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Sample records for deposition stable carbons

  1. Benthic foraminiferal stable isotope record of organic carbon fluxes during deposition of Mediterranean sapropel S1

    NASA Astrophysics Data System (ADS)

    Theodor, Marc; Schmiedl, Gerhard; Mackensen, Andreas

    2016-04-01

    We integrated Late Glacial to Holocene stable isotope records for different epi- and endobenthic foraminifera from the Mediterranean Sea in order to document the sequence of environmental changes across formation of the most recent sapropel S1. The stable carbon isotope record of epibenthic taxa corroborates results from model experiments indicating a Late Glacial onset of deep-water stagnation with short-term reventilation events during cold intervals of the Heinrich event 1, the Younger Dryas, and the 8.2 event. The stable carbon isotope difference between epi- and shallow endobenthic foraminifera exhibits marked temporal fluctuations linked to microhabitat shifts and changes in organic matter fluxes. We generated a transfer function for organic carbon fluxes based on a correlation between the stable carbon isotope signature of modern benthic foraminifera and observed organic carbon flux rates from different Mediterranean basins. Application of this transfer function to the down-core data reveals generally elevated organic matter fluxes during the Last Glacial Maximum and the Younger Dryas, while values drop significantly during the Bølling-Allerød interstadial and with onset of the Holocene. Our results support a scenario where average organic matter fluxes in the eastern Mediterranean Sea were not significantly enhanced during formation of sapropel S1. Instead, our data corroborate earlier results from benthic foraminiferal faunal successions and model experiments suggesting that sufficient amounts of organic matter are buried under oligotrophic conditions in an intermittently hypoxic water column.

  2. Different carbon reservoirs of auriferous fluids in African Archean and Proterozoic gold deposits? Constraints from stable carbon isotopic compositions of quartz-hosted CO2-rich fluid inclusions

    NASA Astrophysics Data System (ADS)

    Lüders, Volker; Klemd, Reiner; Oberthür, Thomas; Plessen, Birgit

    2015-04-01

    Stable carbon (and when present, nitrogen) isotope ratios of fluid inclusions in quartz from selected gold deposits in Ghana and Zimbabwe have been analyzed using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS) in order to constrain possible sources of the auriferous fluids. The study revealed a striking difference in stable carbon isotopic compositions of CO2 in quartz-hosted fluid inclusions from Archean and Paleoproterozoic orogenic gold deposits and points to diverse sources of CO2 in the studied deposits. Whether this finding can be generalized for other Archean and Proterozoic orogenic gold deposits worldwide remains open. However, a significant CO2 contribution by mantle degassing can be ruled out for every deposit studied. Devolatilization of greenstone belt rocks is the most likely source for CO2 in some Archean Au deposits in Zimbabwe, whereas CO2 in Proterozoic vein-type Au deposits in the West African Craton is most likely derived from Corg-bearing metasedimentary rocks. The δ13CCO2 values of high-density CO2-rich, water-poor inclusions hosted in quartz pebbles from the world-class Au-bearing conglomerate deposits at Tarkwa (Ghana) differ considerably from the δ13CCO2 values of similar high-density CO2-rich inclusions in vein quartz from the giant Ashanti deposit (Ghana) and disprove the idea of derivation of the Tarkwaian quartz (and gold?) from an older equivalent to the Ashanti vein-type gold deposit.

  3. Precipitation source inferred from stable isotopic composition of Pleistocene groundwater and carbonate deposits in the western desert of Egypt.

    SciTech Connect

    Sultan, M.; Sturchio, N.; Hassan, F. A.; Abdel, M.; Hamdan, R.; Mahmood, A. M.; Alfy, Z. E.; Stein, T.; Environmental Research; Univ. Coll. London; Cairo Univ.; Ain Shams Univ.; Egyptian Geological survey and Mining Authority; Washington Univ.

    1997-01-01

    An Atlantic source of precipitation can be inferred from stable isotopic data (H and O) for fossil groundwaters and uranium-series-dated carbonate spring deposits from oases in the Western Desert of Egypt. In the context of available stable isotopic data for fossil groundwaters throughout North Africa, the observed isotopic depletions ({delta}D -72 to -81{per_thousand}; {delta}{sup 18}O -10.6 to -11.5{per_thousand}) of fossil ({ge}32,000 yr B.P.) groundwaters from the Nubian aquifer are best explained by progressive condensation of water vapor from paleowesterly wet oceanic air masses that traveled across North Africa and operated at least as far back as 450,000 yr before the present. The values of {delta}{sup 18}O (17.1 to 25.9{per_thousand}) for 45,000- to >450,000-yr-old tufas and vein-filling calcite deposits from the Kharga and Farafra Oases are consistent with deposition from groundwaters having oxygen isotopic compositions similar to those of fossil groundwaters sampled recently at these locations.

  4. Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition.

    PubMed

    Liu, Xue-Yan; Xiao, Hua-Yun; Liu, Cong-Qiang; Li, You-Yi; Xiao, Hong-Wei; Wang, Yan-Li

    2010-06-01

    Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and delta13C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but delta13C(moss) became less negative. With measurements of atmospheric CO2 and delta13CO2, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of delta13C(moss) to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.

  5. Multiple ambient hydrolysis deposition of tin oxide into nanoporous carbon to give a stable anode for lithium-ion batteries.

    PubMed

    Raju, Vadivukarasi; Wang, Xingfeng; Luo, Wei; Ji, Xiulei

    2014-06-16

    A novel ambient hydrolysis deposition (AHD) methodology that employs sequential water adsorption followed by a hydrolysis reaction to infiltrate SnO2 nanoparticles into the nanopores of mesoporous carbon in a conformal and controllable manner is introduced. The empty space in the SnO2/C composites can be adjusted by varying the number of AHD cycles. An SnO2/C composite with an intermediate SnO2 loading exhibited an initial specific delithiation capacity of 1054 mAh g(-1) as an anode for Li-ion batteries. The capacity contribution from SnO2 in the composite electrode approaches the theoretical capacity of SnO2 (1494 mAh g(-1)) if both Sn alloying and SnO2 conversion reactions are considered to be reversible. The composite shows a specific capacity of 573 mAh g(-1) after 300 cycles, that is, one of the most stable cycling performances for SnO2/mesoporous carbon composites. The results demonstrated the importance of well-tuned empty space in nanostructured composites to accommodate expansion of the electrode active mass during alloying/dealloying and conversion reactions.

  6. Stable isotope and fluid inclusion studies of carbonate deposits from the Tolfa Mountains mining district (Latium, central Italy)

    USGS Publications Warehouse

    Masi, U.; Ferrini, V.; O'Neil, J.R.; Batchelder, J.N.

    1980-01-01

    Carbon and oxygen isotope analyses were made of representative samples of calcite and quartz from the carbonate deposits in the Tolfa Mountains mining district. Measurements were also made of hydrogen isotope compositions, filling temperatures and salinities of fluid inclusions in these minerals. There are three stages of mineralization at Tolfa. In stage I, characterized by calc-silicate hornfels, the carbonates have relatively high ?? 18O values of 14.5 to 21.6 suggesting a rather low water/rock ratio. ??13C values of -0.3 to 2.1 indicate that appreciable decarbonation or introduction of deep-seated carbon did not occur. Stage II is marked by phanerocrystalline carbonates; ?? 18O values of 13.1 to 20.0 and ??13C values of 0.7 to 5.0 identify them as hydrothermal veins rather than marbles. ?? D values of -56 to -50 for inclusion fluids suggest a possible magmatic component to the hydrothermal fluid. Filling temperatures of coarse-grained samples of Calcite II are 309?? to 362?? C with a salinity range of 5.3 to 7.1 weight percent NaCl. Calculated ??18O values of 11-12 for these fluids are again indicative of low water/rock ratios. The sparry calcites of stage III have ??18O and ??13C values of 8.1 to 12.9 and -1.7 to 3.2, respectively. ?? D values of inclusion fluids are -40 to -33, clearly heavier than in earlier stages and similar to values of modern local ground waters. A salinity measurement of <0.1 weight percent NaCl in a sample of Calcite III is compatible with a relatively unaltered ground water origin for this fluid. Precipitation of the sparry calcite took place at much lower temperatures, around 160?? C. For quartz, ??18O values of 9.3 to 12.4 and ?? D values for inclusions of -53 to -28 are consistent with its late occurrence and paragenetic link with associated carbonates. ?? 1980 Springer-Verlag.

  7. Testing the sensitivity of stable carbon isotopes of sub-fossil Sphagnum cellulose to past climate variability: a two millennia high resolution stable carbon isotope time series from the peat deposit "Dürres Maar", Germany

    NASA Astrophysics Data System (ADS)

    Moschen, Robert; Kühl, Norbert; Peters, Sabrina; Vos, Heinz; Lücke, Andreas

    2010-05-01

    Peat deposits are terrestrial archives of environmental changes and climate dynamics over time. They are widely distributed and cover a large part of the earth's land surface often within human habitat and, thus, form an excellent basis for evaluating ecosystem and climate dynamics by multiple geochemical and biological methods. Records of the stable carbon composition of cellulose separately extracted from selected Sphagnum plant components (δ13CSphagnum) from the kettle-hole type peat deposit of 'Dürres Maar' are presented. Manually separated Sphagnum stems, branches and the small leaves covering Sphagnum branches were used for cellulose extraction and subsequent isotope measurements, because intra-plant δ13CSphagnum variability between different physical components of individual modern plants has been described (Loader et al. 2007). We observed the same isotopic offset between single plant components of sub-fossil Sphagnum plant components which is statistically highly significant and observable down-core (Moschen et al. 2009). Using the size fraction of 355-630 μm, which almost exclusively consists of single Sphagnum leaves, allows to derive environmental and climate signals based on a plant response to external controls, presumably including temperature and relative humidity. Because down-core changes in the ratio of different plant components in the peat profile seem probable, erroneous interpretations of isotope records are likely if no differentiation into single Sphagnum plant components is possible. A high resolution time series of δ13CSphagnum is presented covering the last two millennia, tracing decadal to sub-decadal past environmental and climate dynamics. The thickness of the water film surrounding the chloroplasts of Sphagnum plants has been suggested as the most important factor influencing δ13CSphagnum. This points to bog surface wetness which is primarily driven by precipitation and evaporation temperature as the major control of δ13

  8. Chemical vapor deposition synthesis of near-zigzag single-walled carbon nanotubes with stable tube-catalyst interface

    PubMed Central

    Zhao, Qiuchen; Xu, Ziwei; Hu, Yue; Ding, Feng; Zhang, Jin

    2016-01-01

    Chemical vapor deposition (CVD) growth is regarded as the most promising method for realizing structure-specific single-walled carbon nanotube (SWNT) growth. In the past 20 years, many efforts dedicated to chirality-selective SWNT growth using various strategies have been reported. However, normal CVD growth under constant conditions could not fully optimize the chirality because the randomly formed cap structure allows the nucleation of all types of SWNTs and the chirality of an SWNT is unlikely to be changed during the following elongation process. We report a new CVD process that allows temperature to be periodically changed to vary SWNT chirality multiple times during elongation to build up the energetically preferred SWNT-catalyst interface. With this strategy, SWNTs with small helix angles (less than 10°), which are predicted to have lower interfacial formation energy than others, are enriched up to ~72%. Kinetic analysis of the process suggests a multiple redistribution feature whereby a large chiral angle SWNT tends to reach the near-zigzag chirality step by step with a small chiral angle change at each step, and hence, we named this method “tandem plate CVD.” This method opens a door to synthesizing chirality-selective SWNTs by rational catalyst design. PMID:27386532

  9. Late Holocene stable carbon and nitrogen isotopic variation of bulk organic matter deposited in Blackwood Sinkhole, Abaco, The Bahamas

    NASA Astrophysics Data System (ADS)

    Tamalavage, A.; van Hengstum, P. J.; Louchouarn, P.; Fall, P. L.; Donnelly, J. P.

    2015-12-01

    In the modern climate of the Bahamas, a latitudinal precipitation gradient only allows Pine (Pinus caribaea var. bahamensis) dominated forests to exist on the more mesic (humid) northern islands (Abaco, Andros, New Providence, Grand Bahamas). Previous research suggests that the northern Bahamas underwent dramatic environmental changes in the late Holocene (e.g., waves of human arrival, shifts in terrestrial vegetation and animal extinctions). However, disentangling the timing and relative forcing (climatic vs. anthropogenic) of these changes has proven challenging without high-resolution terrestrial climate records. Recently, a late Holocene decadal to multi-decadal laminated sedimentary record was recovered from Blackwood Sinkhole, on Abaco Island. The bottom of the sinkhole is characterized by anoxic, saline groundwater, while the upper, brackish meteoric lens provides a habitat to fish, algae and other organisms. Here, we present δ13Corg and δ15Norg values of bulk organic matter (OM) taken every cm of the 110 cm core to help elucidate changes in the chemical composition of the source of OM reaching the anoxic sediments of the sinkhole. δ13Corg values change at 812 Cal yrs BP (2s: 931-681 Cal yrs BP, 31.7 cm depth) from -30.5 ± 1.6‰ in the lower 80 cm of the core to -27.6 ± 1.2‰ in the upper 30 cm. There is a synchronous change from more enriched δ15N values, 3.7 ± 1.1‰, in the lower portion of the core, to lower δ15N values (1.9 ± .5‰), in the upper portion of the core. A pollen-based reconstruction of terrestrial vegetation from the same core indicates that these isotopic shifts are concomitant with a shift from a dominance of Arecaceae (Palms) and tropical dry hardwoods below 30 cm, to Pinus and Conocarpus predominance above 30 cm. These results indicate that the source of sedimentary OM deposited into the sinkhole changed coherently with regional landscape change. Biomarker analyses will be used to further identify the role of autochthonous

  10. 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

  11. Multiproxy Holocene paleoclimate records from the southern Peruvian Andes - what new can we learn from the stable carbon isotope composition of high altitude organic matter deposits?

    NASA Astrophysics Data System (ADS)

    Skrzypek, Grzegorz; Engel, Zbyněk

    2015-04-01

    Interpretation of the Central Andean paleoclimate over the last millennia still represents a research challenge demanding deeper studies [1,2]. Several high-resolution paleoclimate proxies for the last 10,000 years have been developed for the northern hemisphere. However, similar proxies are very limited for South America, particularly for high altitudes where, for example, tree-ring chronologies are not available and instrumental records are very limited. Consequently, our knowledge of high altitude climate changes in arid regions of the Peruvian Andes mainly relies on ice-core and lake deposit studies. In our study, we used a new alternative proxy for interpretation of palaeoclimate conditions based on a peat core taken from the Carhuasanta Valley at the foot of Nevado Mismi in the southern Peruvian Andes (15° 30'S, 71° 43'W, 4809m a.s.l.). The stable carbon isotope composition (δ13C) of Distichia peat reflects mainly the relative variation of the mean air temperature during subsequent growing seasons [3], and allows reconstructions of palaeotemperature changes. In contrast, peat organic carbon concentration (C % wt) records mainly wetness in the valley, directly corresponding to the changes in runoff in the upper part of the catchment. The most prominent climate changes recorded in the peat over last 4ka occurred between 3040 and 2750 cal. yrs BP. The initial warming turned to a very rapid cooling to temperatures at least 2° C lower than the mean for the Late Holocene. Initially drier conditions within this event turned to a short wet phase after 2780 cal. yrs BP, when the temperature increased again. This event coincides with significant changes in peat and ice core records in the Central Andes that match the timing of the global climate event around 2.8 cal. ka BP. Climatic conditions in the study area became relatively dry and stable after the event for about 800 years. Highly variable temperatures and humidity prevailed during the last 2000 years, when

  12. Stable isotope analyses of tooth enamel carbonate of large herbivores from the Tugen Hills deposits: Palaeoenvironmental context of the earliest Kenyan hominids

    NASA Astrophysics Data System (ADS)

    Roche, Damien; Ségalen, Loïc; Senut, Brigitte; Pickford, Martin

    2013-11-01

    Understanding shifts in past climatic and environmental conditions are crucial for throwing light on human evolution. Available reconstructions of the palaeoecology of faunal and floral assemblages indicate that the earliest Kenyan hominids, including Orrorin tugenensis, are associated with forest landscapes. In this study, we present stable isotope data of tooth enamel carbonate of large herbivores associated with these hominids in order further to evaluate their environmental context. Fossil teeth were sampled in the Lukeino Formation (6.1-5.7 Ma, Late Miocene) and the Mabaget Formation (5.3-4.5 Ma, Early Pliocene) at the foot of the Tugen Hills (Great Rift Valley). Despite chemical changes in fossil enamel, preservation of the palaeoenvironmental signals is supported by the difference in δ18O between hippos and terrestrial fauna. Moreover, the giraffid specimen from the Mabaget Formation exhibits one of the highest δ18O values, as expected for a drought-tolerant animal. The δ13C of large herbivores indicates that the earliest Kenyan hominids inhabited a mixed C3-C4 environment as did Ardipithecus (Ethiopia) and Sahelanthropus (Chad), two early putative hominids. The Tugen Hills might have been a wooded grassland with patches of woodland. There is no record of closed-canopy forest at the time of deposition. We emphasize differences in food habits among herbivore groups. Deinotheres, nearly all elephantids and the giraffid individual had a C3 diet which reflected browsing behaviour. The intake of C4 plants prevailed for equids and gomphotheres and was consistent with grazing habits. Most hippos and suids were mixed C3-C4 feeders and consequently were generalist herbivores. Bovids and rhinos had a diet ranging from C3 to C4 plants. Variations in δ13C and δ18O among faunal assemblages suggest changes in local climate and vegetation. Moister conditions likely occurred in the Early Pliocene and the latest Miocene (ca. 5.7 Ma) than before. The C3 plant biomass

  13. Assessment of effects of the rising atmospheric nitrogen deposition on nitrogen uptake and long-term water-use efficiency of plants using nitrogen and carbon stable isotopes.

