman measurements proved that the iron phase is hematite. The SEM observations revealed that the bacterial microfossils and foraminifers are built up of micron-submicron sized pseudohexagonal platy hematite. The bacterial microfossils of the Gallionella iron oxidizer are very well preserved and reaches about 80 µm length and about 2-3 µm width. The above observations raise the following issues: 1. how did these non metamorphic hematitic-carbonatic beds get inside into the metamorphic complex?, 2. what is the age of the formation of these beds?, and 3. what was the source of the iron? If we consider that the hematitic beds contain foraminifers and iron oxidizing bacteria, and no signs of metamorphic alteration nor foliations can be observed in these beds, the only answer for the first question is that the formations are fractures filled with lime-mud, i.e. neptunian dykes, which penetrated into the cracks of the phyllite. The presence of foraminifers and the geotectonic situation of the unit imply marine origin. Considering that these beds are

  13. Determination of magnetic domain state of carbon coated iron nanoparticles via 57Fe zero-external-field NMR

    NASA Astrophysics Data System (ADS)

    Manjunatha, M.; Kumar, Rajeev; Sahoo, Balaram; Damle, Ramakrishna; Ramesh, K. P.

    2018-05-01

    The magnetic domain state of carbon coated iron nanopowder (Fe@C) was studied by the internal field nuclear magnetic resonance (IFNMR) at 77 K using the spin echo technique. The structure and magnetic properties of the sample were further characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy, vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA) and Raman Spectroscopy. The obtained IFNMR results of Fe@C powder were compared with that of micron sized carbonyl iron (CI) and electrolytic iron (EI) powders. The calculated critical size of the single domain iron particles in Fe@C is ∼ 16 nm. A higher enhancement in echo amplitude was observed due to better response of the domain walls of multidomain particles in comparison to the single domain particles. The echo signal of CI and EI particles exhibit a single narrow intense peak corresponding to the domain walls, whereas Fe@C exhibits two low amplitude peaks at two different frequencies: a low frequency (46.6 MHz) peak corresponds to the response of the domain walls of the multidomain particles and the other high frequency (47.2 MHz) signal (a shoulder) corresponding to the response of the magnetic nuclei inside the domain. Our results help in determining the domain state of iron-based magnetic particles using 57Fe-IFNMR.

  14. Organic-inorganic hybrid carbon dots for cell imaging

    NASA Astrophysics Data System (ADS)

    Liu, Huan; Zhang, Hongwen; Li, Jiayu; Tang, Yuying; Cao, Yu; Jiang, Yan

    2018-04-01

    In this paper, nitrogen-doped carbon dots (CDs) had been synthesized directly by one-step ultrasonic treatment under mild conditions. During the functionalization process, Octa-aminopropyl polyhedral oligomeric silsesquioxane hydrochloride salt (OA-POSS) was used as stabilizing and passivation agent, which lead to self-assembling of CDs in aqueous medium solution. OA-POSS was obtained via hydrolytic condensation of γ-aminopropyl triethoxy silane (APTES). The average size of CDs prepared was approximately 3.3 nm with distribution between 2.5 nm and 4.5 nm. The prepared organic-inorganic hybrid carbon dots have several characteristics such as photoluminescence emission wavelength, efficient cellular uptake, and good biocompatibility. The results indicate that OA-POSS can maintain the fluorescence properties of the carbon dots effectively, and reduced cytotoxicity provides the possibility for biomedical applications. More than 89% of the Hela cells were viable when incubated with 2 mg ml‑1 or lesser organic-inorganic hybrid carbon dots. Thus, it provides a potential for multicolor imaging with HeLa cells.

  15. Raman Spectroscopic Characterisation of Australian Banded Iron Formation and Iron Ore

    NASA Astrophysics Data System (ADS)

    Wells, M. A.; Ramanaidou, E. R.

    2012-04-01

    In Australia and world-wide over the past 5-10 years, declining reserves of premium, high-grade (>64% Fe), low-P bearing iron ore, have seen iron ore producers increase their utilisation of lower Fe-grade, higher P/Al/Si ore. In Australia, the channel iron deposits (CID), bedded iron deposits (BID) and, more recently, BIF-derived magnetite iron deposits (MID) have seen increased usage driven mainly by the increased demand from Chinese steel mills (Ramanaidou and Wells, 2011). Efficient exploitation and processing of these lower-grade iron ores requires a detailed understanding of their iron oxide and gangue mineralogy and geochemistry. The common Fe-bearing minerals (e.g., hematite, magnetite, goethite and kenomagnetite) in these deposits, as well as gangue minerals such as quartz and carbonates, are all strongly Raman active (e.g., de Faria et al., 1997). Their distinct Raman spectra enable them to be easily detected and mapped in situ in either unprepared material or samples prepared as polished blocks. In this paper, using representative examples of Australian CID ore, martite-goethite bedded iron deposit (BID) ore and banded iron formation (BIF) examined as polished blocks, we present a range of Raman spectra of the key iron ore minerals, and discuss how Raman spectroscopy can be applied to characterising iron ore mineralogy. Raman imaging micrographs, obtained using a StreamLine Plus Raman imaging system, clearly identified the main Fe-oxide and gangue components in the CID, BID and BIF samples when compared to optical micrographs. Raman analysis enabled the unequivocal identification of diamond in the CID ore as a contaminant from the polishing paste used to prepare the sample, and confirmed the presence of hematite in the BID ore in the form of martite, which can be morphologically similar to magnetite and, thus, difficult to otherwise distinguish. Image analysis of Raman mineral maps could be used to quantify mineral abundance based on the number of 'pixels

  16. Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism

    PubMed Central

    Price, Alex; Pearson, Victoria K.; Schwenzer, Susanne P.; Miot, Jennyfer; Olsson-Francis, Karen

    2018-01-01

    This work considers the hypothetical viability of microbial nitrate-dependent Fe2+ oxidation (NDFO) for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1–3.7 Ga) match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with appropriate

  17. Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism.

    PubMed

    Price, Alex; Pearson, Victoria K; Schwenzer, Susanne P; Miot, Jennyfer; Olsson-Francis, Karen

    2018-01-01

    This work considers the hypothetical viability of microbial nitrate-dependent Fe 2+ oxidation (NDFO) for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe 2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe 2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1-3.7 Ga) match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe 2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with appropriate

  18. Research on MRV system of iron and steel industry and verification mechanism establishment in China

    NASA Astrophysics Data System (ADS)

    Guo, Huiting; Chen, Liang; Chen, Jianhua

    2017-12-01

    The national carbon emissions trading market will be launched in 2017 in China. The iron and steel industry will be covered as one of the first industries. Establishing its MRV system is critical to promote the development of the iron and steel industry in the carbon trading market. This paper studies the requirements and procedures of the accounting, monitoring, reporting and verification of the seven iron and steel industry carbon trading pilots. The construction and operating mechanism of the MRV systems are also analyzed. Combining with the emission feature of the iron and steel industry, we study the suitable national MRV system for the whole iron and steel industry to consummate the future national carbon trading framework of iron and steel industry.

  19. Chemical and carbon isotopic composition of dissolved organic carbon in a regional confined methanogenic aquifer

    USGS Publications Warehouse

    Aravena, R.; Wassenaar, L.I.; Spiker, E. C.

    2004-01-01

    This study demonstrates the advantage of a combined use of chemical and isotopic tools to understand the dissolved organic carbon (DOC) cycle in a regional confined methanogenic aquifer. DOC concentration and carbon isotopic data demonstrate that the soil zone is a primary carbon source of groundwater DOC in areas close to recharge zones. An in-situ DOC source linked to organic rich sediments present in the aquifer matrix is controlling the DOC pool in the central part of the groundwater flow system. DOC fractions, 13C-NMR on fulvic acids and 14C data on DOC and CH4 support the hypothesis that the in-situ DOC source is a terrestrial organic matter and discard the Ordovician bedrock as a source of DOC. ?? 2004 Taylor and Francis Ltd.

  20. [Identification of using organic carbon isotopic composition of soil pollution process].

    PubMed

    Guo, Qing-Jun; Chen, Tong-Bin; Yang, Jun; Strauss, Harald; Lei, Mei; Zhu, Guang-Xu; Li, Yan-Mei; Zhou, Xiao-Yong; Li, Xiao-Yan

    2011-10-01

    This study has taken advantage of the characteristics of concentration of soil organic matter (SOC) and delta13 C(SOC) values to provide proofs for environment quality assessment and to know more about polluted sources, sizes and processes in Beijing steel company area. delta13C values of SOC is good for tracing sources and documenting shifts in community composition and distribution. Two sections (Beijing steel company area and Yongledian, Tongzhou) which belong to two different soil types collected in Beijing, and organic carbon isotopic composition and total soil organic carbon were analyzed. These results shows that SOC of soil samples from Beijing steel company area are quite high, and even 9.7% at the surface sample, however SOC from unpolluted area (Yongledian area) is lower than those of industrial area. delta13 C(SOC) from soils of Beijing steel company area and Yongledian area respectively vary from -24.8 per thousand to -23.1 per thousand and -26.4 per thousand to -20.5 per thousand, the results are quite different. The results reflect that there are different organic carbon sources in different types' soil: Organic carbon from Beijing steel company area has been mainly affected by coal burning, soil organic carbon concentrations are quite high, and pollution can affect on soils 70 cm deep underground; and soils from Yongledian area, have been not polluted, and organic matter is from natural litter (C3 plants). Although there are different soil organic carbon concentrations and isotope compositions, two soil sections have similar variation trends. This study provides proofs for environment quality assessment and know more about polluted and natural sources, sizes in Beijing.