    PubMed

    Yao, F Y; Wang, G A; Liu, X J; Song, L

    2011-07-15

    This study assesses the effects of the atmospheric nitrogen (N) deposition on the N uptake and the long-term water-use efficiency of two C(3) plants (Agropyron cristatum and Leymus chinensis) and two C(4) plants (Amaranthus retroflexus and Setaria viridis) using N and C stable isotopes. In addition, this study explores the potential correlation between leaf N isotope (δ(15)N) values and leaf C isotope (δ(13)C) values. This experiment shows that the atmospheric N deposition has significant effects on the N uptake, δ(15)N and leaf N content (N(m)) of C(3) plants. As the atmospheric N deposition rises, the proportion and the amount of N absorbed from the simulated atmospheric deposition become higher, and the δ(15)N and N(m) of the two C(3) plants both also increase, suggesting that the rising atmospheric N deposition is beneficial for C(3) plants. However, C(4) plants display different patterns in their N uptake and in their variations of δ(15)N and N(m) from those of C(3) plants. C(4) plants absorb less N from the atmospheric deposition, and the leaf N(m) does not change with the elevated atmospheric N deposition. Photosynthetic pathways may account for the differences between C(3) and C(4) plants. This study also shows that atmospheric N deposition does not play a role in determining the δ(13)C and in the long-term water-use efficiency of C(3) and C(4) plants, suggesting that the long-term water-use pattern of the plants does not change with the atmospheric N input. In addition, this study does not observe any relationship between leaf δ(15)N and leaf δ(13)C in both C(3) and C(4) plants.

  14. 3D Binder-free MoSe2 Nanosheets/Carbon Cloth Electrodes for Efficient and Stable Hydrogen Evolution Prepared by Simple Electrophoresis Deposition Strategy

    PubMed Central

    Liu, Yundan; Ren, Long; Zhang, Zhen; Qi, Xiang; Li, Hongxing; Zhong, Jianxin

    2016-01-01

    We successfully developed a simple electrophoretic deposition (EPD) method to decorate the MoSe2 nanosheets on the carbon fiber surface of carbon cloth (MoSe2/CC). With this process, MoSe2 nanosheets can be uniformly and tightly deposited on this flexible conductor to form a 3D binder-free electrode for hydrogen evolution reaction (HER). The film thickness can also be controlled by the EPD time. Directly used as binder-free electrodes for hydrogen evolution reaction, the as-prepared 3D MoSe2/CC samples exhibit excellent catalytic activity in an acidic electrolyte (21 mA/cm2 at an over-potential of 250 mV). Variation of MoSe2 nanosheets film thickness in the electrodes could affect the catalytic activity, and it was found that the MoSe2/CC sample prepared with 60 min EPD time shows the highest HER activity amongst these different thickness samples. Moreover, stability tests though long-term potential cycles (no degradation after 1000 continuous potential cycles) and extended electrolysis confirm the exceptional durability of the catalyst. This development offers us an attractive and active 3D electrode for electrochemical water splitting. PMID:26948283

  15. 3D Binder-free MoSe2 Nanosheets/Carbon Cloth Electrodes for Efficient and Stable Hydrogen Evolution Prepared by Simple Electrophoresis Deposition Strategy

    NASA Astrophysics Data System (ADS)

    Liu, Yundan; Ren, Long; Zhang, Zhen; Qi, Xiang; Li, Hongxing; Zhong, Jianxin

    2016-03-01

    We successfully developed a simple electrophoretic deposition (EPD) method to decorate the MoSe2 nanosheets on the carbon fiber surface of carbon cloth (MoSe2/CC). With this process, MoSe2 nanosheets can be uniformly and tightly deposited on this flexible conductor to form a 3D binder-free electrode for hydrogen evolution reaction (HER). The film thickness can also be controlled by the EPD time. Directly used as binder-free electrodes for hydrogen evolution reaction, the as-prepared 3D MoSe2/CC samples exhibit excellent catalytic activity in an acidic electrolyte (21 mA/cm2 at an over-potential of 250 mV). Variation of MoSe2 nanosheets film thickness in the electrodes could affect the catalytic activity, and it was found that the MoSe2/CC sample prepared with 60 min EPD time shows the highest HER activity amongst these different thickness samples. Moreover, stability tests though long-term potential cycles (no degradation after 1000 continuous potential cycles) and extended electrolysis confirm the exceptional durability of the catalyst. This development offers us an attractive and active 3D electrode for electrochemical water splitting.

  16. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-01-01

    The purpose of obtaining stable carbon isotope analyses of coprocessing products is to determine the amount of coal (or petroleum) carbon that is present in any reaction product. This carbon-sourcing of distillate fractions, soluble resid, and insoluble organic matter, etc. is useful in modeling reactions, and evaluating synergistic effects if they exist.

  17. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-12-31

    The purpose of obtaining stable carbon isotope analyses of coprocessing products is to determine the amount of coal (or petroleum) carbon that is present in any reaction product. This carbon-sourcing of distillate fractions, soluble resid, and insoluble organic matter, etc. is useful in modeling reactions, and evaluating synergistic effects if they exist.

  18. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-01-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application an authentic continuous-unit products. The experimental details used for stable carbon isotope analyses by the organization that performs most of those analyses under this contract are described. A method was developed previously under this contract to correct the carbon sourcing calculations performed from stable carbon isotope analyses for selective isotopic fractionation. The method relies on three assumptions. This quarter, a study was completed to define the sensitivity of the carbon sourcing results to errors in the assumptions. Carbon contents and carbon isotope ratios were determined for the available feeds and product fractions from HRI bench-scale coprocessing Run 238-10 (Texas lignite/Hondo vacuum still bottoms (VSB), Texas lignite/Cold Lake VSB and Westerholt coal/Cold Lake VSB). These data were used for carbon sourcing calculations and individual feedstock conversion calculations. A previously devised means for correcting for selective isotope fractionation was applied. 6 refs., 30 figs., 16 tabs.

  19. Hard Carbon Films Deposited under Various Atmospheres

    NASA Astrophysics Data System (ADS)

    Wei, M.-K.; Chen, S.-C.; Wu, T. C.; Lee, Sanboh

    1998-03-01

    Using a carbon target ablated with an XeCl-excimer laser under various gas atmospheres at different pressures, hard carbon was deposited on silicon, iron and tungsten carbide substrates. The hardness, friction coefficient, and wear rate of the film against steel are better than pure substrate material, respectively, so that it has potential to be used as a protective coating for micromechanical elements. The influences of gas pressure, gas atmosphere, and power density of laser irradiation on the thermal stability of film were analyzed by means of Raman-spectroscope, time-of-flight method, and optical emission spectrum. It was found that the film deposited under higher pressure has less diamond-like character. The film deposited under rest gas or argon atmosphere was very unstable and looked like a little graphite-like character. The film deposited at high vacuum (10-5 mbar rest gas) was the most stable and looked like the most diamond-like character. The film deposited at higher power density was more diamond-like than that at lower power density.

  20. Deposition of diamondlike carbon films

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J.; Sovey, J. S.; Banks, B. A. (Inventor)

    1984-01-01

    A diamondlike carbon film is deposited in the surface of a substrate by exposing the surface to an argon ion beam containing a hydrocarbon. The current density in the ion beam is low during initial deposition of the film. Subsequent to this initial low current condition, the ion beam is increased to full power. At the same time, a second argon ion beam is directed toward the surface of the substrate. The second ion beam has an energy level much greater than that of the ion beam containing the hydrocarbon. This addition of energy to the system increases mobility of the condensing atoms and serves to remove lesser bound atoms.

  1. Carbonate Deposition on Antarctic Shelves

    NASA Astrophysics Data System (ADS)

    Frank, T. D.; James, N. P.; Malcolm, I.

    2011-12-01

    Limestones associated with glaciomarine deposits occur throughout the geologic record but remain poorly understood. The best-described examples formed during major ice ages of the Neoproterozoic and Late Paleozoic. Quaternary analogs on Antarctic shelves have received comparatively little study. Here, we report on the composition, spatial distribution, and stratigraphic context of carbonate sediments contained in piston cores from the Ross Sea. The goals of this work are to (1) document the nature and distribution of carbonate sediments on the Ross Sea continental shelf and (2) examine temporal relationships to Quaternary glaciation. Results will be used to develop criteria that will improve understanding of analogous deposits in the ancient record. All carbonate-rich intervals in piston cores from the Ross Rea, now housed at the Antarctic Marine Geology Research Facility at Florida State University, were examined and described in detail. Sediment samples were disaggregated and sieved into size fractions before description with paleontological analysis carried out on the coarsest size fraction (>250 microns). Carbonate-rich sediments are concentrated in the northwestern Ross Sea, along the distal margins of Mawson and Pennell Banks. Calcareous facies include a spectrum of lithologies that range from fossiliferous mud, sand, and gravel to skeletal floatstone-rudstone and bafflestone. Floatstone-rudstone and bafflestone is most abundant along western-facing slopes in areas protected from the Antarctic Coastal Current. Sand-prone facies dominate the tops of banks and mud-prone, often spicultic, facies occur in deeper areas. The carbonate factory is characterized by a low-diversity, heterozoan assemblage that is dominated by stylasterine hydrocorals, barnacles, and bryozoans. Molluscs and echinoids are present but not abundant. Planktic and benthic foraminifera are ubiquitous components of the sediment matrix, which is locally very rich in sponge spicules. Biota rarely

  2. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Winschel, R.A.; Lancet, M.S.; Burke, F.P.

    1991-04-01

    This is the final report which was a thirty-four month project conducted to develop and demonstrate stable carbon isotope analysis as a method to quantitatively distinguish the source of carbon in products of coal/petroleum coprocessing. The work included assessing precision, accuracy, the range of application and the significance of selective isotopic fractionation effects. A method was devised to correct for selective isotopic fractionation errors. The method was demonstrated through application with samples from twelve continuous-unit coprocessing tests. A data base of carbon isotope analyses is appended. 21 refs.

  3. Air-stable conversion of separated carbon nanotube thin-film transistors from p-type to n-type using atomic layer deposition of high-κ oxide and its application in CMOS logic circuits.

    PubMed

    Zhang, Jialu; Wang, Chuan; Fu, Yue; Che, Yuchi; Zhou, Chongwu

    2011-04-26

    Due to extraordinary electrical properties, preseparated, high purity semiconducting carbon nanotubes hold great potential for thin-film transistors (TFTs) and integrated circuit applications. One of the main challenges it still faces is the fabrication of air-stable n-type nanotube TFTs with industry-compatible techniques. Here in this paper, we report a novel and highly reliable method of converting the as-made p-type TFTs using preseparated semiconducting nanotubes into air-stable n-type transistors by adding a high-κ oxide passivation layer using atomic layer deposition (ALD). The n-type devices exhibit symmetric electrical performance compared with the p-type devices in terms of on-current, on/off ratio, and device mobility. Various factors affecting the conversion process, including ALD temperature, metal contact material, and channel length, have also been systematically studied by a series of designed experiments. A complementary metal-oxide-semiconductor (CMOS) inverter with rail-to-rail output, symmetric input/output behavior, and large noise margin has been further demonstrated. The excellent performance gives us the feasibility of cascading multiple stages of logic blocks and larger scale integration. Our approach can serve as the critical foundation for future nanotube-based thin-film macroelectronics.

  4. Fate of Organic Carbon Deposited in Reservoirs

    NASA Astrophysics Data System (ADS)

    Huntington, T. G.; Rhoton, F. E.; Bennett, S. J.; Hudnall, W. H.

    2002-05-01

    Sedimentation of soil organic carbon (SOC) eroded from uplands and deposited in reservoirs could be an important mechanism for carbon sequestration provided that it is conserved during transport and burial and that uplands are not experiencing net loss. There are uncertainties in both these assumptions and gaining a better understanding of these processes is a key objective of ongoing carbon-cycle investigations. The U.S. Geological Survey, the U. S. Department of Agriculture, and Louisiana State University Agricultural Center are collaborating on an investigation of soils and sediments in the Yalobusha River Basin in Mississippi. Sediment cores were collected from upland soils and from Grenada Lake, a flood control reservoir, in the basin. Suspended sediments have been collected from the Yalobusha River and one of its tributaries upstream of the lake. We are measuring carbon mineralization potential in conjunction with carbon and nitrogen concentrations, 13C, mineralogy, and texture on sediments and upland soils to determine whether eroding SOC is conserved or oxidized during transport and burial. Differences in mineralization potential and other chemical and physical properties are used to infer net changes in the original eroding SOC. Autochthonous production of SOC within reservoirs could replace labile SOC oxidized during transport and burial thereby masking losses due to oxidation. Autochthonous sources can be evaluated by chemical and physical characterization of the sediments. Stable carbon isotope (13C) geochemistry provides a tool for distinguishing the two primary sources of organic carbon incorporated in lake sediments because allochthonous SOC from the surrounding watershed is, in general, less depleted in stable 13C than autochthonous SOC produced in the lake by aquatic organisms such as macrophytes and phytoplankton. The integration of the 13C signature recorded in the organic fraction of the lake sediments with total organic carbon, C/N ratio

  5. Generality of forming stable organic glasses by vapor deposition

    NASA Astrophysics Data System (ADS)

    Zhu, Lei; Yu, Lian

    2010-10-01

    Organic glasses of exceptional thermodynamic and kinetic stability have been prepared for the first time for four substances by vapor deposition in simple sublimation apparatus. This study, together with previous studies, demonstrates the generality of the phenomenon; the simple apparatus makes these interesting materials more accessible for research. Substances forming stable glasses by vapor deposition tend to undergo surface-enhanced crystal growth, suggesting both phenomena could be linked to surface mobility. Stable organic glasses are potentially useful for drug delivery, organic electronics, and thin-film technologies.

  6. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Winschel, R.A.; Lancet, M.S.; Burke, F.P.

    1990-07-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. The program is designed to address a substantial, demonstrated need of coprocessing research (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique currently is in routine use for other applications. Progress is discussed. 7 refs., 7 figs., 12 tabs.

  7. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Lancet, M.S.

    1990-05-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Activities for this quarter include: method development -- investigation of selective fractionation. Three petroleum atmospheric still bottoms (ASBs) were separated by distillation and solubility fractionation to determine the homogeneity of the carbon isotope ratios of the separated fractions. These same three petroleum ASBs and three geographically distinct coals were pyrolyzed at 800{degree}F for 30 min and hydrogenated over a CoMo catalyst at 750{degree}F for 60 min to determine the effects of these treatments on the isotopic compositions of the produce fractions. Twelve coal liquefaction oils were analyzed for carbon isotope ratios. These oils were derived from subbituminous and bituminous coals from the first- and second-stage reactors in the thermal/catalytic and modes; validation and application, analysis. Carbon isotope analyses of samples from HRI bench unit coprocessing run 238-2 (Taiheiyo coal/Maya VSB) were analyzed. A method to correct for selective isotopic fractionation was developed and applied to the data. Five coprocessing samples were analyzed at the request of SRI International. 12 refs., 15 figs., 24 tabs.

  8. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-02-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, when necessary, corrections are applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. Previously reported data on samples from HRI bench-scale coprocessing Runs 227-53 (Texas lignite/Maya ASB and Texas lignite/Maya VSB) and 238-1 (Westerholt coal/Cold Lake VSB) were corrected for selective isotopic fractionation. Carbon sourcing was performed on samples from HRI bench-scale coprocessing Run 227-60 (Texas lignite/Maya VSB) and samples from UOP bench-scale coprocessing Run 26 (Illinois 6 coal/Lloydminster vacuum resid); the latter data were corrected for isotopic fractionation, though the former could not be corrected. A paper presented at the 1990 DOE Direct Liquefaction Contractor's Review Meeting is appended. 15 refs., 21 figs., 22 tabs.

  9. Evaluation of bioremediation systems utilizing stable carbon isotope analysis

    SciTech Connect

    Van de Velde, K.; Nowell, C.; Marley, M.C.

    1994-12-31

    Carbon, whether in an organic or inorganic form, is composed primarily of two stable isotopes, carbon-12 and carbon-13. The ratio of carbon-12 to carbon-13 is approximately 99:1. The stable carbon isotope ratios of most natural carbon materials of biological interest range from approximately 0 to {minus}110 per mil ({per_thousand}) versus the PDB standard. Utilizing stable carbon isotope analysis, it is often possible to determine the source(s) of the liberated carbon dioxide, thereby confirming successful mineralization of the targeted carbon compound(s) and, if the carbon dioxide results from multiple carbon compounds, in what ratio the carbon compounds are mineralized. Basic stable isotope `theory` recommended sampling procedures and analysis protocols are reviewed. A case study involving fuel oil presented on the application of stable carbon isotope analysis for the monitoring and evaluation of in situ bioremediation. At the site, where a field bioventing study was being conducted, multiple potential sources of carbon dioxide production existed. Additional potential applications of stable carbon isotope analysis for bioremediation evaluation and monitoring are discussed.

  10. Infrared study of carbon deposits on catalysts

    SciTech Connect

    Eischens, R.P.

    1989-01-01

    The deposition of carbon on alumina and on catalysts, in which alumina was the support for platinum and rhenium, was followed by simultaneously weighing the total deposit and observing the infrared spectra. At total carbon deposit levels of 1 percent or less, produced by exposure to acetylene at 525 K or ethylene at 625 K, bands were observed near 1580 and 1470 cm/sup /minus/1/. Isotopic labeling with oxygen-18 and deuterium shows that these bands are attributable to the asymmetric and symmetric stretching vibrations of a carbon-oxygen species similar to a carboxylate ion. This species involves about one-sixth of the total carbon in deposits on alumina. Platinum does not markedly affect the total carbon or the fraction that is carboxylate. Rhenium does not affect the total carbon but it significantly lowers the carbon-oxygen species. Pretreatment of desulfurization catalysts with ammonia reduces the total carbon by about one-half and almost eliminates carboxylate formation. Carboxylates are not found in carbon deposits on silica. 15 refs., 5 figs.

  11. Interconnected hollow carbon nanospheres for stable lithium metal anodes

    NASA Astrophysics Data System (ADS)

    Zheng, Guangyuan; Lee, Seok Woo; Liang, Zheng; Lee, Hyun-Wook; Yan, Kai; Yao, Hongbin; Wang, Haotian; Li, Weiyang; Chu, Steven; Cui, Yi

    2014-08-01

    For future applications in portable electronics, electric vehicles and grid storage, batteries with higher energy storage density than existing lithium ion batteries need to be developed. Recent efforts in this direction have focused on high-capacity electrode materials such as lithium metal, silicon and tin as anodes, and sulphur and oxygen as cathodes. Lithium metal would be the optimal choice as an anode material, because it has the highest specific capacity (3,860 mAh g-1) and the lowest anode potential of all. However, the lithium anode forms dendritic and mossy metal deposits, leading to serious safety concerns and low Coulombic efficiency during charge/discharge cycles. Although advanced characterization techniques have helped shed light on the lithium growth process, effective strategies to improve lithium metal anode cycling remain elusive. Here, we show that coating the lithium metal anode with a monolayer of interconnected amorphous hollow carbon nanospheres helps isolate the lithium metal depositions and facilitates the formation of a stable solid electrolyte interphase. We show that lithium dendrites do not form up to a practical current density of 1 mA cm-2. The Coulombic efficiency improves to ˜99% for more than 150 cycles. This is significantly better than the bare unmodified samples, which usually show rapid Coulombic efficiency decay in fewer than 100 cycles. Our results indicate that nanoscale interfacial engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes.

  12. The separation of stable isotopes of carbon

    NASA Astrophysics Data System (ADS)

    Oziashvili, E. D.; Egiazarov, A. S.

    1989-04-01

    The present state of work on the separation of carbon isotopes by diffusion, fractional distillation, chemical isotopic exchange, and the selective excitation and dissociation of molecules in electrical discharges or in the field of laser radiation has been examined. The characteristics of new laboratory and industrial assemblies for separating carbon isotopes have been described. Promising directions of study aimed at developing effective technological processes for separating carbon isotopes have been noted. The bibliography contains 148 references.

  13. Controlled Deposition and Alignment of Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Smits, Jan M. (Inventor); Wincheski, Russell A. (Inventor); Ingram, JoAnne L. (Inventor); Watkins, Anthony Neal (Inventor); Jordan, Jeffrey D. (Inventor)

    2009-01-01

    A carbon nanotube (CNT) attraction material is deposited on a substrate in the gap region between two electrodes on the . substrate. An electric potential is applied to the two electrodes. The CNT attraction material is wetted with a solution defined by a carver liquid having carbon nanotubes (CNTs) suspended therein. A portion of the CNTs align with the electric field and adhere to The CNT attraction material. The carrier liquid and any CNTs not adhered to the CNT attraction material are then removed.

  14. Controlled Deposition and Alignment of Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Smits, Jan M. (Inventor); Wincheski, Russell A. (Inventor); Patry, JoAnne L. (Inventor); Watkins, Anthony Neal (Inventor); Jordan, Jeffrey D. (Inventor)

    2012-01-01

    A carbon nanotube (CNT) attraction material is deposited on a substrate in the gap region between two electrodes on the substrate. An electric potential is applied to the two electrodes. The CNT attraction material is wetted with a solution defined by a carrier liquid having carbon nanotubes (CNTs) suspended therein. A portion of the CNTs align with the electric field and adhere to the CNT attraction material. The carrier liquid and any CNTs not adhered to the CNT attraction material are then removed.

  15. Warming and nitrogen deposition lessen microbial residue contribution to soil carbon pool.

    PubMed

    Liang, Chao; Balser, Teri C

    2012-01-01

    Microorganisms have a role as gatekeepers for terrestrial carbon fluxes, either causing its release to the atmosphere through their decomposition activities or preventing its release by stabilizing the carbon in a form that cannot be easily decomposed. Although research has focused on microbial sources of greenhouse gas production, somewhat limited attention has been paid to the microbial role in carbon sequestration. However, increasing numbers of reports indicate the importance of incorporating microbial-derived carbon into soil stable carbon pools. Here we investigate microbial residues in a California annual grassland after a continuous 9-year manipulation of three environmental factors (elevated CO(2), warming and nitrogen deposition), singly and in combination. Our results indicate that warming and nitrogen deposition can both alter the fraction of carbon derived from microbes in soils, though for two very different reasons. A reduction in microbial carbon contribution to stable carbon pools may have implications for our predictions of global change impacts on soil stored carbon.

  16. Atmospheric deposition of organic carbon via precipitation

    NASA Astrophysics Data System (ADS)

    Iavorivska, Lidiia; Boyer, Elizabeth W.; DeWalle, David R.

    2016-12-01

    Atmospheric deposition is the major pathway for removal of organic carbon (OC) from the atmosphere, affecting both atmospheric and landscape processes. Transfers of OC from the atmosphere to land occur as wet deposition (via precipitation) and as dry deposition (via surface settling of particles and gases). Despite current understanding of the significance of organic carbon inputs with precipitation to carbon budgets, transfers of organic matter between the atmosphere and land are not explicitly included in most carbon cycle models due to limited data, highlighting the need for further information. Studies regarding the abundance of OC in precipitation are relatively sparse, in part due to the fact that concentrations of organics in precipitation and their associated rates of atmospheric deposition are not routinely measured as a part of major deposition monitoring networks. Here, we provide a new data synthesis from 83 contemporary studies published in the peer reviewed literature where organic matter in precipitation was measured around the world. We compiled data regarding the concentrations of organic carbon in precipitation and associated rates of atmospheric deposition of organic carbon. We calculated summary statistics in a common set of units, providing insights into the magnitude and regional variability of OC in precipitation. A land to ocean gradient is evident in OC concentrations, with marine sites generally showing lower values than continental sites. Our synthesis highlights gaps in the data and challenges for data intercomparison. There is a need to concentrate sampling efforts in areas where anthropogenic OC emissions are on the rise (Asia, South America), as well as in remote sites suggesting background conditions, especially in Southern Hemisphere. It is also important to acquire more data for marine rainwater at various distances from the coast in order to assess a magnitude of carbon transfer between the land and the ocean. Our integration of

  17. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    EPA Science Inventory

    The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

  18. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Lancet, M.S.

    1989-06-01

    The program is designed to address a substantial, demonstrated need of the coprocessing community (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique is currently in routine use for other applications. Results achieved this quarter include: Feed and product fractions from a Kentucky 9 coal/Kentucky tar sand bitumen coprocessing bench unit run at the Kentucky Center for Applied Energy Research (CAER) were analyzed for carbon isotope ratios. Corrections were made to the coal carbon recoveries and selectivities from the products of HRI Run 227-53. Feeds (Westerholt coal/Cold Lake VSB) and products from two periods of HRI coprocessing Run 238-1 were analyzed. Three petroleum samples and three coal samples were pyrolyzed at 800{degree}F for 30 min to determine the effect of pyrolysis on the isotopic homogeneity of each petroleum and coal sample. Products from each pyrolysis test were separated into five fractions; an additional set of coprocessing samples and a set of two-stage coal liquefaction samples were obtained from HRI for future work; work performed by the Pennsylvania State University show that microscopy is a promising method for distinguishing coal and petroleum products in residual coprocessing materials; and coal and petroleums that have large differences in carbon isotope ratios were identified for Auburn University. 7 refs., 2 figs., 12 tabs.

  19. Volcanic recycling of carbonate deposits on Mars

    NASA Technical Reports Server (NTRS)

    Schaefer, M. W.

    1992-01-01

    One question of great interest to those who study the evolution of the Martian atmosphere is: if there was an early, dense atmosphere that was removed, is there any mechanism that could restore it? In the case of an atmosphere removed largely by the formation of carbonates, the only obvious means of restoring it is by the thermal decomposition of the carbonates. Decomposition of carbonates under turbulently flowing lava holds great promise as a means of resupplying the atmosphere with CO2. Huppert and colleagues have modeled the emplacement of terrestrial komatiite flows and found that komatiites, even when flowing over previously emplaced and cooled komatiite flows, could melt and erode this rock to a significant depth. Based on this work, I have begun modeling the erosion of Martian carbonate deposits under turbulently flowing, komatiitic lava. Initial results from this modeling indicate that a high-volume lava flow, emerging at a temperature of, say, 1600 degrees, is capable of eroding several meters of carbonate deposits per day. If such a flow is active for a hundred days, several hundreds of meters of carbonate could be decomposed. If this process occurred over a large area, a bar or more of CO2 could be injected back into the atmosphere over an extremely short period of time. The implications of such an occurrence are intriguing. For instance, if a relatively late pulse of volcanism (such as is suggested by Frey) were to cause a large flow of lava over carbonate deposits in the northern lowlands, the resulting pulse of CO2 into the atmosphere could conceivably restore the climate to one in which liquid water could exist on the surface, or ice could flow.

  20. Carbon dioxide-induced homogeneous deposition of nanometer-sized cobalt ferrite (CoFe2O4) on graphene as high-rate and cycle-stable anode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Lingyan; Zhuo, Linhai; Zhang, Chao; Zhao, Fengyu

    2015-02-01

    In the preparation of metal oxide composite materials, the common organic solvents limit the homogenous dispersion of guest component on substrate for their high viscosity, surface tension and low diffusivity. Herein, we take advantage of the unique properties of supercritical carbon dioxide (scCO2) to successfully deposit uniform CoFe2O4 nanoparticles (CFO NPs) on the surface of graphene without need of surfactants or precipitants. The obtained CFO NPs are 8-10 nm in size and homogeneously anchored on graphene sheets as spacers to reduce the degree of graphene restacking. Additionally, the effects of pressure and solvent on the crystallinity, dispersion and particle size of the NPs are discussed. The CFO@G-CE composite synthesized in scCO2-expanded ethanol exhibits excellent cyclability and significantly improved rate capability than the CFO@G-E in pure ethanol and CFO@G-NE in the mixture of high pressure nitrogen and ethanol. It is certified, by the structural and morphological analyses of the intermediates and phase observations, that the reaction medium greatly affects the dispersion and size of the particles, and thus influences their electrochemical performances. The proposed strategy is shortcut (reaction time: 2 h) and effective in execution, hence, we hope that the presented strategy would encourage further studies on other hybrid nanomaterials fabrication.

  1. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-03-01

    Research on coprocessing materials/products continued. Major topics reported here are described below. Microautoclave runs are described in which gases and insoluble organic matter produced from five coals and gases produced from three petroleum resids were analyzed to study feedstock/product selective isotopic fractionation. Selective isotopic fractionation was further explored through isotope analysis of the feed New Mexico coal and products from a continuous coal liquefaction run (HRI CC-10 or 227-68). Feeds (Texas lignite/Maya VSB) and products from two HRI continuous coprocessing runs (227-54 and 238-12) were analyzed. The results were corrected for selective isotopic fractionation and carbon sourcing was performed for the product fractions. {sup 1}H-NMR and phenolic -OH determinations are reported for all continuous unit samples obtained under this contract. 13 refs., 17 figs., 40 tabs.

  2. Rocky Mountain Carbonate Spring Deposit development

    NASA Astrophysics Data System (ADS)

    Rainey, Dustin Kyle

    Relict Holocene carbonate spring deposits containing diverse biotic and abiotic depositional textures are present at Fall Creek cold sulphur springs, Alberta, Fairmont Hot Springs, British Columbia, and Hot Creek cold springs, British Columbia. The relict deposits are formed mainly of low-magnesium crystalline calcite contained in laterally continuous strata. Paleo-flow regimes were characterized by extensive sheet flow that increased the surface area of spring water exposed to the atmosphere. Calcite precipitated inorganically from spring water that attained CaCO3 supersaturation through agitation-induced CO2 degassing that was facilitated by elevated flow rates and a large surface area as spring water flowed down-slope. Thus, the deposits contain only minor amounts of detrital, mechanically deposited, and biogenic carbonate. Evaporation was only a minor contributor to CaCO3 supersaturation, mainly in quiescent environments. Photosynthetic CO2 removal did not measurably contribute to CaCO3 supersaturation. Calcite crystals precipitated in biotic facies formed from low to moderately supersaturated spring water, whereas abiotic dendrite crystals formed rapidly from highly supersaturated spring water. Calcite passively nucleated on cyanobacteria, bryophytes and macrophytes, and was probably facilitated by cyanobacterial extracellular polymeric substances. Cyanobacterial filaments and stromatolites are integral parts of all three deposits, whereas bryophytes were restricted to the Fall Creek and Hot Creek deposits. Diagenetic microbial degradation of crystalline calcite was common to all three deposits, but recrystallization was limited to the Fall Creek deposit. The amount and location of calcite precipitation relative to the vents was controlled by the concentrations of Ca2+ and HCO3- in solution, and discharge volume fluctuations. Spring water with high [Ca2+] and [HCO 3-] precipitated large amounts of calcite proximal to the vents (e.g. Fairmont), whereas spring

  3. Stable three-dimensional metallic carbon with interlocking hexagons

    PubMed Central

    Zhang, Shunhong; Wang, Qian; Chen, Xiaoshuang; Jena, Puru

    2013-01-01

    Design and synthesis of 3D metallic carbon that is stable under ambient conditions has been a long-standing dream. We predict the existence of such phases, T6- and T14-carbon, consisting of interlocking hexagons. Their dynamic, mechanical, and thermal stabilities are confirmed by carrying out a variety of state-of-the-art theoretical calculations. Unlike the previously studied K4 and the simple cubic high pressure metallic phases, the structures predicted in this work are stable under ambient conditions. Equally important, they may be synthesized chemically by using benzene or polyacenes molecules. PMID:24191020

  4. [Stable isotopes of carbon and nitrogen in soil ecological studies].