  1. Dissolved Organic Carbon in Headwater Streams and Riparian Soil Organic Carbon along an Altitudinal Gradient in the Wuyi Mountains, China

    PubMed Central

    Huang, Wei; McDowell, William H.; Zou, Xiaoming; Ruan, Honghua; Wang, Jiashe; Li, Liguang

    2013-01-01

    Stream water dissolved organic carbon (DOC) correlates positively with soil organic carbon (SOC) in many biomes. Does this relationship hold in a small geographic region when variations of temperature, precipitation and vegetation are driven by a significant altitudinal gradient? We examined the spatial connectivity between concentrations of DOC in headwater stream and contents of riparian SOC and water-soluble soil organic carbon (WSOC), riparian soil C:N ratio, and temperature in four vegetation types along an altitudinal gradient in the Wuyi Mountains, China. Our analyses showed that annual mean concentrations of headwater stream DOC were lower in alpine meadow (AM) than in subtropical evergreen broadleaf forest (EBF), coniferous forest (CF), and subalpine dwarf forest (SDF). Headwater stream DOC concentrations were negatively correlated with riparian SOC as well as WSOC contents, and were unrelated to riparian soil C:N ratio. Our findings suggest that DOC concentrations in headwater streams are affected by different factors at regional and local scales. The dilution effect of higher precipitation and adsorption of soil DOC to higher soil clay plus silt content at higher elevation may play an important role in causing lower DOC concentrations in AM stream of the Wuyi Mountains. Our results suggest that upscaling and downscaling of the drivers of DOC export from forested watersheds when exploring the response of carbon flux to climatic change or other drivers must done with caution. PMID:24265737

  2. Black Carbon Contribution to Organic Carbon Stocks in Urban Soil.

    PubMed

    Edmondson, Jill L; Stott, Iain; Potter, Jonathan; Lopez-Capel, Elisa; Manning, David A C; Gaston, Kevin J; Leake, Jonathan R

    2015-07-21

    Soil holds 75% of the total organic carbon (TOC) stock in terrestrial ecosystems. This comprises ecosystem-derived organic carbon (OC) and black carbon (BC), a recalcitrant product of the incomplete combustion of fossil fuels and biomass. Urban topsoils are often enriched in BC from historical emissions of soot and have high TOC concentrations, but the contribution of BC to TOC throughout the urban soil profile, at a regional scale is unknown. We sampled 55 urban soil profiles across the North East of England, a region with a history of coal burning and heavy industry. Through combined elemental and thermogravimetic analyses, we found very large total soil OC stocks (31-65 kg m(-2) to 1 m), exceeding typical values reported for UK woodland soils. BC contributed 28-39% of the TOC stocks, up to 23 kg C m(-2) to 1 m, and was affected by soil texture. The proportional contribution of the BC-rich fraction to TOC increased with soil depth, and was enriched in topsoil under trees when compared to grassland. Our findings establish the importance of urban ecosystems in storing large amounts of OC in soils and that these soils also capture a large proportion of BC particulates emitted within urban areas.

  3. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

  4. Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

    PubMed

    Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek

    2011-08-29

    The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Which is the best oxidant for complexed iron removal from groundwater: The Kogalym case

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

    Munter, R.; Overbeck, P.; Sutt, J.

    2008-07-01

    A short overview of the significance of a preoxidation stage groundwater treatment is presented. As an example the case of complexed iron removal from Kogalym groundwater (Tjumen, Siberia, Russian Federation) using different preoxidants (ozone, oxygen, chlorine, hydrogen peroxide, and potassium permanganate) is discussed. The key problem is stable di- and trivalent iron-organic complexes in groundwater which after aeration tend to pass through the hydroanthracite-sand gravity filters. The total organic carbon (TOC) content in raw groundwater is in the range of 3.2-6.4 mg/L, total iron content 2.7-6.0 mg/L and divalent iron content 2.4-4.0 mg/L. Separation from Kogalym groundwater by XAD-16 adsorbentmore » humic matter fraction was homogeneous, with only 1 peak on the chromatogram with maximum Rt = 10.75 min and corresponding molecular mass 1911 ({lt} 2000). The final developed treatment technology is based on the water oxidation/reduction potential (ORP) optimization according to the iron system pE-pH diagram and consists of intensive aeration of raw water in the Gas-Degas Treatment (GDT) unit with the following sequence: filtration through the hydroanthracite and special anthracite Everzit, with intermediate enrichment of water with pure oxygen between the filtration stages.« less

  6. Biological denitrification process based on the Fe(0)-carbon micro-electrolysis for simultaneous ammonia and nitrate removal from low organic carbon water under a microaerobic condition.

    PubMed

    Deng, Shihai; Li, Desheng; Yang, Xue; Xing, Wei; Li, Jinlong; Zhang, Qi

    2016-11-01

    A combined process between micro-electrolysis and biological denitrification (MEBD) using iron scraps and an activated carbon-based micro-electrolysis carrier was developed for nitrogen removal under a microaerobic condition. The process provided NH4(+)-N and total nitrogen (TN) removal efficiencies of 92.6% and 95.3%, respectively, and TN removal rate of 0.373±0.11kgN/(m(3)d) at corresponding DO of 1.0±0.1mg/L and HRT of 3h, and the optimal pH of 7.6-8.4. High-throughput sequencing analysis verified that dominant classes belonged to β-, α-, and γ-Proteobacteria, and Nitrospira. The dominant genera Hydrogenophaga and Sphaerotilus significantly increased during the operation, covering 13.2% and 6.1% in biofilms attached to the carrier in the middle of the reactor, respectively. Autotrophic denitrification contributed to >80% of the TN removal. The developed MEBD achieved efficient simultaneous nitrification and autotrophic denitrification, presenting significant potential for application in practical low organic carbon water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction.

    PubMed

    Wang, Biwei; Wang, Xinxia; Zou, Jinxiang; Yan, Yancui; Xie, Songhai; Hu, Guangzhi; Li, Yanguang; Dong, Angang

    2017-03-08

    Iron and nitrogen codoped carbons (Fe-N-C) have attracted increasingly greater attention as electrocatalysts for oxygen reduction reaction (ORR). Although challenging, the synthesis of Fe-N-C catalysts with highly dispersed and fully exposed active sites is of critical importance for improving the ORR activity. Here, we report a new type of graphitic Fe-N-C catalysts featuring numerous Fe single atoms anchored on a three-dimensional simple-cubic carbon framework. The Fe-N-C catalyst, derived from self-assembled Fe 3 O 4 nanocube superlattices, was prepared by in situ ligand carbonization followed by acid etching and ammonia activation. Benefiting from its homogeneously dispersed and fully accessible active sites, highly graphitic nature, and enhanced mass transport, our Fe-N-C catalyst outperformed Pt/C and many previously reported Fe-N-C catalysts for ORR. Furthermore, when used for constructing the cathode for zinc-air batteries, our Fe-N-C catalyst exhibited current and power densities comparable to those of the state-of-the-art Pt/C catalyst.

  8. Lunar dust simulant containing nanophase iron and method for making the same

    NASA Technical Reports Server (NTRS)

    Hung, Chin-cheh (Inventor); McNatt, Jeremiah (Inventor)

    2012-01-01

    A lunar dust simulant containing nanophase iron and a method for making the same. Process (1) comprises a mixture of ferric chloride, fluorinated carbon powder, and glass beads, treating the mixture to produce nanophase iron, wherein the resulting lunar dust simulant contains .alpha.-iron nanoparticles, Fe.sub.2O.sub.3, and Fe.sub.3O.sub.4. Process (2) comprises a mixture of a material of mixed-metal oxides that contain iron and carbon black, treating the mixture to produce nanophase iron, wherein the resulting lunar dust simulant contains .alpha.-iron nanoparticles and Fe.sub.3O.sub.4.

  9. Measuring the decomposition of organic carbon sequestered by salt marsh sediment

    NASA Astrophysics Data System (ADS)

    Light, T.; Mctigue, N.; Currin, C.

    2016-12-01

    As atmospheric carbon dioxide concentrations continue to rise, salt marshes are increasingly being recognized as a natural carbon sink, for large amounts of organic carbon are sequestered by salt marsh sediments. However, little is known regarding the fate of this "blue carbon" after salt marsh sediment is disturbed via erosion or lost due to sea level rise. This investigation explored novel methodologies for determining the lability of carbon sequestered by salt marsh sediment. Sediment cores were collected from a Spartina alterniflora-dominated marsh in Camp Lejeune, NC, and elemental analysis revealed that the upper 76 cm of sediment at the site contains a total carbon stock of 28.4 kg /m2. Sediment ranging from 251-545 years old, as determined through radiocarbon dating, was incubated under sub-aerial and aqueous conditions for 18 days and 25 days respectively. Carbon dioxide flux measurements revealed that shallower sediment organic matter decomposed more rapidly than deeper sediment in sub-aerial incubations, but decomposition was fairly slow in both treatments. No significant organic matter decomposition was observed in the aqueous incubations, as revealed by analyses of organic carbon remaining after the incubation period. The aqueous incubation included a treatment that had been "primed" with highly labile yeast extract, but no significant priming effect was observed over 25 days. While further investigation on the fate of this sediment carbon is needed, these preliminary findings indicate that salt marshes facilitate long-term carbon sequestration even after disturbances. This in turn supports the argument for mitigating anthropogenic carbon dioxide emissions through salt marsh restoration, and supports a policy of preserving and conserving coastal wetlands for this valuable ecosystem service.

  10. The size distribution of organic carbon in headwater streams in the Amazon basin.

    PubMed

    de Paula, Joana D'Arc; Luizão, Flávio Jesus; Piedade, Maria Teresa Fernandez

    2016-06-01

    Despite the strong representativeness of streams in the Amazon basin, their role in the accumulation of coarse particulate organic carbon (CPOC), fine particulate organic carbon (FPOC), and dissolved organic carbon (DOC) in transport, an important energy source in these environments, is poorly known. It is known that the arboreal vegetation in the Amazon basin is influenced by soil fertility and rainfall gradients, but would these gradients promote local differences in organic matter in headwater streams? To answer this question, 14 low-order streams were selected within these gradients along the Amazon basin, with extensions that varied between 4 and 8 km. The efficiency of the transformation of particulate into dissolved carbon fractions was assessed for each stream. The mean monthly benthic organic matter storage ranged between 1.58 and 9.40 t ha(-1) month(-1). In all locations, CPOC was the most abundant fraction in biomass, followed by FPOC and DOC. Rainfall and soil fertility influenced the distribution of the C fraction (p = 0.01), showing differentiated particulate organic carbon (POC) storage and DOC transportation along the basin. Furthermore, the results revealed that carbon quantification at the basin level could be underestimated, ultimately influencing the global carbon calculations for the region. This is especially due to the fact that the majority of studies consider only fine particulate organic matter and dissolved organic matter, which represent less than 50 % of the stored and transported carbon in streambeds.