    PubMed

    Tiunov, A V

    2007-01-01

    The development of stable isotope techniques is one of the main methodological advances in ecology of the last decades of the 20th century. Many biogeochemical processes are accompanied by changes in the ratio between stable isotopes of carbon and nitrogen (12C/13C and 14N/15N), which allows different ecosystem components and different ecosystems to be distinguished by their isotopic composition. Analysis of isotopic composition makes it possible to trace matter and energy flows through biological systems and to evaluate the rate of many ecological processes. The main concepts and methods of stable isotope ecology and patterns of stable isotope fractionation during organic matter decomposition are considered with special emphasis on the fractionation of isotopes in food chains and the use of stable isotope studies of trophic relationships between soil animals in the field.

  5. The stable isotopic composition of a phosphorite deposit: δ13C, δ34S, and δ18O

    USGS Publications Warehouse

    Piper, D.Z.; Kolodny, Y.

    1987-01-01

    The stable isotopes of carbon and sulfur in a major marine sedimentary phosphate deposit from the northwestern United States (the Phosphoria Formation of Permian age) characterize the chemical properties of the depositional environment. The δ34S and δ13C analyses suggest deposition under conditions of variable redox from a solution the acidity of which was controlled by reaction with carbonate rocks and exchange with seawater. The δ18O concentration of apetite indicates phosphatization in a shallow sea, during three glacial and intervening interglacial stages. These data tend to corroborate the interpretation of field studies by others, that the apatite formed on a continental shelf in an area of intense oceanic upwelling during several episodes of sea level change. 

  6. Chemical vapor deposited carbon nanotubes for aqueous H2-Cl2 fuel cells.

    PubMed

    Suryavanshi, U B; Bhosale, C H

    2010-06-01

    Carbon nanotubes having large surface area is an interesting material to develop H2-Cl2 fuel cell electrodes. The attempts were made to deposit carbon nanotubes on porous substrates by chemical vapour deposition. Turpentine oil (C10H16) was used as a precursor, decomposed at 1100 degrees C reactor temperature. Nickel, platinum, tin, Ni-Pt, Ni-Sn, Pt-Sn, Ni-Pt-Sn catalysts were used to grow carbon nanotubes. Nickel was deposited with electrodeposition, platinum with sputter coater and tin with vacuum deposition technique. The developed electrodes were characterized by XRD, SEM, TEM, FTIR, and resistivity by van-der Pauw method. Carbon nanotubes have been formed for 0.25 N nickel deposited for 45 and 60 min; 0.5 N, 0.75 N and 1 N nickel deposited for 15 to 60 min, at the interval of 15. Ni-Pt, Ni-Sn, Pt-Sn and Ni-Pt-Sn activated carbon also shows the well grown CNTs. Aqueous H2-Cl2 fuel cell performance was tested with these grown carbon nanotubes. 40% KCl with 1067 mohm(-1) cm(-1) conductivity was used as electrolyte. Linear sweep voltametry shows reduction potential for hydrogen gas. Chronoamperometry results show better half cell performance for nickel, deposited with 1 N, 45 min deposition time period; and combination of Ni-Pt-Sn with 140, and 110-100 mA/cm2 stable current density respectively.

  7. Multiwalled Carbon Nanotube Deposition on Model Environmental Surfaces

    EPA Science Inventory

    Deposition of multiwalled carbon nanotubes (MWNTs) on model environmental surfaces was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Deposition behaviors of MWNTs on positively and negatively charged surfaces were in good agreement with Der...

  8. Stable Isotope Values of Nitrogen and Carbon in Particulate ...

    EPA Pesticide Factsheets

    Data set from “Patterns in stable isotope values of nitrogen and carbon in particulate matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras” by Oczkowski et al. These are the data upon which all results and conclusion are made. Publishing the data allow for use by wider audience. Stable isotope dynamics on the shelf can inform both nearshore and open ocean research efforts, providing an important link along the marine continuum. To our knowledge, this data set is unique in its spatial coverage and variables measured.

  9. Stable isotopes in alpine precipitation as tracers of atmospheric deposition

    NASA Astrophysics Data System (ADS)

    Wasiuta, V. L.; Lafreniere, M. J.; Kyser, T. K.; Norman, A. L.; Mayer, B.; Wieser, M.

    2010-12-01

    Alpine ecosystems, which are generally nutrient poor and exist under extreme climatic conditions, are particularly sensitive to environmental and climatic stressors. Studies in the USA Rocky Mountains and European Alps have shown that alpine terrestrial and aquatic ecosystems are particularly sensitive to enhanced deposition of reactive nitrogen and can show ecologically destructive responses at relatively low levels of nitrogen deposition. However, there is no base line for atmospheric deposition of natural and anthropogenic contaminants in the Canadian alpine. Preliminary results of isotopic and chemical analyses of precipitation from an elevational transect on a glaciated alpine site in the Canadian Rockies are presented. Precipitation accumulating from early autumn through to spring (2008/2009 and 2009/2010) was sampled by means of seasonal snow cover on alpine glaciers. Summer precipitation was sampled through July and August 2010 using bulk collectors installed at the sites of winter sampling. The isotope ratios of dissolved sulphate (δ34S, δ18O), nitrogen (δ15N, δ18O), as well as precipitation (δ2H, δ18O) are utilized in addition to major ion concentrations and trace metal concentrations. Results from 2008/2009 snowpack samples indicate a strong seasonal trend in sulphate (SO42-) and nitrogen (NO3-) deposition which is consistent across the altitudinal transect. Snow horizons representing early autumn and spring precipitation show higher SO42- and NO3- concentrations in contrast to lower concentrations in winter horizons. The aforementioned suite of isotopic and chemical analyses are used to investigate the variability in dominant geographic source regions for atmospheric SO42- and NO3- (local, regional, or long range transported contaminants), as well as to identify contributions from the major biogeochemical source types (e.g. hydrocarbon combustion, lithogenic dust, agricultural emissions).

  10. Coaxial carbon plasma gun deposition of amorphous carbon films

    NASA Technical Reports Server (NTRS)

    Sater, D. M.; Gulino, D. A.; Rutledge, S. K.

    1984-01-01

    A unique plasma gun employing coaxial carbon electrodes was used in an attempt to deposit thin films of amorphous diamond-like carbon. A number of different structural, compositional, and electrical characterization techniques were used to characterize these films. These included scanning electron microscopy, scanning transmission electron microscopy, X ray diffraction and absorption, spectrographic analysis, energy dispersive spectroscopy, and selected area electron diffraction. Optical absorption and electrical resistivity measurements were also performed. The films were determined to be primarily amorphous, with poor adhesion to fused silica substrates. Many inclusions of particulates were found to be present as well. Analysis of these particulates revealed the presence of trace impurities, such as Fe and Cu, which were also found in the graphite electrode material. The electrodes were the source of these impurities. No evidence of diamond-like crystallite structure was found in any of the film samples. Details of the apparatus, experimental procedure, and film characteristics are presented.

  11. Stable isotopic composition of cryptocrystalline magnesite from deposits in Turkey and Austria

    NASA Astrophysics Data System (ADS)

    Horkel, K.; Ebner, F.; Spötl, Ch

    2009-04-01

    Cryptocrystalline magnesite (CM) occurs all over the world predominantly in ultramafic rocks and within those mainly in ophiolite zones. The mineralization forms either veins and networks, which are strictly controlled by regional fault tectonics (Kraubath-type), or nodules and layers, which occur in sediments above the ophiolite close to the paleosurface (Bela Stena type). These types are well established and named after their type deposits in Austria and Serbia, respectively (Pohl, 1990; Prochaska, 2000; Wilson & Ebner, 2006). Stable isotopic studies of CM showed that in comparison to sparry magnesite CM has lower δ13C values (-18‰ to -6‰) and more constant δ18O values (+22‰ to +29‰) (Kralik et al., 1989). Furthermore, it was observed that the Kraubath-type and Bela Stena-type CM differ in their isotopic composition in that the latter is characterised by higher δ13C (-1‰ to +4‰) and δ18O values (+26‰ to +36‰) (Jurković & Pamić, 2003). The formation of CM is still a subject of debate. The δ18O values suggests formation temperatures below 80°C (Kralik et al., 1989; Ece et al., 2005). The C isotope data indicate that the C was either derived from the atmosphere or by decarboxylation of organic-rich sediments (Zedef et al. 2000). Our research addresses the following major questions: (a) What are the reasons for the difference in stable isotopic composition between the Kraubath and the Bela Stena-type? (b) Is it possible to distinguish different types of mineralizations within a deposit using stable isotope data and can this information be applied as a tool for CM exploration? (c) Do the individual isotopic patterns of the individual deposits reflect different conditions for formation or later (post-mineralization) alteration events? Our investigations were concentrated on the type locality in Kraubath (Austria) as well as on some currently operating deposits in the magnesite districts of Eskişehir and Tavşanlı (western Anatolia/ Turkey

  12. Influence of carbonization conditions on the pyrolytic carbon deposition in acacia and eucalyptus wood chars

    SciTech Connect

    Kumar, M.; Gupta, R.C.

    1997-04-01

    The amount of deposited pyrolytic carbon (resulting from the cracking of volatile matter) was found to depend on wood species and carbonization conditions, such as temperature and heating rate. Maximum pyrolytic carbon deposition in both the acacia and eucalyptus wood chars has been observed at a carbonization temperature of 800 C. Rapid carbonization (higher heating rate) of wood significantly reduces the amount of deposited pyrolytic carbon in resulting chars. Results also indicate that the amount of deposited pyrolytic carbon in acacia wood char is less than that in eucalyptus wood char.

  13. Enhanced selectivity of zeolites by controlled carbon deposition

    DOEpatents

    Nenoff, Tina M.; Thoma, Steven G.; Kartin, Mutlu

    2006-05-09

    A method for carbonizing a zeolite comprises depositing a carbon coating on the zeolite pores by flowing an inert carrier gas stream containing isoprene through a regenerated zeolite at elevated temperature. The carbonized zeolite is useful for the separation of light hydrocarbon mixtures due to size exclusion and the differential adsorption properties of the carbonized zeolite.

  14. Stable carbon isotope biogeochemistry of lakes along a trophic gradient

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.

    2014-05-01

    The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFA) were studied in a survey of 22 North American oligotrophic to eutrophic lakes. The δ13C of different PLFA were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the δ13C of DIC. All organic-carbon pools showed larger isotopic variability in eutrophic lakes compared to oligo-mesotrophic lakes because of the high variability in δ13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton δ13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25 ‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

  15. Stable carbon isotope biogeochemistry of lakes along a trophic gradient

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.

    2014-11-01

    The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFAs) was studied in a survey of 22 North American oligotrophic to eutrophic lakes. The δ13C of different PLFAs were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the δ13C of DIC. All organic-carbon pools showed overall higher isotopic variability in eutrophic lakes (n = 11) compared to oligo-mesotrophic lakes (n = 11) because of the high variability in δ13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton δ13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

  16. USE OF FATTY ACID STABLE CARBON ISOTOPE RATIO TO INDICATE MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory


    We use measurements of the concentration and stable carbon isotope ratio of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels, broad microbial community structure, and microbial carbon source. For studies of soil o...

  17. Late Glacial Tropical Savannas in Sundaland Inferred From Stable Carbon Isotope Records of Cave Guano

    NASA Astrophysics Data System (ADS)

    Wurster, C. M.; Bird, M. I.; Bull, I.; Dungait, J.; Bryant, C. L.; Ertunç, T.; Hunt, C.; Lewis, H. A.; Paz, V.

    2008-12-01

    During the Last Glacial Period (LGP), reduced global sea level exposed the continental shelf south of Thailand to Sumatra, Java, and Borneo to form the contiguous continent of Sundaland. However, the type and extent of vegetation that existed on much of this exposed landmass during the LGP remains speculative. Extensive bird and bat guano deposits in caves throughout this region span beyond 40,000 yr BP, and contain a wealth of untapped stratigraphic palaeoenvironmental information. Stable carbon isotope ratios of insectivorous bird and bat guano contain a reliable record of the animal's diet and, through non-specific insect predation, reflect the relative abundance of major physiological pathways in plants. Various physiological pathways of carbon fixation in plants yield differing stable carbon isotope ratios. Stable carbon isotope values of C3 plants are lower than C4 vegetation due to different enzymatic discriminations of the heavy isotope through the carbon fixing pathways. In tropical locales, grasses nearly always follow the C4 photosynthetic pathway, whereas tropical rainforest uses C3 photosynthesis, providing a proxy for vegetation and therefore climate change in the past. Here we discuss four guano stable-isotope records, based on insect cuticle and n-alkane analysis, supplemented by pollen analysis. All sites suggest a C3 dominated ecosystem for the Holocene, consistent with the wet tropical forest vegetation present at all locations. Two sites from Palawan Island, Philippines, record stable carbon isotope values of guano that document a drastic change from C3 (forest) to C4 (savanna) dominated ecosystems during the Last Glacial Maximum (LGM). A third location, at Niah Great Cave, Malaysia, indicates C3-dominant vegetation throughout the record, but does display variation in stable carbon isotope values likely linked to humidity changes. A fourth location, Batu Caves in Peninsular Malaysia, also indicates open vegetation during the LGM. Vegetation

  18. Carbon Doping of Compound Semiconductor Epitaxial Layers Grown by Metalorganic Chemical Vapor Deposition Using Carbon Tetrachloride.

    NASA Astrophysics Data System (ADS)

    Cunningham, Brian Thomas

    1990-01-01

    A dilute mixture of CCl_4 in high purity H_2 has been used as a carbon dopant source for rm Al_ {x}Ga_{1-x}As grown by low pressure metalorganic chemical vapor deposition (MOCVD). To understand the mechanism for carbon incorporation from CCl_4 doping and to provide experimental parameters for the growth of carbon doped device structures, the effects of various crystal growth parameters on CCl _4 doping have been studied, including growth temperature, growth rate, V/III ratio, Al composition, and CCl_4 flow rate. Although CCl _4 is an effective p-type dopant for MOCVD rm Al_{x}Ga_ {1-x}As, injection of CCl_4 into the reactor during growth of InP resulted in no change in the carrier concentration or carbon concentration. Abrupt, heavy carbon doping spikes in GaAs have been obtained using CCl_4 without a dopant memory effect. By annealing samples with carbon doping spikes grown within undoped, n-type, and p-type GaAs, the carbon diffusion coefficient in GaAs at 825 ^circC has been estimated and has been found to depend strongly on the GaAs background doping. Heavily carbon doped rm Al_{x}Ga _{1-x}As/GaAs superlattices have been found to be more stable against impurity induced layer disordering (IILD) than Mg or Zn doped superlattices, indicating that the low carbon diffusion coefficient limits the IILD process. Carbon doping has been used in the base region on an Npn AlGaAs/GaAs heterojunction bipolar transistor (HBT). Transistors with 3 x 10 μm self-aligned emitter fingers have been fabricated which exhibit a current gain cutoff frequency of f_ {rm t} = 26 GHz.

  19. Stable Carbon Fractionation In Size Segregated Aerosol Particles Produced By Controlled Biomass Burning

    NASA Astrophysics Data System (ADS)

    Masalaite, Agne; Garbaras, Andrius; Garbariene, Inga; Ceburnis, Darius; Martuzevicius, Dainius; Puida, Egidijus; Kvietkus, Kestutis; Remeikis, Vidmantas

    2014-05-01

    Biomass burning is the largest source of primary fine fraction carbonaceous particles and the second largest source of trace gases in the global atmosphere with a strong effect not only on the regional scale but also in areas distant from the source . Many studies have often assumed no significant carbon isotope fractionation occurring between black carbon and the original vegetation during combustion. However, other studies suggested that stable carbon isotope ratios of char or BC may not reliably reflect carbon isotopic signatures of the source vegetation. Overall, the apparently conflicting results throughout the literature regarding the observed fractionation suggest that combustion conditions may be responsible for the observed effects. The purpose of the present study was to gather more quantitative information on carbonaceous aerosols produced in controlled biomass burning, thereby having a potential impact on interpreting ambient atmospheric observations. Seven different biomass fuel types were burned under controlled conditions to determine the effect of the biomass type on the emitted particulate matter mass and stable carbon isotope composition of bulk and size segregated particles. Size segregated aerosol particles were collected using the total suspended particle (TSP) sampler and a micro-orifice uniform deposit impactor (MOUDI). The results demonstrated that particle emissions were dominated by the submicron particles in all biomass types. However, significant differences in emissions of submicron particles and their dominant sizes were found between different biomass fuels. The largest negative fractionation was obtained for the wood pellet fuel type while the largest positive isotopic fractionation was observed during the buckwheat shells combustion. The carbon isotope composition of MOUDI samples compared very well with isotope composition of TSP samples indicating consistency of the results. The measurements of the stable carbon isotope ratio in

  20. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, [OH]dt) of the different VOC. It is found that [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform [OH]dt for VOC with different reactivity is not justified and that the observed values for [OH]dt are the result of mixing of VOC from air masses with different values for [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine [OH]dt would result in values for [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform [OH]dt for an air mass has to be replaced by the concept of individual values of an average [OH]dt for VOC with different reactivity.

  1. A stable carbon isotope and biological marker study of Polish bituminous coals and carbonaceous shales

    USGS Publications Warehouse

    Kotarba, M.J.; Clayton, J.L.

    2003-01-01

    Biological marker and carbon isotopic compositions of coals and carbonaceous shales from the Upper Carboniferous strata of the Upper Silesian (USCB), Lower Silesian (LSCB), and Lublin (LCB) coal basins were determined to assess depositional conditions and sources of the organic matter. n-Alkane, sterane, and isoprenoid distribution, and carbon isotope ratios are consistent with an origin from higher plants. In some cases, pristane/phytane (Pr/Ph) ratios of carbonaceous shales (roof and floor shales) are < 1.0, while the associated coals have high ratios (??? 1.0). This suggests that reducing conditions prevailed during deposition of the shales, but a period of oxidizing conditions accompanied deposition of the coals. Steranes present in coal extracts are dominated by the 14??(H)17??(H)20R C29 stereoisomers, typical, but not conclusive, of higher plant origin. Carbonaceous shales exhibit a wider range of sterane composition, suggesting local, significant input of algal organic matter. Significant amounts of benzohopanes and gammacerane are present in some coals. Although benzohopanes are present at least in small amounts in samples from many different environments, they have been reported to occur most commonly in marine environments. The present study seems to provide the first example where benzohopanes have been reported in significant amounts in terrestrial organic matter. Gammacerane is abundant in rocks or sediments deposited in carbonate or highly saline marine environments. The finding of high gammacerane concentrations in the coals expands the depositional settings in which it has been observed and questions its utility as an independent indicator of hypersaline carbonate environments. Stable carbon isotope composition of coals, and type III kerogen in carbonaceous shales as well as correlation of stable carbon isotope composition of saturated and aromatic hydrocarbons in carbonaceous shales from both the USCB and the LSCB indicate terrigenous origin

  2. Stable doping of carbon nanotubes via molecular self assembly

    SciTech Connect

    Lee, B.; Chen, Y.; Podzorov, V.; Cook, A.; Zakhidov, A.

    2014-10-14

    We report a novel method for stable doping of carbon nanotubes (CNT) based on methods of molecular self assembly. A conformal growth of a self-assembled monolayer of fluoroalkyl trichloro-silane (FTS) at CNT surfaces results in a strong increase of the sheet conductivity of CNT electrodes by 60–300%, depending on the CNT chirality and composition. The charge carrier mobility of undoped partially aligned CNT films was independently estimated in a field-effect transistor geometry (~100 cm²V⁻¹s⁻¹). The hole density induced by the FTS monolayer in CNT sheets is estimated to be ~1.8 ×10¹⁴cm⁻². We also show that FTS doping of CNT anodes greatly improves the performance of organic solar cells. This large and stable doping effect, easily achieved in large-area samples, makes this approach very attractive for applications of CNTs in transparent and flexible electronics.

  3. Cobalamin Catalytic Centers for Stable Fuels Generation from Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Robertson, Wesley D.; Jawdat, Benmaan I.; Ennist, Nathan M.; Warncke, Kurt

    2010-03-01

    Our aim is to design and construct protein-based artificial photosynthetic systems that reduce carbon dioxide (CO2) to stable fuel forms within the robust and adaptable (βα)8 TIM-barrel protein structure. The EutB subunit of the adenosylcobalamin-dependent enzyme, ethanolamine ammonia-lyase, from Salmonella typhimurium, was selected as the protein template. This system was selected because the Co^I forms of the native cobalamin (Cbl) cofactor, and the related cobinamide (Cbi), possess redox properties that are commensurate with reduction of CO2. The kinetics of photo- (excited 5'-deazariboflavin electron donor) and chemical [Ti(III)] reduction, and subsequent reaction, of the Cbl and Cbi with CO2 are measured by time-resolved UV/visible absorption spectroscopy. Products are quantified by NMR spectroscopy. The results address the efficacy of the organocobalt catalytic centers for CO2 reduction to stable fuels, towards protein device integration.

  4. STABLE CARBON ISOTOPE ANALYSIS OF SUBFOSSIL WOOD FROM AUSTRIAN ALPS

    PubMed Central

    KŁUSEK, MARZENA; PAWEŁCZYK, SŁAWOMIRA

    2015-01-01

    The presented studies were carried out in order to check the usefulness of subfossil wood for stable isotope analysis. The aim of research was also to define the optimal method of subfossil samples preparation. Subfossil samples used during the presented studies are a part of the multi-century dendrochronological scale. This chronology originates in an area situated around a small mountain lake — Schwarzersee, in Austria. The obtained results of stable carbon isotope measurements confirmed that the method of α-cellulose extraction by the application of acidic sodium chlorite and sodium hydroxide solutions removes resins and other mobile compounds from wood. Therefore, in the case of the analysed samples, the additional chemical process of extractives removing was found to be unnecessary. Studied wood samples contained an adequate proportion of α-cellulose similar to the values characteristic for the contemporary trees. This proved an adequate wood preservation which is essential for the conduction of isotopic research. PMID:26346297

  5. Large and stable emission current from synthesized carbon nanotube/fiber network

    SciTech Connect

    Di, Yunsong; Xiao, Mei; Zhang, Xiaobing Wang, Qilong; Li, Chen; Lei, Wei; Cui, Yunkang

    2014-02-14

    In order to obtain a large and stable electron field emission current, the carbon nanotubes have been synthesized on carbon fibers by cold wall chemical vapor deposition method. In the hierarchical nanostructures, carbon fibers are entangled together to form a conductive network, it could provide excellent electron transmission and adhesion property between electrode and emitters, dispersed clusters of carbon nanotubes with smaller diameters have been synthesized on the top of carbon fibers as field emitters, this kind of emitter distribution could alleviate electrostatic shielding effect and protect emitters from being wholly destroyed. Field emission properties of this kind of carbon nanotube/fiber network have been tested, up to 30 mA emission current at an applied electric field of 6.4 V/μm was emitted from as-prepared hierarchical nanostructures. Small current degradation at large emission current output by DC power operation indicated that carbon nanotube/fiber network could be a promising candidate for field emission electron source.

  6. Stable Carbon Isotope Fractionation by Methylotrophic Methanogenic Archaea

    PubMed Central

    Penger, Jörn; Conrad, Ralf

    2012-01-01

    In natural environments methane is usually produced by aceticlastic and hydrogenotrophic methanogenic archaea. However, some methanogens can use C1 compounds such as methanol as the substrate. To determine the contributions of individual substrates to methane production, the stable-isotope values of the substrates and the released methane are often used. Additional information can be obtained by using selective inhibitors (e.g., methyl fluoride, a selective inhibitor of acetoclastic methanogenesis). We studied stable carbon isotope fractionation during the conversion of methanol to methane in Methanosarcina acetivorans, Methanosarcina barkeri, and Methanolobus zinderi and generally found large fractionation factors (−83‰ to −72‰). We further tested whether methyl fluoride impairs methylotrophic methanogenesis. Our experiments showed that even though a slight inhibition occurred, the carbon isotope fractionation was not affected. Therefore, the production of isotopically light methane observed in the presence of methyl fluoride may be due to the strong fractionation by methylotrophic methanogens and not only by hydrogenotrophic methanogens as previously assumed. PMID:22904062

  7. Patterns in Stable Isotope Values of Nitrogen and Carbon in ...

    EPA Pesticide Factsheets

    Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is critical to interpreting values in these ecosystems. While base-level isotope data are generally readily available for estuaries, nearshore coastal waters, and the open ocean, the continental shelf is less studied. To address this, and as a first step toward developing a surrogate for base-level isotopic signature in this region, we collected surface and deep water samples from the United States’ eastern continental shelf in the Western Atlantic Ocean, from the Gulf of Maine to Cape Hatteras, periodically between 2000 and 2013. During the study, particulate matter 15dN values ranged from 0.8 to 17.4‰, and 13dC values from −26.4 to −15.6‰over the region. We used spatial autocorrelation analysis and random forest modeling to examine the spatial trends and potential environmental drivers of the stable isotope values. We observed general trends toward lower values for both nitrogen and carbon isotopes at the seaward edge of the shelf. Conversely, higher 15dN and 13dC values were observed on the landward edge of the shelf, in particular in the southern portion of the sampling area. Across all sites, the magnitude of the difference between the 15dN of subsurface and surface particulate m

  8. Edgecliff reefs - Devonian temperate water carbonate deposition

    SciTech Connect

    Wolosz, T.H. )

    1991-03-01

    The Middle Devonian Edgecliff Member of the Onondaga Formation in New York and Ontario, Canada, is a coral-rich, reefy,' crinoidal grainstone/packstone. The reefs contain only rare stromatoporoids and are devoid of algae, having been constructed by a fauna of mound and thicket-forming branching colonial rugosans, and large sheet favositids that populated grainstone/packstone flank beds and banks. Despite the restricted fauna, the reefs display a variety of growth patterns. Rugosan mounds range in size from 2-3 m diameter by 1 m thick, up to 230 m diameter by 15 m thick. Composite structures consist of interbedded rugosan buildups and packstone/grainstone flanks, ranging from shield-shaped reefs (240 m diameter by 6 m thick) in which the rugosans occur only as thickets, to pinnacle reefs (up to 3 km diameter by 60 m thick) in which rugosan mounds are interbedded with crinoidal flanks. Geographic distribution of these reef types and analysis of surrounding facies suggests that reef growth pattern was controlled by water depth and local rate of subsidence. Despite superfacial resemblance to modern deep water ahermatypic coral mounds and thickets, abundant coral breakage and overturning, and erosion of at least one reef core during an intermediate stage of reef growth supports a shallow water origin of these reefs. It is suggested that the Edgecliff and its reefs represent an example of Devonian cool water carbonate deposition, a hypothesis supported by a trend of increasing stromatoporoid abundance westwards across New York (in the direction of the paleo-equator).

  9. Methodologies for extraction of dissolved inorganic carbon for stable carbon isotope studies : evaluation and alternatives

    USGS Publications Warehouse

    Hassan, Afifa Afifi

    1982-01-01

    The gas evolution and the strontium carbonate precipitation techniques to extract dissolved inorganic carbon (DIC) for stable carbon isotope analysis were investigated. Theoretical considerations, involving thermodynamic calculations and computer simulation pointed out several possible sources of error in delta carbon-13 measurements of the DIC and demonstrated the need for experimental evaluation of the magnitude of the error. An alternative analytical technique, equilibration with out-gassed vapor phase, is proposed. The experimental studies revealed that delta carbon-13 of the DIC extracted from a 0.01 molar NaHC03 solution by both techniques agreed within 0.1 per mil with the delta carbon-13 of the DIC extracted by the precipitation technique, and an increase of only 0.27 per mil in that extracted by the gas evolution technique. The efficiency of extraction of DIC decreased with sulfate concentration in the precipitation technique but was independent of sulfate concentration in the gas evolution technique. Both the precipitation and gas evolution technique were found to be satisfactory for extraction of DIC from different kinds of natural water for stable carbon isotope analysis, provided appropriate precautions are observed in handling the samples. For example, it was found that diffusion of atmospheric carbon dioxide does alter the delta carbon-13 of the samples contained in polyethylene bottles; filtration and drying in the air change the delta carbon-13 of the samples contained in polyethylene bottles; filtration and drying in the air change the delta carbon-13 of the precipitation technique; hot manganese dioxide purification changes the delta carbon-13 of carbon dioxide. (USGS)

  10. Carbon sequestration in depleted oil shale deposits

    DOEpatents

    Burnham, Alan K; Carroll, Susan A

    2014-12-02

    A method and apparatus are described for sequestering carbon dioxide underground by mineralizing the carbon dioxide with coinjected fluids and minerals remaining from the extraction shale oil. In one embodiment, the oil shale of an illite-rich oil shale is heated to pyrolyze the shale underground, and carbon dioxide is provided to the remaining depleted oil shale while at an elevated temperature. Conditions are sufficient to mineralize the carbon dioxide.

  11. Carbon deposition characteristics of LO2/HC propellants

    NASA Technical Reports Server (NTRS)

    Hernandez, Rosemary; Mercer, Steve D.

    1987-01-01

    The generation and deposition of carbon have been studied using subscale hardware with LO2/RP-1, LO2/propane, and LO2/methane at low mixture ratio conditions. The deposition of carbon on the turbine simulator tubes was evaluated at mixture ratios of 0.20 to 0.60, and at chamber pressures from 720 to 1650 psia. The carbon-deposition rate is a strong function of mixture ratio and a weak function of chamber pressure. There is a mixture ratio that will minimize deposition for LO2/RP-1; a threshold mixture ratio for LO2/propane; and no deposition for LO2/methane at any mixture ratio tested. The turbine drive operating limits were defined for each fuel tested.

  12. Air-stable ink for scalable, high-throughput layer deposition

    DOEpatents

    Weil, Benjamin D; Connor, Stephen T; Cui, Yi

    2014-02-11

    A method for producing and depositing air-stable, easily decomposable, vulcanized ink on any of a wide range of substrates is disclosed. The ink enables high-volume production of optoelectronic and/or electronic devices using scalable production methods, such as roll-to-roll transfer, fast rolling processes, and the like.

  13. Carbon deposition model for oxygen-hydrocarbon combustion, volume 1

    NASA Technical Reports Server (NTRS)

    Hernandez, R.; Ito, J. I.; Niiya, K. Y.

    1987-01-01

    Presented are details of the design, fabrication, and testing of subscale hardware used in the evaluation of carbon deposition characteristics of liquid oxygen and three hydrocarbon fuels for both main chamber and preburner/gas generator operating conditions. In main chamber conditions, the deposition of carbon on the combustion chamber wall was investigated at mixture ratios of 2.0 to 4.0 and at pressures of 1000 to 1500 psia. No carbon deposition on the chamber walls was detected at these main chamber mixture ratios. In preburner/gas generator operating conditions, the deposition of carbon on the turbine simulator tubes was evaluated at mixture ratios of 0.20 to 0.60 and at chamber pressures of 720 to 1650 psia. The results of the tests showed carbon deposition rate to be a strong function of mixture ratio and a weak function of chamber pressure. Further analyses evaluated the operational consequences of carbon deposition on preburner/gas generator performance. The report is in two volumes, of which this is Volume 1 covering the main body of the report plus Appendixes A through D.

  14. Deposition of carbon on gold using synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Rosenberg, Richard A.; Mancini, Derrick C.

    1990-05-01

    Carbon contamination on the surfaces of optical components in beamlines is known to cause severe loss of flux, particularly for photon energies above the C K edge (˜ 280 eV). In order to gain insight into the mechanisms by which carbon deposition occurs we have used focussed, broadband synchrotron radiation (SR) to deposit carbon on gold under controlled conditions. Carbon was deposited by photolysis of various gases at pressures in the range of 10 -8 to 10 -6 Torr. Deposition was found to be localized to the area where the SR was incident on the surface. The relative concentration of carbon was monitored using Auger electron spectroscopy. The rate of deposition was found to be proportional to pressure and inversely proportional to substrate temperature. Effects of gas composition were also studied. Of the seven gases examined, acetone and methyl methacrylate had the highest deposition rate, while ethylene had the lowest. The ramifications of these findings on carbon contamination of beamline optical components are discussed.

  15. Carbon Deposition Model for Oxygen-Hydrocarbon Combustion, Volume 2

    NASA Technical Reports Server (NTRS)

    Hernandez, R.; Ito, J. I.; Niiya, K. Y.

    1987-01-01

    Presented are details of the design, fabrication, and testing of subscale hardware used in the evaluation of carbon deposition characteristics of liquid oxygen and three hydrocarbon fuels for both main chamber and preburner/gas generator operating conditions. In main chamber conditions, the deposition of carbon on the combustion chamber wall was investigated at mixture ratios of 2.0 to 4.0 and at chamber pressures of 1000 to 1500 psia. No carbon deposition on chamber walls was detected at these main chamber mixture ratios. In preburner/gas generator operating conditions, the deposition of carbon on the turbine simulator tubes was evaluated at mixture ratios of 0.20 to 0.60 and at chamber pressures of 720 to 1650 psia. The results of the tests showed carbon deposition rate to be a strong function of mixture ratio and a weak function of chamber pressure. Further analyses evaluated the operational concequences of carbon deposition on preburner/gas generator performance. This is Volume 2 of the report, which contains data plots of all the test programs.