  11. Molecular Fractionation of Dissolved Organic Matter in a Shallow Subterranean Estuary: The Role of the Iron Curtain

    PubMed Central

    2016-01-01

    Iron that precipitates under aerobic conditions in natural aquatic systems scavenges dissolved organic matter (DOM) from solution. Subterranean estuaries (STEs) are of major importance for land–ocean biogeochemical fluxes. Their specific redox boundaries, coined the “iron curtain” due to the abundance of precipitated iron(III) (oxy)hydroxides, are hot spots for the removal and redissolution of iron, associated nutrients, and DOM. We used ultra-high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to molecularly characterize the iron-coagulating fractions of 32 groundwater and seawater DOM samples along a salinity gradient from a shallow STE on Spiekeroog Island, North Sea, Germany, and linked our findings to trace metal and nutrient concentrations. We found systematic iron coagulation of large (>450 Da), oxygen-rich, and highly aromatic DOM molecules of terrestrial origin. The extent of coagulation increased with growing terrestrial influence along the salinity gradient. Our study is the first to show that the iron curtain may be capable of retaining terrigenous DOM fractions in marine sediments. We hypothesize that the iron curtain serves as an inorganic modulator for the supply of DOM from groundwaters to the sea, and that the STE has the potential to act as a temporal storage or even sink for terrigenous aromatic DOM compounds. PMID:27976873

  12. [Characteristics of organic carbon forms in the sediment of Wuliangsuhai and Daihai Lakes].

    PubMed

    Mao, Hai-Fang; He, Jiang; Lü, Chang-Wei; Liang, Ying; Liu, Hua-Lin; Wang, Feng-Jiao

    2011-03-01

    The characteristics and differences of organic carbon forms in the sediments of the Wuliangsuhai and the Daihai Lakes with different eutrophication types were discussed in the present study. The results showed that the range of total organic carbon content (TOC) in Wuliangsuhai Lake was 4.50-22.83 g x kg(-1) with the average of 11.80 g x kg(-1). The range of heavy-fraction organic carbon content was 3.38-21.67 g x kg(-1) with the average of 10.76 g x kg(-1). The range of light-fraction organic carbon content was 0.46-1.80 g x kg(-1) with the average of 1.04 g x kg(-1); The range of ROC content was 0.62-3.64 g x kg(-1) with the average of 2.11 g x kg(-1), while the range of total organic carbon content in Daihai lake was 6.84-23.46 g x kg(-1) with the average of 14.94 g x kg(-1). The range of heavy-fraction organic carbon content was 5.27-22.23 g x kg(-1) with the average of 13.89 g x kg(-1). The range of light-fraction organic carbon content was 0.76-1.57 g x kg(-1). The range of ROC content was 1.54-7.08 g x kg(-1) with the average of 3.62 g x kg(-1). The results indicated that the heavy-fraction organic carbon was the major component of the organic carbon and plays an important role in the accumulation of organic carbon in the sediments of two Lakes. The content of light-fraction organic carbon was similar in the sediments of two lakes, whereas, the contents of total organic carbon and heavy-fraction organic carbon in the sediment of Wuliangsuhai Lake were less than those in the sediment of Daihai Lake, and the value of LFOC/TOC in the Wuliangsuhai Lake was larger than that in the Daihai Lake. The humin was the dominant component of the sediment humus, followed by fulvic acid in the two lakes. The values of HM/HS in the sediments of Wuliangsuhai lake range from 43.06% to 77.25% with the average of 62.15% and values of HM/HS in the sediments of Dahai lake range from 49.23% to 73.85% with the average of 65.30%. The tightly combined humus was the dominant form in

  13. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    NASA Technical Reports Server (NTRS)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  14. X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor.

    PubMed

    Lancaster, Kyle M; Roemelt, Michael; Ettenhuber, Patrick; Hu, Yilin; Ribbe, Markus W; Neese, Frank; Bergmann, Uwe; DeBeer, Serena

    2011-11-18

    Nitrogenase is a complex enzyme that catalyzes the reduction of dinitrogen to ammonia. Despite insight from structural and biochemical studies, its structure and mechanism await full characterization. An iron-molybdenum cofactor (FeMoco) is thought to be the site of dinitrogen reduction, but the identity of a central atom in this cofactor remains unknown. Fe Kβ x-ray emission spectroscopy (XES) of intact nitrogenase MoFe protein, isolated FeMoco, and the FeMoco-deficient nifB protein indicates that among the candidate atoms oxygen, nitrogen, and carbon, it is carbon that best fits the XES data. The experimental XES is supported by computational efforts, which show that oxidation and spin states do not affect the assignment of the central atom to C(4-). Identification of the central atom will drive further studies on its role in catalysis.

  15. Diurnal variation in the coupling of photosynthetic electron transport and carbon fixation in iron-limited phytoplankton in the NE subarctic Pacific

    NASA Astrophysics Data System (ADS)

    Schuback, N.; Flecken, M.; Maldonado, M. T.; Tortell, P. D.

    2015-10-01

    Active chlorophyll a fluorescence approaches, including fast repetition rate fluorometry (FRRF), have the potential to provide estimates of phytoplankton primary productivity at unprecedented spatial and temporal resolution. FRRF-derived productivity rates are based on estimates of charge separation at PSII (ETRRCII), which must be converted into ecologically relevant units of carbon fixation. Understanding sources of variability in the coupling of ETRRCII and carbon fixation provides physiological insight into phytoplankton photosynthesis, and is critical for the application of FRRF as a primary productivity measurement tool. In the present study, we simultaneously measured phytoplankton carbon fixation and ETRRCII in the iron-limited NE subarctic Pacific, over the course of a diurnal cycle. We show that rates of ETRRCII are closely tied to the diurnal cycle in light availability, whereas rates of carbon fixation appear to be influenced by endogenous changes in metabolic energy allocation under iron-limited conditions. Unsynchronized diurnal oscillations of the two rates led to 3.5 fold changes in the conversion factor coupling ETRRCII and carbon fixation (Φe:C / nPSII). Consequently, diurnal variability in phytoplankton carbon fixation cannot be adequately captured with FRRF approaches if a constant conversion factor is applied. Utilizing several auxiliary photophysiological measurements, we observed that a high conversion factor is associated with conditions of excess light, and correlates with the expression of non-photochemical quenching (NPQ) in the pigment antenna, as derived from FRRF measurements. The observed correlation between NPQ and the conversion factor Φe:C / nPSII has the potential to improve estimates of phytoplankton carbon fixation rates from FRRF measurements alone.

  16. Diurnal variation in the coupling of photosynthetic electron transport and carbon fixation in iron-limited phytoplankton in the NE subarctic Pacific

    NASA Astrophysics Data System (ADS)

    Schuback, Nina; Flecken, Mirkko; Maldonado, Maria T.; Tortell, Philippe D.

    2016-02-01

    Active chlorophyll a fluorescence approaches, including fast repetition rate fluorometry (FRRF), have the potential to provide estimates of phytoplankton primary productivity at an unprecedented spatial and temporal resolution. FRRF-derived productivity rates are based on estimates of charge separation in reaction center II (ETRRCII), which must be converted into ecologically relevant units of carbon fixation. Understanding sources of variability in the coupling of ETRRCII and carbon fixation provides physiological insight into phytoplankton photosynthesis and is critical for the application of FRRF as a primary productivity measurement tool. In the present study, we simultaneously measured phytoplankton carbon fixation and ETRRCII in the iron-limited NE subarctic Pacific over the course of a diurnal cycle. We show that rates of ETRRCII are closely tied to the diurnal cycle in light availability, whereas rates of carbon fixation appear to be influenced by endogenous changes in metabolic energy allocation under iron-limited conditions. Unsynchronized diurnal oscillations of the two rates led to 3.5-fold changes in the conversion factor between ETRRCII and carbon fixation (Kc / nPSII). Consequently, diurnal variability in phytoplankton carbon fixation cannot be adequately captured with FRRF approaches if a constant conversion factor is applied. Utilizing several auxiliary photophysiological measurements, we observed that a high conversion factor is associated with conditions of excess light and correlates with the increased expression of non-photochemical quenching (NPQ) in the pigment antenna, as derived from FRRF measurements. The observed correlation between NPQ and Kc / nPSII requires further validation but has the potential to improve estimates of phytoplankton carbon fixation rates from FRRF measurements alone.

  17. Iron oxide and iron carbide particles produced by the polyol method

    NASA Astrophysics Data System (ADS)

    Yamada, Y.; Shimizu, R.; Kobayashi, Y.

    2016-12-01

    Iron oxide ( γ-Fe2O3) and iron carbide (Fe3C) particles were produced by the polyol method. Ferrocene, which was employed as an iron source, was decomposed in a mixture of 1,2-hexadecandiol, oleylamine, and 1-octadecene. Particles were characterized using Mössbauer spectroscopy, X-ray diffraction, and transmission electron microscopy. It was found that oleylamine acted as a capping reagent, leading to uniform-sized (12-16 nm) particles consisting of γ-Fe 2O3. On the other hand, 1-octadecene acted as a non-coordinating solvent and a carbon source, which led to particles consisting of Fe3C and α-Fe with various sizes.