  16. Seasonal variation in stable carbon and nitrogen isotope values of bats reflect environmental baselines.

    PubMed

    Popa-Lisseanu, Ana G; Kramer-Schadt, Stephanie; Quetglas, Juan; Delgado-Huertas, Antonio; Kelm, Detlev H; Ibáñez, Carlos

    2015-01-01

    The stable carbon and nitrogen isotope composition of animal tissues is commonly used to trace wildlife diets and analyze food chains. Changes in an animal's isotopic values over time are generally assumed to indicate diet shifts or, less frequently, physiological changes. Although plant isotopic values are known to correlate with climatic seasonality, only a few studies restricted to aquatic environments have investigated whether temporal isotopic variation in consumers may also reflect environmental baselines through trophic propagation. We modeled the monthly variation in carbon and nitrogen isotope values in whole blood of four insectivorous bat species occupying different foraging niches in southern Spain. We found a common pattern of isotopic variation independent of feeding habits, with an overall change as large as or larger than one trophic step. Physiological changes related to reproduction or to fat deposition prior to hibernation had no effect on isotopic variation, but juvenile bats had higher δ13C and δ15N values than adults. Aridity was the factor that best explained isotopic variation: bat blood became enriched in both 13C and 15N after hotter and/or drier periods. Our study is the first to show that consumers in terrestrial ecosystems reflect seasonal environmental dynamics in their isotope values. We highlight the danger of misinterpreting stable isotope data when not accounting for seasonal isotopic baselines in food web studies. Understanding how environmental seasonality is integrated in animals' isotope values will be crucial for developing reliable methods to use stable isotopes as dietary tracers.

  17. RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

    EPA Science Inventory

    We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...

  18. Characterization of Northern California petroleum by stable carbon isotopes

    USGS Publications Warehouse

    Lillis, Paul G.; Magoon, Leslie B.; Stanley, Richard G.; McLaughlin, Robert J.; Warden, Augusta

    2001-01-01

    The purpose of this study is to characterize natural occurrences of petroleum at the surface and in the subsurface within northern California in order to define and map petroleum systems for U.S. Geological Survey energy resource assessments. Furthermore, the chemical characterization and mapping of natural petroleum occurrences could also be used to discriminate natural occurrences from accidental oil spills during the activities of extraction or transportation of petroleum. Samples include petroleum from exploratory well tests, producing fields, natural seeps, and oil-stained rocks, and condensates from gas wells. Most of the sample localities are in northern California but a few samples from central and southern California are included for comparison (table 1). Even though other analyses were performed, only stable carbon isotope (δ13C) data are presented here for brevity and because δ13C values are one of the most discriminating characteristics of California petroleum.

  19. Deposition of superhard amorphous carbon films by pulsed arc sources

    SciTech Connect

    Scheibe, H.J.; Schultrich, B.; Ziegele, H.; Siemroth, P.

    1996-12-31

    Hydrogen-free amorphous carbon films with hardness comparable to crystalline superhard materials have been deposited by special Pulsed arc techniques. By the combination of very high hardness, low adhesion and high smoothness, these films show superior behaviour in wear and glide applications. The influence of plasma and deposition conditions on these film properties and the choice of optimum conditions are discussed.

  20. Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

    NASA Astrophysics Data System (ADS)

    Munro, L. E.; Longstaffe, F. J.; White, C. D.

    2003-12-01

    Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by

  1. Late Quaternary carbonate deposition at the bottom of the world

    NASA Astrophysics Data System (ADS)

    Frank, Tracy D.; James, Noel P.; Bone, Yvonne; Malcolm, Isabelle; Bobak, Lindsey E.

    2014-05-01

    Carbonate sediments on polar shelves hold great potential for improving understanding of climate and oceanography in regions of the globe that are particularly sensitive to global change. Such deposits have, however, not received much attention from sedimentologists and thus remain poorly understood. This study investigates the distribution, composition, diagenesis, and stratigraphic context of Late Quaternary calcareous sediments recovered in 15 piston cores from the Ross Sea shelf, Antarctica. Results are used to develop a depositional model for carbonate deposition on glaciated, polar shelves. The utility of the deposits as analogs for the ancient record is explored. In the Ross Sea, carbonate-rich lithofacies, consisting of poorly sorted skeletal sand and gravel, are concentrated in the west and along the outer reaches of the continental shelf and upper slope. Analysis of fossil assemblages shows that deposits were produced by numerous low-diversity benthic communities dominated locally by stylasterine hydrocorals, barnacles, or bryozoans. Radiocarbon dating indicates that carbonate sedimentation was episodic, corresponding to times of reduced siliciclastic deposition. Most accumulation occurred during a time of glacial expansion in the lead-up to the Last Glacial Maximum. A more recent interval of carbonate accumulation postdates the early Holocene sea level rise and the establishment of the modern grounding line for the Ross Ice Shelf. When carbonate factories were inactive, fossil debris was subjected to infestation by bioeroders, dissolution, fragmentation, and physical reworking. This study reveals the episodic nature of carbonate deposition in polar settings and a reciprocal relationship with processes that deliver and redistribute siliciclastic debris. Carbonate production is most active during colder periods of the glacial-interglacial cycle, a potential new sedimentological paradigm for polar carbonate systems. Low accumulation rates and long residence

  2. Enthalpy and high temperature relaxation kinetics of stable vapor-deposited glasses of toluene

    SciTech Connect

    Bhattacharya, Deepanjan; Sadtchenko, Vlad

    2014-09-07

    Stable non-crystalline toluene films of micrometer and nanometer thicknesses were grown by vapor deposition at distinct rates and probed by fast scanning calorimetry. Fast scanning calorimetry is shown to be extremely sensitive to the structure of the vapor-deposited phase and was used to characterize simultaneously its kinetic stability and its thermodynamic properties. According to our analysis, transformation of vapor-deposited samples of toluene during heating with rates in excess 10{sup 5} K s{sup −1} follows the zero-order kinetics. The transformation rate correlates strongly with the initial enthalpy of the sample, which increases with the deposition rate according to sub-linear law. Analysis of the transformation kinetics of vapor-deposited toluene films of various thicknesses reveal a sudden increase in the transformation rate for films thinner than 250 nm. The change in kinetics seems to correlate with the surface roughness scale of the substrate. The implications of these findings for the formation mechanism and structure of vapor-deposited stable glasses are discussed.

  3. Boron carbon nitride films deposited by sequential pulses laser deposition

    NASA Astrophysics Data System (ADS)

    Dinescu, M.; Perrone, A.; Caricato, A. P.; Mirenghi, L.; Gerardi, C.; Ghica, C.; Frunza, L.

    1998-05-01

    In this paper, we report the successful growth of c-BCN thin films by reactive pulsed laser ablation (RPLA) of a rotating target (3 Hz) formed of two semidisks: one of h-BN and the other one of graphite, with the substrate at room temperature. The irradiations were performed in vacuum (10 -5 Pa) and in N 2 ambient gas (1-100 Pa) using a XeCl excimer laser ( λ=308 nm, τFWHM=30 ns) with a fluence of 5 J/cm 2. Series of 10,000 pulses at a repetition rate of 10 Hz were directed to target. Different analysis techniques pointed out the synthesis of h-BCN and c-BCN. Microhardness measurements at the deposited films evidence high values up to 2.9 GPa. Secondary ion mass spectroscopy (SIMS) profiles showed the presence of layers of 600-700 nm thickness, with uniform concentrations of B, C and N in the films. Uniform signals of BN and CN, which are related to the BCN bond, are also present. X-ray photoelectron spectroscopy (XPS) studies pointed out the BCN compound formation. The deconvolution of B 1s recorded spectra evidenced a strong peak (centered at 188 eV) assigned to B bonded in BC 2N; the N 1s and C 1s spectra also confirm the BCN formation. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) analysis evidenced the presence of c-BCN phase (with crystallites of 30-80 nm) and h-BCN phase as well. The N 2 pressure strongly influenced the BCN formation and, consequently, the properties of the deposited films.

  4. Plasma deposited diamond-like carbon films for large neutralarrays

    SciTech Connect

    Brown, I.G.; Blakely, E.A.; Bjornstad, K.A.; Galvin, J.E.; Monteiro, O.R.; Sangyuenyongpipat, S.

    2004-07-15

    To understand how large systems of neurons communicate, we need to develop methods for growing patterned networks of large numbers of neurons. We have found that diamond-like carbon thin films formed by energetic deposition from a filtered vacuum arc carbon plasma can serve as ''neuron friendly'' substrates for the growth of large neural arrays. Lithographic masks can be used to form patterns of diamond-like carbon, and regions of selective neuronal attachment can form patterned neural arrays. In the work described here, we used glass microscope slides as substrates on which diamond-like carbon was deposited. PC-12 rat neurons were then cultured on the treated substrates and cell growth monitored. Neuron growth showed excellent contrast, with prolific growth on the treated surfaces and very low growth on the untreated surfaces. Here we describe the vacuum arc plasma deposition technique employed, and summarize results demonstrating that the approach can be used to form large patterns of neurons.

  5. Plasma reactor for deposition of carbon nanowalls at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Dimitrov, Zh; Mitev, D.; Kiss'ovski, Zh

    2016-10-01

    In this study a novel plasma reactor for deposition of carbon nanowalls at atmospheric pressure is constructed and characterized. A low power microwave discharge is used as a plasma source and working gas of Ar/H2/CH4 gas mixture. The substrate is heated by plasma flame and its temperature is in the range 600-700 C. The chemical composition of the plasma and the gas mixture effect on the concentration of the various particles in the plasma is investigated by optical emission spectroscopy. The emission spectrum of the plasma jet in Ar/H2/CH4 mixture shows the presence of carbon (Swan band) and an intensive line of CH (388 nm), which are necessary species for deposition of carbon nanostructures. Additional voltage in the range from -20 V to -100 V is applied in order to ensure the vertical growth of graphene walls. Results of deposited carbon nanostructures on metal substrate are shown.

  6. Low Speed Carbon Deposition Process for Hermetic Optical Fibers

    SciTech Connect

    ABRAMCZYK,JAROSLAW; ARTHUR,SARA E. TALLANT,DAVID R.; HIKANSSON,ADAM S.; LINDHOLM,ERIC A.; LO,JIE

    1999-09-29

    For optical fibers used in adverse environments, a carbon coating is frequently deposited on the fiber surface to prevent water and hydrogen ingression that lead respectively to strength degradation through fatigue and hydrogen-induced attenuation. The deposition of a hermetic carbon coating onto an optical fiber during the draw process holds a particular challenge when thermally-cured specialty coatings are subsequently applied because of the slower drawing rate. In this paper, we report on our efforts to improve the low-speed carbon deposition process by altering the composition and concentration of hydrocarbon precursor gases. The resulting carbon layers have been analyzed for electrical resistance, Raman spectra, coating thickness, and surface roughness, then compared to strength data and dynamic fatigue behavior.

  7. PHOTOCHEMICALLY-INDUCED ALTERATION OF STABLE CARBON ISOTOPE RATIOS (DELTA C-13) IN TERRIGENOUS DISSOLVED ORGANIC CARBON

    EPA Science Inventory

    Exposure of riverine waters to natural sunlight initiated alterations in stable carbon isotope ratios (delta C-13) of the associated dissolved organic carbon (DOC). Water samples were collected from two compositionally distinct coastal river systems in the southeastern United Sta...

  8. Carbonate replacement of lacustrine gypsum deposits in two Neogene continental basins, eastern Spain

    NASA Astrophysics Data System (ADS)

    Anadón, P.; Rosell, L.; Talbot, M. R.

    1992-07-01

    Bedded nonmarine gypsum deposits in the Miocene Teruel and Cabriel basins, eastern Spain, are partly replaced by carbonate. The Libros gypsum (Teruel Graben) is associated with fossiliferous carbonate wackestones and finely laminated, organic matter-rich mudstones which accumulated under anoxic conditions in a meromictic, permanent lake. The gypsum is locally pseudomorphed by aragonite or, less commonly, replaced by calcite. Low δ 13C values indicate that sulphate replacement resulted from bacterial sulphate reduction processes that were favoured by anacrobic conditions and abundant labile organic matter in the sediments. Petrographic evidence and oxygen isotopic composition suggest that gypsum replacement by aragonite occurred soon after deposition. A subsequent return to oxidising conditions caused some aragonite to be replaced by diagenetic gypsum. Native sulphur is associated with some of these secondary gypsum occurrences. The Los Ruices sulphate deposits (Cabriel Basin) contain beds of clastic and selenitic gypsum which are associated with limestones and red beds indicating accumulation in a shallow lake. Calcite is the principal replacement mineral. Bacterial sulphate reduction was insignificant in this basin because of a scarcity of organic matter. Stable isotope composition of diagenetic carbonate indicates that gypsum replacement occurred at shallow burial depths due to contact with dilute groundwaters of meteoric origin. Depositional environment evidently has a major influence upon the diagenetic history of primary sulphate deposits. The quantity of preserved organic matter degradable by sulphate-reducing bacteria is of particular importance and, along with groundwater composition, is the main factor controlling the mechanism of gypsum replacement by carbonate.

  9. Landscape deposition of Carbon after rill erosion

    NASA Astrophysics Data System (ADS)

    Kuhn, Nikolaus J.; Schwanghart, Wolfgang

    2010-05-01

    Conventionally, sediment generated by rill erosion is considered to have identical properties to the soil it is derived from because of the non-selective nature of rill erosion. However, this assumption is not valid once the rill sediment is transported through an agricultural landscape. Here a differentiation of sediment may occur due to cyclic rilling or changes in topography and flow obstruction, e.g. at field borders. In undisturbed rill systems, a regular pattern of erosion and deposition evolves due to the cyclic nature of energy expenditure on erosion and transport. Deposition of sediment is not uniform, but affects large particles first. Similar differentiation of sediment also occurs when rills are obstructed at the edges of fields or when slope angles are declining. Organic C content of sediment varies with grain size. Therefore, deposition of rill sediment leads to a differentiation of C content of both the deposited sediment and the sediment that is transported further downslope. In this study, soil and rill sediment organic C-data collected in March 2008 after the storm "Emma" near the town of Oberkail (50°02'N, 6°43'E) in the Eifel region of Germany are presented. To ensure that spatially averaged values of organic C content were achieved, sampling of soil and rill sediment was conducted along bodies of sediment deposition and the rills which had delivered the deposited sediment. A pairwise comparison of source area soil and corresponding rill sediment confirmed that the soil had a significantly higher organic C content than the sediment. Consequently, the sediment that remained in suspension had a higher organic C content than the sediment deposited at rill mouths and field edges. Such differentiation of sediment along its pathway through a geomorphic system highlights a critical issue for estimating the organic C balance along slopes. "Balance" is based on the assumption that sediment moved from a source to a sink does not change in quality

  10. Will it form a stable glass? How the stability of vapor deposited glasses depends on molecular structure

    NASA Astrophysics Data System (ADS)

    Tylinski, Michael; Beasley, Madeleine; Chua, Yeong Zen; Schick, Christoph; Ediger, Mark

    Over the past nine years physical vapor deposition has been used to prepare molecular glasses with exceptional properties. When heated, transformation of these highly stable glasses takes orders of magnitude longer than the transformation of liquid-cooled glasses. Until recently, it appeared that most organic molecules could form stable glasses when vapor deposited. We test the generality of stable glass formation by vapor-depositing a wide range of small organic molecules, including hydroxyl, carbonyl, phosphate, aromatic, and aliphatic functional groups. When prepared under conditions expected to yield highly stable glasses, we observe glasses with a wide range of kinetic stabilities, depending on the functional groups in the molecule. In general, alcohols and molecules with long aliphatic chains do not form highly stable glasses while aromatic molecules do. We also test the hypothesis that the surface mobility during deposition determines if a molecule is able to create highly stable glasses.

  11. Influence of variable rates of neritic carbonate deposition on atmospheric carbon dioxide and pelagic sediments

    NASA Technical Reports Server (NTRS)

    Walker, J. C.; Opdyke, B. C.