  18. The removal of uranium onto carbon-supported nanoscale zero-valent iron particles

    NASA Astrophysics Data System (ADS)

    Crane, Richard A.; Scott, Thomas

    2014-12-01

    In the current work carbon-supported nanoscale zero-valent iron particles (CS nZVI), synthesised by the vacuum heat treatment of ferric citrate trihydrate absorbed onto carbon black, have been tested for the removal of uranium (U) from natural and synthetic waters. Two types of CS nZVI were tested, one vacuum annealed at 600 °C for 4 h and the other vacuum annealed at 700 °C for 4 h, with their U removal behaviour compared to nZVI synthesised via the reduction of ferrous iron using sodium borohydride. The batch systems were analysed over a 28-day reaction period during which the liquid and nanoparticulate solids were periodically analysed to determine chemical evolution of the solutions and particulates. Results demonstrate a well-defined difference between the two types of CS nZVI, with greater U removal exhibited by the nanomaterial synthesised at 700 °C. The mechanism has been attributed to the CS nZVI synthesised at 700 °C exhibiting (i) a greater proportion of surface oxide Fe2+ to Fe3+ (0.34 compared to 0.28); (ii) a greater conversion of ferric citrate trihydrate [2Fe(C6H5O7)·H2O] to Fe0; and (iii) a larger surface area (108.67 compared to 88.61 m2 g-1). Lower maximum U uptake was recorded for both types of CS nZVI in comparison with the borohydride-reduced nZVI. A lower decrease in solution Eh and DO was also recorded, indicating that less chemical reduction of U was achieved by the CS nZVI. Despite this, lower U desorption in the latter stages of the experiment (>7 days) was recorded for the CS nZVI synthesised at 700 °C, indicating that carbon black in the CS nZVI is likely to have contributed towards U sorption and retention. Overall, it can be stated that the borohydride-reduced nZVI were significantly more effective than CS nZVI for U removal over relatively short timescales (e.g. <48 h), however, they were more susceptible to U desorption over extended time periods.

  19. Pathways of organic carbon oxidation in three continental margin sediments

    NASA Technical Reports Server (NTRS)

    Canfield, D. E.; Jorgensen, B. B.; Fossing, H.; Glud, R.; Gundersen, J.; Ramsing, N. B.; Thamdrup, B.; Hansen, J. W.; Nielsen, L. P.; Hall, P. O.

    1993-01-01

    We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

  20. The preservation and degradation of filamentous bacteria and biomolecules within iron oxide deposits at Rio Tinto, Spain.

    PubMed

    Preston, L J; Shuster, J; Fernández-Remolar, D; Banerjee, N R; Osinski, G R; Southam, G

    2011-05-01

    One of the keys to understanding and identifying life on other planets is to study the preservation of organic compounds and their precursor micro-organisms on Earth. Rio Tinto in southwestern Spain is a well documented site of microbial preservation within iron sulphates and iron oxides over a period of 2.1 Ma. This study has investigated the preservation of filamentous iron oxidising bacteria and organics through optical microscopy, scanning electron microscopy (SEM) and Fourier transform infra-red (FTIR) spectroscopy, from laboratory cultures of natural samples to contemporary natural materials to million-year old river terraces. Up to 40% elemental carbon and >7% nitrogen has been identified within microbial filaments and cell clusters in all samples through SEM EDS analyses. FTIR spectroscopy identified C-H(x) absorption bands between 2960 and 2800 cm(-1), Amide I and II absorption bands at 1656 and 1535 cm(-1), respectively and functional group vibrations from within nucleic acids at 917, 1016 and 1124 cm(-1). Absorption bands tracing the diagenetic transformation of jarosite to goethite to hematite through the samples are also identified. This combination of mineralogy, microbial morphology and biomolecular evidence allows us to further understand how organic fossils are created and preserved in iron-rich environments, and ultimately will aid in the search for the earliest life on Earth and potential organics on Mars. © 2011 Blackwell Publishing Ltd.

  1. ESTIMATING DISSOLVED ORGANIC CARBON PARTITION COEFFICIENTS FOR NONIONIC ORGANIC CHEMICALS

    EPA Science Inventory

    A literature search was performed for dissolved organic carbon/water partition coefficients for nonionic chemicals (Kdoc) and Kdoc data was taken from more than sixty references. The Kdoc data were evaluated as a function of the n-octanol/water partition coefficients (Kow). A pre...

  2. Peculiarities of antioxidant system and iron metabolism in organism during development of tumor resistance to cisplatin.

    PubMed

    Chekhun, V F; Lozovska, Y V; Burlaka, A P; Lukyanova, N Y; Todor, I N; Naleskina, L A

    2014-09-01

    To study in vivo the peculiarities of changes of iron metabolism and antioxidant system in dynamics of growth of Guerin carcinoma with different sensitivity to cisplatin. In order to evaluate the content of metallothionein-1 (MT-1) in tumor homogenates and blood serum of rats with cisplatin-sensitive and cisplatin-resistant Guerin carcinoma the immunoenzyme method was used. The evaluation of ceruloplasmin activity, content of "free iron" complexes, superoxide and NO-generating acti-vity of NADPH-oxidase and iNOS activity in neutrophils, blood serum and tumor homogenates was measured by EPR-spectro-scopy. Maximal accumulation of MT-1 in blood serum and tumor, more pronounced in resistant strain, at the border of latent and exponential phase of growth has been shown that is the evidence of protective role of this protein in the respect to the generation of free radical compounds. It has been determined that in animals with cisplatin-resistant strain of Guerin carcinoma, increase of "free iron" complexes is more apparent both on the level of tumor and organism on the background on increase of CP/TR ratio that is the consequence of organism antioxidant protection system disorder. Mentioned changes in metabolism of iron with its accumulation in tumor and further reprogramming of mitochondria metabolism and activity of NADPH-oxidase for non-transformed cells are favorable conditions for the formation of oxidative phenotype of tumor.

  3. Measurement and importance of dissolved organic carbon. Chapter 13

    Treesearch

    Randall Kolka; Peter Weishampel; Mats Froberg

    2008-01-01

    The flux of dissolved organic carbon (DOC) from an ecosystem can be a significant component of carbon (C) budgets especially in watersheds containing wetlands. Although internal ecosystem cycling of DOC is generally greater than the fluxes to ground or surface waters, it is the transport out of the system that is a main research focus for carbon accounting. In...

  4. Micropore clogging by leachable pyrogenic organic carbon: A new perspective on sorption irreversibility and kinetics of hydrophobic organic contaminants to black carbon.

    PubMed

    Wang, Bingyu; Zhang, Wei; Li, Hui; Fu, Heyun; Qu, Xiaolei; Zhu, Dongqiang

    2017-01-01

    Black carbon (BC) plays a crucial role in sequestering hydrophobic organic contaminants in the environment. This study investigated key factors and mechanisms controlling nonideal sorption (e.g., sorption irreversibility and slow kinetics) of model hydrophobic organic contaminants (nitrobenzene, naphthalene, and atrazine) by rice-straw-derived BC. After removing the fraction of leachable pyrogenic organic carbon (LPyOC) (referring to composites of dissoluble non-condensed organic carbon and associated mineral components) with deionized water or 0.5 M NaOH, sorption of these sorbates to BC was enhanced. The sorption enhancement was positively correlated with sorbate molecular size in the order of atrazine > naphthalene > nitrobenzene. The removal of LPyOC also accelerated sorption kinetics and reduced sorption irreversibility. These observations were attributed to increased accessibility of BC micropores initially clogged by the LPyOC. Comparison of BC pore size distributions before and after atrazine sorption further suggested that the sorbate molecules preferred to access the micropores that were more open, and the micropore accessibility was enhanced by the removal of LPyOC. Consistently, the sorption of nitrobenzene and atrazine to template-synthesized mesoporous carbon (CMK3), a model sorbent with homogeneous pore structures, showed decreased kinetics, but increased irreversibility by impregnating sorbent pores with surface-grafted alkylamino groups and by subsequent loading of humic acid. These findings indicated an important and previously unrecognized role of LPyOC (i.e., micropore clogging) in the nonideal sorption of organic contaminants to BC. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Munsell color value as related to organic carbon in Devonian shale of Appalachian basin

    USGS Publications Warehouse

    Hosterman, J.W.; Whitlow, S.I.

    1981-01-01

    Comparison of Munsell color value with organic carbon content of 880 samples from 50 drill holes in Appalachian basin shows that a power curve is the best fit for the data. A color value below 3 to 3.5 indicates the presence of organic carbon but is meaningless in determining the organic carbon content because a large increase in amount of organic carbon causes only a minor decrease in color value. Above 4, the color value is one of the factors that can be used in calculating the organic content. For samples containing equal amounts of organic carbon, calcareous shale containing more than 5% calcite is darker than shale containing less than 5% calcite.-Authors

  6. Tectonic control of the crustal organic carbon reservoir during the Precambrian

    NASA Technical Reports Server (NTRS)

    Des Marais, D. J.

    1994-01-01

    Carbon isotopic trends indicate that the crustal reservoir of reduced, organic carbon increased during the Proterozoic, particularly during periods of widespread continental rifting and orogeny. No long-term trends are apparent in the concentration of organic carbon in shales, cherts and carbonates. The age distribution of 261 sample site localities sampled for well-preserved sedimentary rocks revealed a 500-700-Ma periodicity which coincided with tectonic cycles. It is assumed that the numbers of sites are a proxy for mass of sediments. A substantial increase in the number of sites in the late Archean correlates with the first appearance between 2.9 and 2.5 Ga of extensive continental platforms and their associated sedimentation. It is proposed that the size of the Proterozoic crustal organic carbon reservoir has been modulated by tectonic control of the volume of sediments deposited in environments favorable for the burial and preservation of organic matter. Stepwise increases in this reservoir would have caused the oxidation state of the Proterozoic environment to increase in a stepwise fashion.