    1995-01-01

    Short-term imbalances in the global cycle of shallow water calcium carbonate deposition and dissolution may be responsible for much of the observed Pleistocene change in atmospheric carbon dioxide content. However, any proposed changes in the alkalinity balance of the ocean must be reconciled with the sedimentary record of deep-sea carbonates. The possible magnitude of the effect of shallow water carbonate deposition on the dissolution of pelagic carbonate can be tested using numerical simulations of the global carbon cycle. Boundary conditions can be defined by using extant shallow water carbonate accumulation data and pelagic carbonate deposition/dissolution data. On timescales of thousands of years carbonate deposition versus dissolution is rarely out of equilibrium by more than 1.5 x 10(13) mole yr-1. Results indicate that the carbonate chemistry of the ocean is rarely at equilibrium on timescales less than 10 ka. This disequilibrium is probably due to sea level-induced changes in shallow water calcium carbonate deposition/dissolution, an interpretation that does not conflict with pelagic sedimentary data from the central Pacific.

  12. Direct Deposition of Low Resistance Thermally Stable Ohmic Contacts to n-SiC

    DTIC Science & Technology

    2001-06-01

    Direct Deposition of Low Resistance Thermally Stable Ohmic Contacts to n-SiC by M. W. Cole, P. C. Joshi, M. H . Ervin, J. D. Demaree, M...SiC M. W. Cole, P. C. Joshi, J. D. Demaree, C. W. Hubbard, and J. K. Hirvonen Weapons and Materials Research Directorate, ARL M. H . Ervin and...device operation. ii Acknowledgments The authors would like to acknowledge H . Kim, A. Pique, D. B. Chrisey, C. K. Richardson, and M. H . Wisnioski

  13. Mesoproterozoic graphite deposits, New Jersey Highlands: Geologic and stable isotopic evidence for possible algal origins

    USGS Publications Warehouse

    Volkert, R.A.

    2000-01-01

    Graphite deposits of Mesoproterozoic age are locally abundant in the eastern New Jersey Highlands, where they are hosted by sulphidic biotite-quartz-feldspar gneiss, metaquartzite, and anatectic pegmatite. Gneiss and metaquartzite represent a shallow marine shelf sequence of locally organic-rich sand and mud. Graphite from massive deposits within metaquartzite yielded ??13C values of -26 ?? 2??? (1??), and graphite from massive deposits within biotite-quartz-feldspar gneiss yielded ??13C values of -23 ??4???. Disseminated graphite from biotite-quartz-feldspar gneiss country rock was -22 ??3???, indistinguishable from the massive deposits hosted by the same lithology. Anatectic pegmatite is graphitic only where generated from graphite-bearing host rocks; one sample gave a ??13C value of -15???. The ??34S values of trace pyrrhotite are uniform within individual deposits, but vary from 0 to 9??? from one deposit to another. Apart from pegmatitic occurrences, evidence is lacking for long-range mobilization of carbon during Grenvillian orogenesis or post-Grenvillian tectonism. The field, petrographic, and isotope data suggest that massive graphite was formed by granulite-facies metamorphism of Proterozoic accumulations of sedimentary organic matter, possibly algal mats. Preservation of these accumulations in the sedimentary environment requires anoxic basin waters or rapid burial. Anoxia would also favour the accumulation of dissolved ferrous iron in basin waters, which may explain some of the metasediment-hosted massive magnetite deposits in the New Jersey Highlands. ?? 2000 NRC.

  14. Ceres: Sulfur deposits and graphitized carbon

    NASA Astrophysics Data System (ADS)

    Hendrix, Amanda R.; Vilas, Faith; Li, Jian-Yang

    2016-09-01

    We report new results from observations of the dwarf planet Ceres using the Hubble Space Telescope in the spectral range 1160-5700 Å. Comparisons between Ceres' UV-visible spectra and laboratory measurements indicate that both sulfur species and graphitized carbon are important on Ceres' surface. We find a latitudinal gradient in UV absorption, with northern latitudes being more UV absorbing than southern latitudes, a trend that can be explained by increasing abundances of sulfur and SO2 toward northern latitudes. The presence of graphitized carbon is consistent with the surface of this airless body being carbonized in response to processes such as charged particle bombardment. The presence of volatile sulfur species is consistent with the idea that Ceres exhibits geothermal activity. Spectral differences with previous UV observations are likely due to the changing sulfurous and carbonaceous surface of Ceres.

  15. Carbon stable isotopes as indicators of coastal eutrophication.

    PubMed

    Oczkowski, Autumn; Markham, Erin; Hanson, Alana; Wigand, Cathleen

    2014-04-01

    Coastal ecologists and managers have frequently used nitrogen stable isotopes (delta15N) to trace and monitor sources of anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of delta15N data can often be challenging, as the isotope values fractionate substantially due to preferential retention and uptake by biota. There is a growing body of evidence that carbon isotopes may be a useful alternative indicator for eutrophication, as they may be sensitive to changes in primary production that result from anthropogenic nutrient inputs. We provide three examples of systems where delta13C values sensitively track phytoplankton production. First, earlier (1980s) mesocosm work established positive relationships between delta13C and dissolved inorganic nitrogen and dissolved silica concentrations. Consistent with these findings, a contemporary mesocosm experiment designed to replicate a temperate intertidal salt marsh environment also demonstrated that the system receiving supplementary nutrient additions had higher nutrient concentrations, higher chlorophyll concentrations, and higher delta13C values. This trend was particularly pronounced during the growing season, with differences less evident during senescence. And finally, these results were replicated in the open waters of Narragansett Bay, Rhode Island, USA, during a spring phytoplankton bloom. These three examples, taken together with the pre-existing body of literature, suggest that, at least in autotrophic, phytoplankton-dominated systems, delta13C values can be a useful and sensitive indicator of eutrophication.

  16. Effects of carbonate leaching on foraminifer stable isotopes ratios

    NASA Astrophysics Data System (ADS)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.

    2011-12-01

    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

  17. Thermodynamics and kinetics of carbon deposits on cobalt: a combined density functional theory and kinetic Monte Carlo study.

    PubMed

    Jansen, Antonius P J; Agrawal, Ravi; Spanu, Leonardo

    2016-10-19

    We have built a lattice gas model for cobalt-carbon interaction to investigate the thermodynamics and kinetics of carbon deposition on Co(0001) surfaces. The formation of carbon structures on cobalt is considered to be one of the causes of deactivation of a cobalt Fischer-Tropsch (FT) catalyst. The formation of graphene - the most thermodynamically stable phase under FT conditions - is kinetically inhibited during the first 30 hours of exposure of the surface to carbon, while the build-up of surface carbide is the fastest reaction. Our simulations clearly show that the kinetics of carbon deposition is the result of two competing effects: a fast subsurface diffusion and a slower surface diffusion to form a carbon-carbon bond.

  18. Carbon nanotube forests growth using catalysts from atomic layer deposition

    SciTech Connect

    Chen, Bingan; Zhang, Can; Esconjauregui, Santiago; Xie, Rongsi; Zhong, Guofang; Robertson, John; Bhardwaj, Sunil; Cepek, Cinzia

    2014-04-14

    We have grown carbon nanotubes using Fe and Ni catalyst films deposited by atomic layer deposition. Both metals lead to catalytically active nanoparticles for growing vertically aligned nanotube forests or carbon fibres, depending on the growth conditions and whether the substrate is alumina or silica. The resulting nanotubes have narrow diameter and wall number distributions that are as narrow as those grown from sputtered catalysts. The state of the catalyst is studied by in-situ and ex-situ X-ray photoemission spectroscopy. We demonstrate multi-directional nanotube growth on a porous alumina foam coated with Fe prepared by atomic layer deposition. This deposition technique can be useful for nanotube applications in microelectronics, filter technology, and energy storage.

  19. Stable isotopes of carbon dioxide in soil gas over massive sulfide mineralization at Crandon, Wisconsin

    USGS Publications Warehouse

    Alpers, C.N.; Dettman, D.L.; Lohmann, K.C.; Brabec, D.

    1990-01-01

    Stable isotope ratios of oxygen and carbon were determined for CO2 in soil gas in the vicinity of the massive sulfide deposit at Crandon, Wisconsin with the objective of determining the source of anomalously high CO2 concentrations detected previously by McCarthy et al. (1986). Values of ??13C in soil gas CO2 from depths between 0.5 and 1.0 m were found to range from -12.68??? to -20.03??? (PDB). Organic carbon from the uppermost meter of soil has ??13C between -24.1 and -25.8??? (PDB), indicating derivation from plant species with the C3 (Calvin) type of photosynthetic pathway. Microbial decomposition of the organic carbon and root respiration from C3 and C4 (Hatch-Slack) plants, together with atmospheric CO2 are the likely sources of carbon in soil gas CO2. Values of ??18O in soil-gas CO2 range from 32 to 38??? (SMOW). These ??18O values are intermediate between that calculated for CO2 gas in isotopic equilibrium with local groundwaters and that for atmospheric CO2. The ??18O data indicate that atmospheric CO2 has been incorporated by mixing or diffusion. Any CO2 generated by microbial oxidation of organic matter has equilibrated its oxygen isotopes with the local groundwaters. The isotopic composition of soil-gas CO2 taken from directly above the massive sulfide deposit was not distinguishable from that of background samples taken 1 to 2 km away. No enrichment of the ??13C value of soil-gas CO2 was observed, contrary to what would be expected if the anomalous CO2 were derived from the dissolution of Proterozoic marine limestone country rock or of Paleozoic limestone clasts in glacial till. Therefore, it is inferred that root respiration and decay of C3 plant material were responsible for most CO2 generation both in the vicinity of the massive sulfide and in the "background" area, on the occasion of our sampling. Interpretation of our data is complicated by the effects of rainfall, which significantly reduced the magnitude of the CO2 anomaly. Therefore, we cannot

  20. Alunite in the Pascua-Lama high-sulfidation deposit: Constraints on alteration and ore deposition using stable isotope geochemistry

    USGS Publications Warehouse

    Deyell, C.L.; Leonardson, R.; Rye, R.O.; Thompson, J.F.H.; Bissig, T.; Cooke, D.R.

    2005-01-01

    The Pascua-Lama high-sulfidation system, located in the El Indio-Pascua belt of Chile and Argentina, contains over 16 million ounces (Moz) Au and 585 Moz Ag. The deposit is hosted primarily in granite rocks of Triassic age with mineralization occurring in several discrete Miocene-age phreatomagmatic breccias and related fracture networks. The largest of these areas is Brecha Central, which is dominated by a mineralizing assemblage of alunite-pyrite-enargite and precious metals. Several stages of hydrothermal alteration related to mineralization are recognized, including all types of alunite-bearing advanced argillic assemblages (magmatic-hydrothermal, steam-heated, magmatic steam, and supergene). The occurrence of alunite throughout the paragenesis of this epithermal system is unusual and detailed radiometric, mineralogical, and stable isotope studies provide constraints on the timing and nature of alteration and mineralization of the alunite-pyiite-enargite assemblage in the deposit. Early (preore) alteration occurred prior to ca. 9 Ma and consists of intense silicic and advanced argillic assemblages with peripheral argillic and widespread propylitic zones. Alunite of this stage occurs as fine intergrowths of alunite-quartz ?? kaolinite, dickite, and pyrophyllite that selectively replaced feldspars in the host rock. Stable isotope systematics suggest a magmatic-hydrothermal origin with a dominantly magmatic fluid source. Alunite is coeval with the main stage of Au-Ag-Cu mineralization (alunite-pyrite-enargite assemblage ore), which has been dated at approximately 8.8 Ma. Ore-stage alunite has an isotopic signature similar to preore alunite, and ?? 34Salun-py data indicate depositional temperatures of 245?? to 305??C. The ??D and ?? 18O data exclude significant involvement of meteoric water during mineralization and indicate that the assemblage formed from H2S-dominated magmatic fluids. Thick steam-heated alteration zones are preserved at the highest elevations in

  1. Nitrogen: Unraveling the Secret to Stable Carbon-Supported Pt-Alloy Electrocatalysts

    DTIC Science & Technology

    2013-10-01

    design and optimization of next generation high performance catalyst materials. Nitrogen: unraveling the secret to stable carbon-supported Pt- alloy ...acquired on an aberration-corrected scanning transmission electron microscope (STEM). Improved catalyst–support interactions correlated to high ...release; distribution is unlimited. Nitrogen: unraveling the secret to stable carbon-supported Pt- alloy electrocatalysts The views, opinions and/or

  2. Mathematical modeling of stable carbon isotope ratios in natural gases^@?

    NASA Astrophysics Data System (ADS)

    Tang, Y.; Perry, J. K.; Jenden, P. D.; Schoell, M.

    2000-08-01

    A new approach is presented for mathematical modeling of stable carbon isotope ratios in hydrocarbon gases based on both theoretical and experimental data. The kinetic model uses a set of parallel first-order gas generation reactions in which the relative cracking rates of isotopically substituted (k∗) and unsubstituted (k) bonds are represented by the equation k∗/k=(Af∗/Af) exp(-ΔEa/RT), where R is the gas constant and T is temperature. Quantum chemistry calculations have been used to estimate the entropic (A f∗/A f) and enthalpic (ΔEa) terms for homolytic bond cleavage in a variety of simple molecules. For loss of a methyl group from a short-chain n-alkane (≤ C 6), for example, we obtain an average ΔEa of 42.0 cal/mol and an average A f∗/A f of 1.021. Expressed differently, 13C-methane generation is predicted to be 2.4% (24‰) slower than 12C-methane generation (from a short-chain n-alkane) in a sedimentary basin at 200°C but only 0.7% (7‰) slower in a laboratory heating experiment at 500°C. Similar calculations carried out for homolytic bond cleavage in other molecules show that with few exceptions, ΔEa varies between 0 and 60 cal/mol and A f∗/A f between 1.00 and 1.04. Examination of this larger data set reveals: (1) a weak sigmoid relationship between ΔEa and bond dissociation energy; and (2) a strong positive correlation between ΔEa and A f∗/A f. The significance of these findings is illustrated by fitting a kinetic model to chemical and isotopic data for the generation of methane from n-octadecane under isothermal closed-system conditions. For a specific temperature history, the fitted model provides quantitative relationships among methane carbon isotope composition, total methane yield and methane generation rate which may have relevance to the cracking of oil-prone kerogens and crude oil. The observed variability of the kinetic reactivity of various methane source rocks highlights the need to apply and adequately calibrate such

  3. Hard, amorphous carbon deposited from a fullerene discharge

    SciTech Connect

    Maiken, E.B.; Taborek, P.

    1995-12-31

    Hard, amorphous carbon films were deposited from an ion source using fullerite as carbon feedstock. For fixed ion energies, the film resistivities decreased exponentially with substrate temperature, suggesting activated growth of a conductive phase. Resistivity at 300 K ranged from 10{sup -3} to 10{sup 4} {Omega}m. E{sub -4} optical gaps of conductive films ranged from 0.1 to 1.1 eV.

  4. Atmospheric Plasma Deposition of Diamond-like Carbon Coatings

    SciTech Connect

    Ladwig, Angela

    2008-01-23

    There is great demand for thin functional coatings in the semiconductor, optics, electronics, medical, automotive and aerospace industries [1-13]. As fabricated components become smaller and more complex, the properties of the materials’ surface take on greater importance. Thin coatings play a key role in tailoring surfaces to give them the desired hardness, wear resistance, chemical inertness, and electrical characteristics. Diamond-like carbon (DLC) coatings possess an array of desirable properties, including outstanding abrasion and wear resistance, chemical inertness, hardness, a low coefficient of friction and exceptionally high dielectric strength [14-22]. Diamond-like carbon is considered to be an amorphous material, containing a mixture of sp2 and sp3 bonded carbon. Based on the percentage of sp3 carbon and the hydrogen content, four different types of DLC coatings have been identified: tetrahedral carbon (ta-C), hydrogenated amorphous carbon (a-C:H) hard, a-C:H soft, and hydrogenated tetrahedral carbon (ta-C:H) [20,24,25]. Possessing the highest hardness of 80 GPa, ta-C possesses an sp3 carbon content of 80 to 88u%, and no appreciable hydrogen content whereas a-C:H soft possesses a hardness of less than 10 GPa, contains an sp3 carbon content of 60% and a hydrogen content between 30 to 50%. Methods used to deposit DLC coatings include ion beam deposition, cathodic arc spray, pulsed laser ablation, argon ion sputtering, and plasma-enhanced chemical vapor deposition [73-83]. Researchers contend that several advantages exist when depositing DLC coatings in a low-pressure environment. For example, ion beam processes are widely utilized since the ion bombardment is thought to promote denser sp3-bonded carbon networks. Other processes, such as sputtering, are better suited for coating large parts [29,30,44]. However, the deposition of DLC in a vacuum system has several disadvantages, including high equipment cost and restrictions on the size and shape of

  5. Filtration properties of hierarchical carbon nanostructures deposited on carbon fibre fabrics

    NASA Astrophysics Data System (ADS)

    Kurzyp, M.; Mills, C. A.; Rhodes, R.; Pozegic, T. R.; Smith, C. T. G.; Beliatis, M. J.; Rozanski, L. J.; Werbowy, A.; Silva, S. R. P.