  7. Spatial Variability in Decomposition of Organic Carbon Along a Meandering River Floodplain

    NASA Astrophysics Data System (ADS)

    Sutfin, N. A.; Rowland, J. C.; Tfaily, M. M.; Bingol, A. K.; Washton, N.

    2017-12-01

    Rivers are an important component of the terrestrial carbon cycle and floodplains can provide significant storage of organic carbon. Quantification of long-term storage, however, requires determination of the residence time of sediment and the decomposition rate of organic carbon in floodplains. We use fourier transform ion cyclotron resonance (FTICR) mass spectrometry to examine the organic carbon compounds present in sediment within three floodplain settings: point bars, cutbanks, and abandoned channels. We define decomposition of organic carbon in floodplain sediment as the ratio between the number of protein versus lignin, which serve as proxies for microbial-derived and terrestrial-derived organic carbon, respectively. Samples were collected at 0-5 cm, 5-15cm, and 15-30 cm depth along four transects that span a longitudinal valley distance of 8 km on the East River near Crested Butte, CO. Although no significant trends in decomposition ratio exist longitudinally between the fours transects, floodplain settings exhibit significant differences. At shallow depths (0-5 cm), there are no significant differences among settings, with the exception of gravel portions of point bars below bankfull flow, where the highest decomposition is present. Conversely, cutbanks contain significantly lower decomposition ratios compared with point bars, gravel bars, and abandoned channels when considering all depth intervals. Pointbars exhibit significantly greater protein vs. lignin at the surface compared to greater depth. Higher decomposition ratios along abandoned channels and point bars suggest that frequent wetting and drying periods, abundant oxygen, and continuous downstream movement and decomposition of organic matter occurs within the channel. Lower decomposition ratios and consistent trends with depth along cutbanks, suggest that these stable surfaces serve as organic carbon reservoirs that could become an increased source of carbon to the channel with increasing bank

  8. Controlled preparation of carbon nanotube-iron oxide nanoparticle hybrid materials by a modified wet impregnation method

    NASA Astrophysics Data System (ADS)

    Tsoufis, Τheodoros; Douvalis, Alexios P.; Lekka, Christina E.; Trikalitis, Pantelis N.; Bakas, Thomas; Gournis, Dimitrios

    2013-09-01

    We report a novel, simple, versatile, and reproducible approach for the in situ synthesis of iron oxide nanoparticles (NP) on the surface of carbon nanotubes (CNT). Chemically functionalized single- or multi-wall CNT were used as nanotemplates for the synthesis of a range of very small (<10 nm) ferrimagnetic and/or anti-ferromagnetic iron oxide NP on their surface. For the synthesis of the hybrid materials, we employed for the first time a modified wet impregnation method involving the adsorption of ferric cations (as nanoparticle's precursor) on the functionalized nanotube surface and the subsequent interaction with acetic acid vapors followed by calcination at 400 °C under different atmospheres (air, argon, and oxygen). X-ray diffraction, transmission electron microscopy, Mössbauer spectroscopy, and magnetization measurements were used to study in-detail the morphology, size, and type of crystalline phases in the resulting hybrid materials. In addition, Raman measurements were used to monitor possible structural changes of the nanotubes during the synthetic approach. The experimental results were further supported by density functional theory calculations. These calculations were also used to disclose, how the type of the carbon nanotube template affects the nature and the size of the resulting NP in the final hybrids.

  9. Dissolved organic carbon in the precipitation of Seoul, Korea: Implications for global wet depositional flux of fossil-fuel derived organic carbon

    NASA Astrophysics Data System (ADS)

    Yan, Ge; Kim, Guebuem

    2012-11-01

    Precipitation was sampled in Seoul over a one-year period from 2009 to 2010 to investigate the sources and fluxes of atmospheric dissolved organic carbon (DOC). The concentrations of DOC varied from 15 μM to 780 μM, with a volume-weighted average of 94 μM. On the basis of correlation analysis using the commonly acknowledged tracers, such as vanadium, the combustion of fossil-fuels was recognized to be the dominant source. With the aid of air mass backward trajectory analyses, we concluded that the primary fraction of DOC in our precipitation samples originated locally in Korea, albeit the frequent long-range transport from eastern and northeastern China might contribute substantially. In light of the relatively invariant organic carbon to sulfur mass ratios in precipitation over Seoul and other urban regions around the world, the global magnitude of wet depositional DOC originating from fossil-fuels was calculated to be 36 ± 10 Tg C yr-1. Our study further underscores the potentially significant environmental impacts that might be brought about by this anthropogenically derived component of organic carbon in the atmosphere.

  10. Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

    USGS Publications Warehouse

    Pohlman, J.W.; Bauer, J.E.; Waite, W.F.; Osburn, C.L.; Chapman, N.R.

    2011-01-01

    Marine sediments contain about 500-10,000 Gt of methane carbon, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined, but it releases relatively little methane to the ocean and atmosphere. Sedimentary microbes convert most of the dissolved methane to carbon dioxide. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use ??14 C and ??13 C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13 C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000-6,000 year age of dissolved organic carbon in the deep ocean, and provide reduced organic matter and energy to deep-ocean microbial communities. ?? 2011 Macmillan Publishers Limited. All rights reserved.

  11. Changes in carbon fractions during composting and maturation of organic wastes

    NASA Astrophysics Data System (ADS)

    Garcia, Carlos; Hernandez, Teresa; Costa, Francisco

    1991-05-01

    Seven mixtures from four organic residues—an aerobic sewage sludge, a city refuse, a peat residue, and a grape debris—were composted, and the changes undergone by their different carbon fractions during their composting and maturation were studied. In most cases a decrease in carbon fractions during the composting and maturation processes was observed. The extractable carbon, however, increased during maturation. Organic matter mineralization was greater in the composts with city refuse than in those with sewage sludge. The samples with peat residue showed the lowest decreases in carbon fractions. During maturation, an increase of humiclike fraction was observed, which was reflected by a decrease in the soluble carbon-precipitated carbon ratio at pH 2. Water-soluble carbon was the carbon fraction most easily degradable by microorganisms, and its amount correlated significantly with composting time in all the samples.

  12. Hematite Core Nanoparticles with Carbon Shell: Potential for Environmentally Friendly Production from Iron Mining Sludge

    NASA Astrophysics Data System (ADS)

    Stević, Dragana; Mihajlović, Dijana; Kukobat, Radovan; Hattori, Yoshiyuki; Sagisaka, Kento; Kaneko, Katsumi; Atlagić, Suzana Gotovac

    2016-08-01

    Hematite nanoparticles with amorphous, yet relatively uniform carbon shell, were produced based exclusively on the waste sludge from the iron mine as the raw material. The procedure for acid digestion-based purification of the sludge with the full recovery of acid vapors and the remaining non-toxic rubble is described. Synthesis of the hematite nanoparticles was performed by the arrested precipitation method with cationic surfactant. The particles were thoroughly characterized and the potential of their economical production for the battery industry is indicated.

  13. Electron Spectroscopy Studies of Iron, Iron Sulfides and Supported Iron Surfaces: Chemisorption of Simple Gases.

    NASA Astrophysics Data System (ADS)

    Lee, Yiu Chung

    EELS was used to investigate the chemisorption of oxygen and carbon on iron. The EELS spectra of oxidized iron show characteristic features with strong enhancement of the interband transitions involving the Fe 3d band (4.6 and 7.5 eV) and moderate enhancement of the M(,2,3) transition doublet (54.4 and 58.2 eV). The changes in the electron energy loss structures with an overlayer of graphitic or carbidic carbon were investigated. The adsorption and growth of iron on Ni(100) has been studied using the combined techniques of LEED and EELS. Initially iron grows by a layer-by-layer mechanism for the first few layers. High iron coverages result in the observation of complex LEED patterns with satellites around the main (1 x 1) diffraction sports. This is due to the formation of b.c.c. Fe(110) crystallites arranged in domains with different orientations. EELS studies show the presence of three stages in the growth of iron on Ni(100): low-coverage, film-like and bulk-like. Auger and EELS were used to study the iron sulfide (FeS(,2), Fe(,7)S(,8) and FeS) surfaces. A characteristic M(,2,3) VV Auger doublet with a separation of 5.0 eV was observed on the sulfides. An assignment of the electron energy loss peaks was made based on the energy dependence of the loss peaks and previous photoemission results. The effect of argon ion bombardment was studied. Peaks with strong iron and sulfur character were observed. Heating the damaged sulfides results in reconstruction of the sulfide surfaces. The reactions of the sulfides with simple gases, such as H(,2), CO, CH(,4), C(,2)H(,4), NH(,3) and O(,2) were also studied. Using XPS, the chemisorption of SO(,2) on CaO(100) has been studied. The chemical state of sulfur has been identified as that of sulfate. The kinetics of SO(,2) chemisorption on CaO are discussed. The binding states of Fe and Na on CaO were determined to be Fe('2+) and Na('+) respectively. At low Fe or Na coverages (< 0.5 ML), there is a large increase in the rate of

  14. Organic carbonates: experiment and ab initio calculations for prediction of thermochemical properties.

    PubMed

    Verevkin, Sergey P; Emel'yanenko, Vladimir N; Kozlova, Svetlana A

    2008-10-23

    This work has been undertaken in order to obtain data on thermodynamic properties of organic carbonates and to revise the group-additivity values necessary for predicting their standard enthalpies of formation and enthalpies of vaporization. The standard molar enthalpies of formation of dibenzyl carbonate, tert-butyl phenyl carbonate, and diphenyl carbonate were measured using combustion calorimetry. Molar enthalpies of vaporization of these compounds were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. Molar enthalpy of sublimation of diphenyl carbonate was measured in the same way. Ab initio calculations of molar enthalpies of formation of organic carbonates have been performed using the G3MP2 method, and results are in excellent agreement with the available experiment. Then the group-contribution method has been developed to predict values of the enthalpies of formation and enthalpies of vaporization of organic carbonates.

  15. New insights into iron deficiency and iron deficiency anemia.

    PubMed

    Camaschella, Clara

    2017-07-01

    Recent advances in iron metabolism have stimulated new interest in iron deficiency (ID) and its anemia (IDA), common conditions worldwide. Absolute ID/IDA, i.e. the decrease of total body iron, is easily diagnosed based on decreased levels of serum ferritin and transferrin saturation. Relative lack of iron in specific organs/tissues, and IDA in the context of inflammatory disorders, are diagnosed based on arbitrary cut offs of ferritin and transferrin saturation and/or marker combination (as the soluble transferrin receptor/ferritin index) in an appropriate clinical context. Most ID patients are candidate to traditional treatment with oral iron salts, while high hepcidin levels block their absorption in inflammatory disorders. New iron preparations and new treatment modalities are available: high-dose intravenous iron compounds are becoming popular and indications to their use are increasing, although long-term side effects remain to be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Iron Containing Metal-Organic Frameworks: Structure, Synthesis, and Applications in Environmental Remediation.

    PubMed

    Liu, Xiaocheng; Zhou, Yaoyu; Zhang, Jiachao; Tang, Lin; Luo, Lin; Zeng, Guangming

    2017-06-21

    Metal-organic frameworks (MOFs) with Fe content are gradually developing into an independent branch in environmental remediation, requiring economical, effective, low-toxicity strategies to the complete procedure. In this review, recent advancements in the structure, synthesis, and environmental application focusing on the mechanism are presented. The unique structure of novel design proposed specific characteristics of different iron-containing MOFs with potential innovation. Synthesis of typical MILs, NH 2 -MILs and MILs based materials reveal the basis and defect of the current method, indicating the optimal means for the actual requirements. The adsorption of various contamination with multiple interaction as well as the catalytic degradation over radicals or electron-hole pairs are reviewed. This review implied considerable prospects of iron-containing MOFs in the field of environment and a more comprehensive cognition into the challenges and potential improvement.

  17. Iron and vegetarian diets.

    PubMed

    Saunders, Angela V; Craig, Winston J; Baines, Surinder K; Posen, Jennifer S

    2013-08-19

    Vegetarians who eat a varied and well balanced diet are not at any greater risk of iron deficiency anaemia than non-vegetarians. A diet rich in wholegrains, legumes, nuts, seeds, dried fruits, iron-fortified cereals and green leafy vegetables provides an adequate iron intake. Vitamin C and other organic acids enhance non-haem iron absorption, a process that is carefully regulated by the gut. People with low iron stores or higher physiological need for iron will tend to absorb more iron and excrete less. Research to date on iron absorption has not been designed to accurately measure absorption rates in typical Western vegetarians with low ferritin levels.

  18. Organic carbon stock modelling for the quantification of the carbon sinks in terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Durante, Pilar; Algeet, Nur; Oyonarte, Cecilio

    2017-04-01

    Given the recent environmental policies derived from the serious threats caused by global change, practical measures to decrease net CO2 emissions have to be put in place. Regarding this, carbon sequestration is a major measure to reduce atmospheric CO2 concentrations within a short and medium term, where terrestrial ecosystems play a basic role as carbon sinks. Development of tools for quantification, assessment and management of organic carbon in ecosystems at different scales and management scenarios, it is essential to achieve these commitments. The aim of this study is to establish a methodological framework for the modeling of this tool, applied to a sustainable land use planning and management at spatial and temporal scale. The methodology for carbon stock estimation in ecosystems is based on merger techniques between carbon stored in soils and aerial biomass. For this purpose, both spatial variability map of soil organic carbon (SOC) and algorithms for calculation of forest species biomass will be created. For the modelling of the SOC spatial distribution at different map scales, it is necessary to fit in and screen the available information of soil database legacy. Subsequently, SOC modelling will be based on the SCORPAN model, a quantitative model use to assess the correlation among soil-forming factors measured at the same site location. These factors will be selected from both static (terrain morphometric variables) and dynamic variables (climatic variables and vegetation indexes -NDVI-), providing to the model the spatio-temporal characteristic. After the predictive model, spatial inference techniques will be used to achieve the final map and to extrapolate the data to unavailable information areas (automated random forest regression kriging). The estimated uncertainty will be calculated to assess the model performance at different scale approaches. Organic carbon modelling of aerial biomass will be estimate using LiDAR (Light Detection And Ranging

  19. The interaction of natural organic matter with iron in a wetland (Tennessee Park, Colorado) receiving acid mine drainage

    USGS Publications Warehouse

    Peiffer, Stefan; Walton-Day, Katherine; Macalady, Donald L.

    1999-01-01

    Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

  20. Impact of carbon, oxygen and sulfur content of microscale zerovalent iron particles on its reactivity towards chlorinated aliphatic hydrocarbons.

    PubMed

    Velimirovic, Milica; Larsson, Per-Olof; Simons, Queenie; Bastiaens, Leen

    2013-11-01

    Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Isolation of iron bacteria from terrestrial and aquatic environments

    NASA Astrophysics Data System (ADS)

    Schmidt, Bertram; Szewzyk, Ulrich

    2010-05-01

    Bacteria, which are capable of iron oxidation or at least iron deposition are widely distributed in environments where zones of dissolved ferrous iron and oxygen gradients are overlapping [1]. They take part in the biological cycling of iron and influence other cycles of elements for example carbon [2]. Manganese can be used for similar metabolic purposes as iron, because it can be biologically oxidized by chemolithotrophs or can be reduced by respirating bacteria as well [3, 4]. Bacterial activity is responsible for the accumulation of ferric iron compounds in their surroundings. The formation of bog ore is a well known example for a soil horizon, with an extreme enrichment of biogenic ferric iron [5]. We focused on the isolation of neutrophilic iron bacteria and bacteria capable of manganese oxidation. We used samples from Tierra del Fuego (Argentina) the National Park "Unteres Odertal" (Germany) and Berlin ground water wells. Microscopic examination of the samples revealed a considerable diversity of iron encrusted structures of bacterial origin. Most of these morphologic types are already well known. The taxonomic classification of many of these organisms is based on morphologic features and is not reliable compared to recent methods of molecular biology. That is mainly due to the fact, that most of these bacteria are hardly culturable or do not show their characteristic morphologic features under culture conditions. We established a collection of more than 300 iron depositing strains. Phylogenetic analyses showed that we have many yet uncultured strains in pure culture. We obtained many isolates which form distinct branches within long known iron bacteria groups like the Sphaerotilus-Leptothrix cluster. But some of the strains belong to groups, which have not yet been associated with iron oxidation activity. The strains deposit high amounts of oxidized iron and manganese compounds under laboratory conditions. However it is unclear if these precipitations are

  2. Microbial Breakdown of Organic Carbon in the Diverse Sediments of Guaymas Basin

    NASA Astrophysics Data System (ADS)

    Hoarfrost, A.; Snider, R.; Arnosti, C.

    2015-12-01

    Guaymas Basin is characterized by sediments under conditions ranging from hemipelagic to hydrothermal. This wide range in geochemical contexts results in diverse microbial communities that may have varying abilities to access organic matter. We can address these functional differences by comparing enzyme activities initializing the breakdown of organic matter across these sediment types; however, previous direct measurements of the extracellular hydrolysis of complex organic carbon in sediments are sparse. We measured this first step of heterotrophic processing of organic matter in sediments at 5-10cm and 55-60cm depth from a wide range of environmental settings in Guaymas Basin. Sediment sources included sulfidic seeps on the Sonora Margin, hemipelagic ridge flank sediments, and hydrothermically altered Sonora Margin sediments bordering a methane seep site. Hydrolysis of organic substrates varied by depth and by sediment source, but despite high energy potential and organic carbon load in sulfidic sediments, activity was not highest where hydrothermal influence was highest. These results suggest that heterotrophic breakdown of organic carbon in Guaymas Basin sediments may be sensitive to factors including varying composition of organic carbon available in different sediment types, or differences in microbial community capacities to access specific organic substrates.

  3. Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols.

    PubMed

    Thomas, Daniel A; Coggon, Matthew M; Lignell, Hanna; Schilling, Katherine A; Zhang, Xuan; Schwantes, Rebecca H; Flagan, Richard C; Seinfeld, John H; Beauchamp, J L

    2016-11-15

    The complexation of iron(III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron(II) and the carbon dioxide anion radical. Importantly, iron(III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown. This study utilizes glycolaldehyde as a model organic species to examine the oxidation pathways and evolution of organic aerosol initiated by the photodissociation of aqueous iron(III) oxalate complexes. Hanging droplets (radius 1 mm) containing iron(III), oxalic acid, glycolaldehyde, and ammonium sulfate (pH ∼3) are exposed to irradiation at 365 nm and sampled at discrete time points utilizing field-induced droplet ionization mass spectrometry (FIDI-MS). Glycolaldehyde is found to undergo rapid oxidation to form glyoxal, glycolic acid, and glyoxylic acid, but the formation of high molecular weight oligomers is not observed. For comparison, particle-phase experiments conducted in a laboratory chamber explore the reactive uptake of gas-phase glycolaldehyde onto aqueous seed aerosol containing iron and oxalic acid. The presence of iron oxalate in seed aerosol is found to inhibit aerosol growth. These results suggest that photodissociation of iron(III) oxalate can lead to the formation of volatile oxidation products in tropospheric aqueous aerosols.

  4. Speleothem records of acid sulphate deposition and organic carbon mobilisation

    NASA Astrophysics Data System (ADS)

    Wynn, Peter; Fairchild, Ian; Bourdin, Clement; Baldini, James; Muller, Wolfgang; Hartland, Adam; Bartlett, Rebecca

    2017-04-01

    Dramatic increases in measured surface water DOC in recent decades have been variously attributed to either temperature rise, or destabilisation of long-term soil carbon pools following sulphur peak emissions status. However, whilst both drivers of DOC dynamics are plausible, they remain difficult to test due to the restricted nature of the available records of riverine DOC flux (1978 to present), and the limited availability of SO2 emissions inventory data at the regional scale. Speleothems offer long term records of both sulphur and carbon. New techniques to extract sulphur concentrations and isotopes from speleothem calcite have enabled archives of pollution history and environmental acidification to be reconstructed. Due to the large dynamic range in sulphur isotopic values from end member sources (marine aerosol +21 ‰ to continental biogenic emissions -30 ‰) and limited environmental fractionation under oxidising conditions, sulphur isotopes form an ideal tracer of industrial pollution and environmental acidification in the palaeo-record. We couple this acidification history to the carbon record, using organic matter fluorescence and trace metals. Trace metal ratios and abundance can be used to infer the type and size of organic ligand and are therefore sensitive to changes in temperature as a driver of organic carbon processing and biodegradation. This allows fluorescent properties and ratios of trace metals in speleothem carbonate to be used to represent both the flux of organic carbon into the cave as well as the degradation pathway. Here we present some of the first results of this work, exploring sulphur acidification as a mechanistic control on carbon solubility and export throughout the twentieth century.

  5. Distribution of Organic Carbon in the Sediments of Xinxue River and the Xinxue River Constructed Wetland, China.

    PubMed

    Cao, Qingqing; Wang, Renqing; Zhang, Haijie; Ge, Xiuli; Liu, Jian

    2015-01-01

    Wetland ecosystems are represented as a significant reservoir of organic carbon and play an important role in mitigating the greenhouse effect. In order to compare the compositions and distribution of organic carbon in constructed and natural river wetlands, sediments from the Xinxue River Constructed Wetland and the Xinxue River, China, were sampled at two depths (0-15 cm and 15-25 cm) in both upstream and downstream locations. Three types of organic carbon were determined: light fraction organic carbon, heavy fraction organic carbon, and dissolved organic carbon. The results show that variations in light fraction organic carbon are significantly larger between upstream and downstream locations than they are between the two wetland types; however, the opposite trend is observed for the dissolved organic carbon. There are no significant differences in the distribution of heavy fraction organic carbon between the discrete variables (e.g., between the two depths, the two locations, or the two wetland types). However, there are significant cross-variable differences; for example, the distribution patterns of heavy fraction organic carbon between wetland types and depths, and between wetland types and locations. Correlation analysis reveals that light fraction organic carbon is positively associated with light fraction nitrogen in both wetlands, while heavy fraction organic carbon is associated with both heavy fraction nitrogen and the moisture content in the constructed wetland. The results of this study demonstrate that the constructed wetland, which has a relatively low background value of heavy fraction organic carbon, is gradually accumulating organic carbon of different types, with the level of accumulation dependent on the balance between carbon accumulation and carbon decomposition. In contrast, the river wetland has relatively stable levels of organic carbon.

  6. Site-Specific Carbon Isotopes in Organics

    NASA Astrophysics Data System (ADS)

    Piasecki, A.; Eiler, J. M.

    2012-12-01

    Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 μm. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural

  7. Black Carbon in Estuarine (Coastal) High-molecular-weight Dissolved Organic Matter

    NASA Technical Reports Server (NTRS)

    Mannino, Antonio; Harvey, H. Rodger

    2003-01-01

    Dissolved organic matter (DOM) in the ocean constitutes one of the largest pools of organic carbon in the biosphere, yet much of its composition is uncharacterized. Observations of black carbon (BC) particles (by-products of fossil fuel combustion and biomass burning) in the atmosphere, ice, rivers, soils and marine sediments suggest that this material is ubiquitous, yet the contribution of BC to the ocean s DOM pool remains unknown. Analysis of high-molecular-weight DOM isolated from surface waters of two estuaries in the northwest Atlantic Ocean finds that BC is a significant component of DOM, suggesting that river-estuary systems are important exporters of BC to the ocean through DOM. We show that BC comprises 4-7% of the dissolved organic carbon (DOC) at coastal ocean sites, which supports the hypothesis that the DOC pool is the intermediate reservoir in which BC ages prior to sedimentary deposition. Flux calculations suggest that BC could be as important as vascular plant-derived lignin in terms of carbon inputs to the ocean. Production of BC sequesters fossil fuel- and biomass-derived carbon into a refractory carbon pool. Hence, BC may represent a significant sink for carbon to the ocean.

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

    DOE PAGES

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

    2016-01-16

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

  9. Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

    USGS Publications Warehouse

    Pohlman, John; Waite, William F.; Bauer, James E.; Osburn, Christopher L.; Chapman, N. Ross

    2011-01-01

    Marine sediments contain about 500–10,000 Gt of methane carbon1, 2, 3, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined1, 4, but it releases relatively little methane to the ocean and atmosphere5. Sedimentary microbes convert most of the dissolved methane to carbon dioxide6, 7. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use Δ14C and δ13C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000–6,000 year age of dissolved organic carbon in the deep ocean8, and provide reduced organic matter and energy to deep-ocean microbial communities.

  10. Carbon-carbon cylinder block

    NASA Technical Reports Server (NTRS)

    Ransone, Philip O. (Inventor)

    1995-01-01

    A lightweight cylinder block composed of carbon-carbon is disclosed. The use of carbon-carbon over conventional materials, such as cast iron or aluminum, reduces the weight of the cylinder block and improves thermal efficiency of the internal combustion reciprocating engine. Due to the negligible coefficient of thermal expansion and unique strength at elevated temperatures of carbon-carbon, the piston-to-cylinder wall clearance can be small, especially when the carbon-carbon cylinder block is used in conjunction with a carbon-carbon piston. Use of the carbon-carbon cylinder has the effect of reducing the weight of other reciprocating engine components allowing the piston to run at higher speeds and improving specific engine performance.

  11. Proxies for soil organic carbon derived from remote sensing

    NASA Astrophysics Data System (ADS)

    Rasel, S. M. M.; Groen, T. A.; Hussin, Y. A.; Diti, I. J.

    2017-07-01

    The possibility of carbon storage in soils is of interest because compared to vegetation it contains more carbon. Estimation of soil carbon through remote sensing based techniques can be a cost effective approach, but is limited by available methods. This study aims to develop a model based on remotely sensed variables (elevation, forest type and above ground biomass) to estimate soil carbon stocks. Field observations on soil organic carbon, species composition, and above ground biomass were recorded in the subtropical forest of Chitwan, Nepal. These variables were also estimated using LiDAR data and a WorldView 2 image. Above ground biomass was estimated from the LiDAR image using a novel approach where the image was segmented to identify individual trees, and for these trees estimates of DBH and Height were made. Based on AIC (Akaike Information Criterion) a regression model with above ground biomass derived from LiDAR data, and forest type derived from WorldView 2 imagery was selected to estimate soil organic carbon (SOC) stocks. The selected model had a coefficient of determination (R2) of 0.69. This shows the scope of estimating SOC with remote sensing derived variables in sub-tropical forests.

  12. Ferroportin-mediated iron transport: expression and regulation

    PubMed Central

    Ward, Diane; Kaplan, Jerry

    2013-01-01

    The distinguishing feature between iron homeostasis in single versus multicellular organisms is the need for multicellular organisms to transfer iron from sites of absorption to sites of utilization and storage. Ferroportin is the only known iron exporter and ferroportin plays an essential role in the export of iron from cells to blood. Ferroportin can be regulated at many different levels including transcriptionally, post-transcriptionally, through mRNA stability and post-translationally, through protein turnover. Additionally, ferroportin may be regulated in both cell-dependent and cell-autonomous fashions. Regulation of ferroportin is critical for iron homeostasis as alterations in ferroportin may result in either iron deficiency or iron overload. PMID:22440327

  13. Iron-impregnated granular activated carbon for arsenic removal from drinking water

    NASA Astrophysics Data System (ADS)

    Chang, Qigang

    A new multi-step iron impregnation method was developed in this study to impregnate GAC with a high amount of iron that possesses desired characteristics: stable, even distribution, and high arsenic adsorption capacity. Research was carried out to investigate the impact of the amount of impregnated iron on arsenic adsorption properties: capacity, affinity, and kinetics. Fe-GACs were characterized in terms of the amount, stability, distribution, morphology, and species of impregnated iron. It was found that a high amount of iron was stably impregnated in GAC. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) analysis demonstrated that the impregnated iron was evenly distributed on the internal surface of GAC. Impregnated iron formed nano-size particles and existed in both crystalline (akaganeite) and amorphous iron. Arsenic adsorption tests were conducted using Fe-GACs with iron content of 1.64--28.90% in a low arsenic concentration that is typical for drinking water treatment. The amount of impregnated iron affects arsenic maximum adsorption capacity (qm) but has little impact on the Langmuir constant h (the affinity of adsorbent for adsorbate). The qm for both As(V) and As(III) adsorptions increased significantly with increase of the amount of impregnated iron up to 13.59%. Further increase of iron amounts caused a gradual decrease of qm for As(V). BET analysis indicated impregnated iron possesses the highest surface area at iron content of 13.59%. A new second-order kinetic model was developed to investigate the impact of the amounts of impregnated iron on arsenic adsorption kinetics. With iron content increased from 1.64% to 28.90%, the intrinsic adsorption rate constants reduced from 4.6x10-2 1/hr to 1.18x10 -3 1/hr, which indicates that impregnated iron slows arsenic intraparticle diffusion rate in Fe-GAC. The decreased arsenic intraparticle diffusion rate was most likely caused by reduced pore size of Fe-GACs. Column tests were

  14. MIL-100 derived nitrogen-embodied carbon shells embedded with iron nanoparticles

    NASA Astrophysics Data System (ADS)

    Mao, Chengyu; Kong, Aiguo; Wang, Yuan; Bu, Xianhui; Feng, Pingyun

    2015-06-01

    The use of metal-organic frameworks (MOFs) as templates and precursors to synthesize new carbon materials with controllable morphology and pre-selected heteroatom doping holds promise for applications as efficient non-precious metal catalysts. Here, we report a facile pyrolysis pathway to convert MIL-100 into nitrogen-doped carbon shells encapsulating Fe nanoparticles in a comparative study involving multiple selected nitrogen sources. The hierarchical porous architecture, embedded Fe nanoparticles, and nitrogen decoration endow this composite with a superior oxygen reduction activity. Furthermore, the excellent durability and high methanol tolerance even outperform the commercial Pt-C catalyst.The use of metal-organic frameworks (MOFs) as templates and precursors to synthesize new carbon materials with controllable morphology and pre-selected heteroatom doping holds promise for applications as efficient non-precious metal catalysts. Here, we report a facile pyrolysis pathway to convert MIL-100 into nitrogen-doped carbon shells encapsulating Fe nanoparticles in a comparative study involving multiple selected nitrogen sources. The hierarchical porous architecture, embedded Fe nanoparticles, and nitrogen decoration endow this composite with a superior oxygen reduction activity. Furthermore, the excellent durability and high methanol tolerance even outperform the commercial Pt-C catalyst. Electronic supplementary information (ESI) available: Material synthesis and elemental analysis, electrochemistry measurements, and additional figures. See DOI: 10.1039/c5nr02346g

  15. Methods to Predict Stresses in Cutting Inserts Brazed Using Iron-Carbon Brazing Alloy

    NASA Astrophysics Data System (ADS)

    Konovodov, V. V.; Valentov, A. V.; Retuynskiy, O. Yu; Esekuev, Sh B.

    2016-04-01

    This work describes a method for predicting residual and operating stresses in a flat-form tool insert made of tungsten free carbides brazed using iron-carbon alloy. According to the studies’ results it is concluded that the recommendations relating to the limitation of a melting point of tool brazing alloys (950-1100°C according to different data) are connected with a negative impact on tools as a composite made of dissimilar materials rather than on hard alloys as a tool material. Due to the cooling process stresses inevitably occur in the brazed joint of dissimilar materials, and these stresses increase with the higher solidification temperature of the brazing alloy.

  16. Ferritin accumulation under iron scarcity in Drosophila iron cells.

    PubMed

    Mehta, A; Deshpande, A; Bettedi, L; Missirlis, F

    2009-10-01

    Ferritins are highly stable, multi-subunit protein complexes with iron-binding capacities that reach 4500 iron atoms per ferritin molecule. The strict dependence of cellular physiology on an adequate supply of iron cofactors has likely been a key driving force in the evolution of ferritins as iron storage molecules. The insect intestine has long been known to contain cells that are responsive to dietary iron levels and a specialized group of "iron cells" that always accumulate iron-loaded ferritin, even when no supplementary iron is added to the diet. Here, we further characterize ferritin localization in Drosophila melanogaster larvae raised under iron-enriched and iron-depleted conditions. High dietary iron intake results in ferritin accumulation in the anterior midgut, but also in garland (wreath) cells and in pericardial cells, which together filter the circulating hemolymph. Ferritin is also abundant in the brain, where levels remain unaltered following dietary iron chelation, a treatment that depletes ferritin from the aforementioned tissues. We attribute the stability of ferritin levels in the brain to the function of the blood-brain barrier that may shield this organ from systemic iron fluctuations. Most intriguingly, our dietary manipulations demonstrably iron-depleted the iron cells without a concomitant reduction in their production of ferritin. Therefore, insect iron cells may constitute an exception from the evolutionary norm with respect to iron-dependent ferritin regulation. It will be of interest to decipher both the physiological purpose served and the mechanism employed to untie ferritin regulation from cellular iron levels in this cell type.

  17. The carbon cycle and associated redox processes through time

    PubMed Central

    Hayes, John M; Waldbauer, Jacob R

    2006-01-01

    Earth's biogeochemical cycle of carbon delivers both limestones and organic materials to the crust. In numerous, biologically catalysed redox reactions, hydrogen, sulphur, iron, and oxygen serve prominently as electron donors and acceptors. The progress of these reactions can be reconstructed from records of variations in the abundance of 13C in sedimentary carbonate minerals and organic materials. Because the crust is always receiving new CO2 from the mantle and a portion of it is being reduced by photoautotrophs, the carbon cycle has continuously released oxidizing power. Most of it is represented by Fe3+ that has accumulated in the crust or been returned to the mantle via subduction. Less than 3% of the estimated, integrated production of oxidizing power since 3.8 Gyr ago is represented by O2 in the atmosphere and dissolved in seawater. The balance is represented by sulphate. The accumulation of oxidizing power can be estimated from budgets summarizing inputs of mantle carbon and rates of organic-carbon burial, but levels of O2 are only weakly and indirectly coupled to those phenomena and thus to carbon-isotopic records. Elevated abundances of 13C in carbonate minerals ca 2.3 Gyr old, in particular, are here interpreted as indicating the importance of methanogenic bacteria in sediments rather than increased burial of organic carbon. PMID:16754608

  18. Distribution of Organic Carbon in the Sediments of Xinxue River and the Xinxue River Constructed Wetland, China

    PubMed Central

    Cao, Qingqing; Wang, Renqing; Zhang, Haijie; Ge, Xiuli; Liu, Jian

    2015-01-01

    Wetland ecosystems are represented as a significant reservoir of organic carbon and play an important role in mitigating the greenhouse effect. In order to compare the compositions and distribution of organic carbon in constructed and natural river wetlands, sediments from the Xinxue River Constructed Wetland and the Xinxue River, China, were sampled at two depths (0–15 cm and 15–25 cm) in both upstream and downstream locations. Three types of organic carbon were determined: light fraction organic carbon, heavy fraction organic carbon, and dissolved organic carbon. The results show that variations in light fraction organic carbon are significantly larger between upstream and downstream locations than they are between the two wetland types; however, the opposite trend is observed for the dissolved organic carbon. There are no significant differences in the distribution of heavy fraction organic carbon between the discrete variables (e.g., between the two depths, the two locations, or the two wetland types). However, there are significant cross-variable differences; for example, the distribution patterns of heavy fraction organic carbon between wetland types and depths, and between wetland types and locations. Correlation analysis reveals that light fraction organic carbon is positively associated with light fraction nitrogen in both wetlands, while heavy fraction organic carbon is associated with both heavy fraction nitrogen and the moisture content in the constructed wetland. The results of this study demonstrate that the constructed wetland, which has a relatively low background value of heavy fraction organic carbon, is gradually accumulating organic carbon of different types, with the level of accumulation dependent on the balance between carbon accumulation and carbon decomposition. In contrast, the river wetland has relatively stable levels of organic carbon. PMID:26230255

  19. On the location of acid-hydrolysable carbon in lunar soil fines

    NASA Technical Reports Server (NTRS)

    Fallick, A. E.; Wright, I. P.; Pillinger, C. T.; Stephenson, A.; Morris, R. V.

    1982-01-01

    Soil fines exposed on the lunar surface accumulate small metallic iron particles and solar wind-derived carbon. In previous work, it has been suggested that an intimate association exists between one particular carbon phase, hydrolysable carbon, and very fine iron droplets, where the carbon is in solid solution in the iron. The earlier hypothesis of a constant carbon in iron concentration across a broad range of droplet sizes is testable by combining hydrolysable carbon determinations with a variety of magnetic measurements sensitive to different droplet diameters. New measurements of ferromagnetic resonance response on density and magnetic separates from size fractions of soil 12023 are interpreted as evidence that hydrolysable carbon is preferentially associated with the larger, magnetically stable single-domain iron particles rather than with the smaller superparamagnetic droplets. For the former, there is a quite uniform ratio of iron to carbon both within a series of separates from a single soil, and among soils of widely varying FeO content.

  20. ORCHIDEE-SOM: modeling soil organic carbon (SOC) and dissolved organic carbon (DOC) dynamics along vertical soil profiles in Europe

    NASA Astrophysics Data System (ADS)

    Camino-Serrano, Marta; Guenet, Bertrand; Luyssaert, Sebastiaan; Ciais, Philippe; Bastrikov, Vladislav; De Vos, Bruno; Gielen, Bert; Gleixner, Gerd; Jornet-Puig, Albert; Kaiser, Klaus; Kothawala, Dolly; Lauerwald, Ronny; Peñuelas, Josep; Schrumpf, Marion; Vicca, Sara; Vuichard, Nicolas; Walmsley, David; Janssens, Ivan A.

    2018-03-01

    Current land surface models (LSMs) typically represent soils in a very simplistic way, assuming soil organic carbon (SOC) as a bulk, and thus impeding a correct representation of deep soil carbon dynamics. Moreover, LSMs generally neglect the production and export of dissolved organic carbon (DOC) from soils to rivers, leading to overestimations of the potential carbon sequestration on land. This common oversimplified processing of SOC in LSMs is partly responsible for the large uncertainty in the predictions of the soil carbon response to climate change. In this study, we present a new soil carbon module called ORCHIDEE-SOM, embedded within the land surface model ORCHIDEE, which is able to reproduce the DOC and SOC dynamics in a vertically discretized soil to 2 m. The model includes processes of biological production and consumption of SOC and DOC, DOC adsorption on and desorption from soil minerals, diffusion of SOC and DOC, and DOC transport with water through and out of the soils to rivers. We evaluated ORCHIDEE-SOM against observations of DOC concentrations and SOC stocks from four European sites with different vegetation covers: a coniferous forest, a deciduous forest, a grassland, and a cropland. The model was able to reproduce the SOC stocks along their vertical profiles at the four sites and the DOC concentrations within the range of measurements, with the exception of the DOC concentrations in the upper soil horizon at the coniferous forest. However, the model was not able to fully capture the temporal dynamics of DOC concentrations. Further model improvements should focus on a plant- and depth-dependent parameterization of the new input model parameters, such as the turnover times of DOC and the microbial carbon use efficiency. We suggest that this new soil module, when parameterized for global simulations, will improve the representation of the global carbon cycle in LSMs, thus helping to constrain the predictions of the future SOC response to global

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