    2015-03-01

    Hierarchical carbon nanostructures have been produced and examined for their use in liquid filtration experiments. The nanostructures are based on carbon nanotube growth and graphite oxide sponge deposition on the surface of commercially available carbon fibre fabrics. The hierarchical nanomaterial construction on the carbon fibre fabric is made possible due to the chemical vapour deposited carbon nanotubes which act as anchoring sites for the solution deposited sponge nanomaterial. The nanomaterials show a high capacity for Rhodamine B filtration, with the carbon fibre—carbon nanotube—graphite oxide sponge fabric showing filtering performance comparable to a commercial activated carbon filter. After 40 successive filtrations of 10 mg ml-1 Rhodamine B solution, the filtrate of dual modified fabrics returned an increase in transparency of 94% when measured at approx. 550 nm compared to 72% for the commercial carbon filter. When normalised with respect to the areal density of the commercial filter, the increase in optical transparency of the filtrate from the dual modified fabrics reduces to 65%. The Rhodamine B is found to deposit in the carbon nanomaterials via a nucleation, growth and saturation mechanism.

  6. The Stable and Radio- Carbon Isotopic Content of Labile and Refractory Carbon in Atmospheric Particulate Matter

    NASA Astrophysics Data System (ADS)

    McNichol, A. P.; Rosenheim, B. E.; Gerlach, D. S.; Hayes, J. M.

    2006-12-01

    Studies of the isotopic content of atmospheric particulate matter are hampered by difficulties in chemically defining the pools of carbon and analytically isolating the different pools. We are conducting studies on reference materials and atmospheric aerosol samples to develop a method to measure stable and radio- carbon isotopes on the labile and refractory carbon. We are using a flow-through combustion system that allows us to combust, collect and measure the isotopic content of the gases produced at all stages of heating/oxidizing. We compare our results to those measured using a chemothermal oxidation method (CTO) (Gustafsson et al., 2001). In this method, refractory carbon is defined as the material remaining after pre- combusting a sample at 375°C in the presence of oxygen for 24 hours. The reference materials are diesel soot, apple leaves and a hybrid of the two (DiesApple), all from NIST. These provide carbon with two well-defined fractions -- the soot provides refractory carbon that is radiocarbon dead and the apple leaves provide organic carbon that is radiocarbon modern. Radiocarbon results from DiesApple indicate that the "refractory" carbon defined by the CTO method is actually a mixture of old and modern carbon that contains over 25% modern carbon. This suggests that charred material formed from the apples leaves during the pre-combustion step is contributing to the fraction we identify as refractory carbon. We are studying this by analyzing the individual materials and the mixture using our flow-through system. First results with this system indicate that the refractory fraction trapped from the DiesApple contains much less modern carbon than the CTO method, less than 7%. We will present detailed concentration and isotopic results of the generation of carbon dioxide during programmed combustion of each of the reference materials. We studied the radiocarbon content of both the total carbon (TC) and refractory carbon in the fine particulate matter (PM

  7. Stable and radioactive carbon in forest soils of Chhattisgarh, Central India: Implications for tropical soil carbon dynamics and stable carbon isotope evolution

    NASA Astrophysics Data System (ADS)

    Laskar, A. H.; Yadava, M. G.; Ramesh, R.

    2016-06-01

    Soils from two sites viz. Kotumsar and Tirathgarh, located ∼5 km apart in a tropical reserve forest (18°52‧N, 81°56‧E) in central India, have been explored for soil organic carbon (SOC) content, its mean residence time (MRT) and the evolution of stable carbon isotopic composition (δ13C). SOC stocks in the upper 30 cm of soil layers are ∼5.3 kg/m2 and ∼3.0 kg/m2; in the upper 110 m are ∼10.7 kg/m2 and ∼7.8 kg/m2 at Kotumsar and Tirathgarh, respectively. SOC decreases with increasing depth. Bomb carbon signature is observed in the upper ∼10 cm. Organic matters in the top soil layers (0-10 cm) have MRTs of the order of a century which increases gradually with depths, reaching 3500-5000 yrs at ∼100 cm. δ13C values of SOC increase with depth, the carbon isotopic fractionation is obtained to be -1.2‰ and -3‰ for soils at Kotumsar and Tirathgarh, respectively, confirmed using Rayleigh isotopic fractionation model. The evolution of δ13C in soils was also studied using a modified Rayleigh fractionation model incorporating a continuous input into the reservoir: the depth profiles of δ13C for SOC show that the input organic matter from surface into the deeper soil layers is either insignificant or highly labile and decomposes quite fast in the top layers, thus making little contribution to the residual biomasses of the deeper layers. This is an attempt to understand the distillation processes that take place in SOC, assess the extent of decomposition by microbes and effect of percolation of fresh organic matter into dipper soil layers which are important for stable isotope based paleoclimate and paleovegetation reconstruction and understanding the dynamics of organic carbon in soils.

  8. Carbonate deposition, climate stability, and Neoproterozoic ice ages.

    PubMed

    Ridgwell, Andy J; Kennedy, Martin J; Caldeira, Ken

    2003-10-31

    The evolutionary success of planktic calcifiers during the Phanerozoic stabilized the climate system by introducing a new mechanism that acts to buffer ocean carbonate-ion concentration: the saturation-dependent preservation of carbonate in sea-floor sediments. Before this, buffering was primarily accomplished by adjustment of shallow-water carbonate deposition to balance oceanic inputs from weathering on land. Neoproterozoic ice ages of near-global extent and multimillion-year duration and the formation of distinctive sedimentary (cap) carbonates can thus be understood in terms of the greater sensitivity of the Precambrian carbon cycle to the loss of shallow-water environments and CO2-climate feedback on ice-sheet growth.

  9. Soil Organic Carbon Stocks in Depositional Landscapes of Bavaria

    NASA Astrophysics Data System (ADS)

    Kriegs, Stefanie; Schwindt, Daniel; Völkel, Jörg; Kögel-Knabner, Ingrid

    2016-04-01

    Erosion leads to redistribution and accumulation of soil organic matter (SOM) within agricultural landscapes. These fluvic and colluvic deposits are characterized by a highly diverse vertical structure and can contain high amounts of soil organic carbon (SOC) over the whole soil profile. Depositional landscapes are therefore not only productive sites for agricultural use but also influence carbon dynamics which is of great interest with regard on the recent climate change debate. The aim of our study is to elucidate the spatial distribution of organic carbon stocks, as well as its depth function and the role of these landscapes as a reservoir for SOM. Therefore we compare two representative depositional landscapes in Bavaria composed of different parent materials (carbonate vs. granitic). We hypothesize that the soils associated with different depositional processes (fluvial vs. colluvial) differ in SOC contents and stocks, also because of different hydromorphic regimes in fluvic versus colluvic soil profiles. Sampling sites are located in the Alpine Foreland (quaternary moraines with carbonatic parent material) and the foothills of the Bavarian Forest (Granite with Loess) with the main soil types Fluvisols, Gleysols and Luvisols. At both sites we sampled twelve soil profiles up to 150 cm depth, six in the floodplain and six along a vertical slope transect. We took undisturbed soil samples from each horizon and analyzed them for bulk density, total Carbon (OC and IC) and total Nitrogen (N) concentrations. This approach allows to calculate total OC contents and OC stocks and to investigate vertical and horizontal distribution of OC stocks. It will also reveal differences in OC stocks due to the location of the soil profile in fluvic or colluvic deposition scenarios.

  10. Stable isotope, chemical, and mineral compositions of the Middle Proterozoic Lijiaying Mn deposit, Shaanxi Province, China

    USGS Publications Warehouse

    Yeh, Hsueh-Wen; Hein, James R.; Ye, Jie; Fan, Delian

    1999-01-01

    The Lijiaying Mn deposit, located about 250 km southwest of Xian, is a high-quality ore characterized by low P and Fe contents and a mean Mn content of about 23%. The ore deposit occurs in shallow-water marine sedimentary rocks of probable Middle Proterozoic age. Carbonate minerals in the ore deposit include kutnahorite, calcite, Mn calcite, and Mg calcite. Carbon (−0.4 to −4.0‰) and oxygen (−3.7 to −12.9‰) isotopes show that, with a few exceptions, those carbonate minerals are not pristine low-temperature marine precipitates. All samples are depleted in rare earth elements (REEs) relative to shale and have negative Eu and positive Ce anomalies on chondrite-normalized plots. The Fe/Mn ratios of representative ore samples range from about 0.034 to <0.008 and P/Mn from 0.0023 to <0.001. Based on mineralogical data, the low ends of those ranges of ratios are probably close to ratios for the pure Mn minerals. Manganese contents have a strong positive correlation with Ce anomaly values and a moderate correlation with total REE contents. Compositional data indicate that kutnahorite is a metamorphic mineral and that most calcites formed as low-temperature marine carbonates that were subsequently metamorphosed. The braunite ore precursor mineral was probably a Mn oxyhydroxide, similar to those that formed on the deep ocean-floor during the Cenozoic. Because the Lijiaying precursor mineral formed in a shallow-water marine environment, the atmospheric oxygen content during the Middle Proterozoic may have been lower than it has been during the Cenozoic.

  11. Stable isotopes in seafloor hydrothermal systems: Vent fluids, hydrothermal deposits, hydrothermal alteration, and microbial processes

    USGS Publications Warehouse

    Shanks, Wayne C.

    2001-01-01

    The recognition of abundant and widespread hydrothermal activity and associated unique life-forms on the ocean floor is one of the great scientific discoveries of the latter half of the twentieth century. Studies of seafloor hydrothermal processes have led to revolutions in understanding fluid convection and the cooling of the ocean crust, the chemical and isotopic mass balance of the oceans, the origin of stratiform and statabound massive-sulfide ore-deposits, the origin of greenstones and serpentinites, and the potential importance of the subseafloor biosphere. Stable isotope geochemistry has been a critical and definitive tool from the very beginning of the modern era of seafloor exploration.

  12. Cenomanian-turonian stable isotope signatures and depositional sequences in northeast Egypt and central Jordan

    NASA Astrophysics Data System (ADS)

    Farouk, Sherif; Ahmad, Fayez; Powell, John H.

    2017-02-01

    Lithostratigraphic, biostratigraphic and microfacies studies of two Cenomanian-Turonian shallow-marine, siliciclastic-carbonate successions at Gebel Ekma plateau (southwestern Sinai, Egypt) and Wadi Karak section (central Jordan) are calibrated with δ13C-, profiles to reveal relative sea-level changes within a sequence stratigraphic framework. The study provides significantly enhanced stratigraphic resolution and key sections for regional correlation. Lithofacies are dominated by well-developed peritidal to subtidal facies associations indicating deposition in a rimmed carbonate shelf setting. Biostratigraphic analysis indicates the presence of 6 ammonite zones, 3 calcareous nannofossil zones and 3 planktonic foraminiferal zones within the Cenomanian to Turonian succession. Six, third-order depositional sequences, bounded by correlatable sequence boundaries can be traced across the African-Arabian platform. Comparison with δ13C records in deeper water pelagic sequences help to improve the resolution of the boundaries of each depositional sequence. Recognition of time gaps at the sequence boundaries on the platform, recorded in different parts of African-Arabian platform, is attributed to local tectonic activity, associated with the change from passive to active margins, which are overprinted by the global eustatic signature.

  13. Mixed fuel strategy for carbon deposition mitigation in solid oxide fuel cells at intermediate temperatures.

    PubMed

    Su, Chao; Chen, Yubo; Wang, Wei; Ran, Ran; Shao, Zongping; Diniz da Costa, João C; Liu, Shaomin

    2014-06-17

    In this study, we propose and experimentally verified that methane and formic acid mixed fuel can be employed to sustain solid oxide fuel cells (SOFCs) to deliver high power outputs at intermediate temperatures and simultaneously reduce the coke formation over the anode catalyst. In this SOFC system, methane itself was one part of the fuel, but it also played as the carrier gas to deliver the formic acid to reach the anode chamber. On the other hand, the products from the thermal decomposition of formic acid helped to reduce the carbon deposition from methane cracking. In order to clarify the reaction pathways for carbon formation and elimination occurring in the anode chamber during the SOFC operation, O2-TPO and SEM analysis were carried out together with the theoretical calculation. Electrochemical tests demonstrated that stable and high power output at an intermediate temperature range was well-maintained with a peak power density of 1061 mW cm(-2) at 750 °C. With the synergic functions provided by the mixed fuel, the SOFC was running for 3 days without any sign of cell performance decay. In sharp contrast, fuelled by pure methane and tested at similar conditions, the SOFC immediately failed after running for only 30 min due to significant carbon deposition. This work opens a new way for SOFC to conquer the annoying problem of carbon deposition just by properly selecting the fuel components to realize their synergic effects.

  14. Were fossil spring-associated carbonates near Zaca Lake, Santa Barbara, California deposited under an ambient or thermal regime?

    NASA Astrophysics Data System (ADS)

    Ibarra, Yadira; Corsetti, Frank A.; Cheetham, Michael I.; Feakins, Sarah J.

    2014-03-01

    A previously undescribed succession of currently-inactive spring-associated carbonates located near Zaca Lake, Southern California, was investigated in order to determine the nature of deposition (ambient temperature or hydrothermal water, as both are found within the region). The carbonate deposits are up to ~ 1 m thick and formed discontinuously for over 200 m in a narrow valley between two ridges that drain Miocene Monterey Formation bedrock. Depositional facies along the presently dry fluvial path include barrage deposits, narrow fluvial channels, and cascade deposits. The carbonates are mesoscopically banded and contain ubiquitous micro- to macrophyte calcite encrusted fabrics. All of the depositional facies contain alternating bands (~ .05 mm to 5 mm thick) of dark brown and light brown isopachous calcite; the dark brown bands are composed of dense isopachous bladed calcite, whereas the light brown bands are composed of bundles of calcite tubules interpreted as the biosignature of the desmid microalgae Oocardium stratum. Oxygen isotope thermometry utilizing modern water δ18O values from the piped spring reveal depositional water temperature estimates that collectively range from ~ 11 to 16 °C. Stable isotope carbon values exhibit a mean δ13C value of - 9.01 ± 0.62‰ (1σ, n = 27). Our petrographic and geochemical data demonstrate that (1) inactive carbonates were likely sourced from ambient temperature water with a strong soil-zone δ13C signal, (2) the Oocardium calcite biosignature can be used to infer depositional temperature and flow conditions, and (3) the occurrence of extensive carbonates (especially the presence of a perched cascade deposit) indicate the carbonates formed when conditions were much wetter.

  15. Stable carbon isotope evidence for nitrogenous fertilizer impact on carbonate weathering in a small agricultural watershed.

    PubMed

    Brunet, F; Potot, C; Probst, A; Probst, J-L

    2011-10-15

    The isotopic signature of Dissolved Inorganic Carbon (DIC), δ(13)C(DIC), has been investigated in the surface waters of a small agricultural catchment on calcareous substratum, Montoussé, located at Auradé (south-west France). The Montoussé catchment is subjected to intense farming (wheat/sunflower rotation) and a moderated application of nitrogenous fertilizers. During the nitrification of the NH(4)(+), supplied by fertilization, nitrate and H(+) ions are produced in the soil. This anthropogenic acidity is combined with the natural acidity due to carbonic acid in weathering processes. From an isotopic point of view, with 'natural weathering', using carbonic acid, δ(13)C(DIC) is intermediate between the δ(13)C of soil CO(2) produced by organic matter oxidation and that of the carbonate rocks, while it has the same value as the carbonates when carbonic acid is substituted by another acid like nitric acid derived from nitrogen fertilizer. The δ(13)C(DIC) values range from -17.1‰ to -10.7‰ in Montoussé stream waters. We also measured the δ(13)C of calcareous molassic deposits (average -7.9‰) and of soil organic carbon (between -24.1‰ and -26‰) to identify the different sources of DIC and to estimate their contribution. The δ(13) C(DIC) value indicates that weathering largely follows the carbonic acid pathway at the springs (sources of the stream). At the outlet of the basin, H(+) ions, produced during the nitrification of N-fertilizer, also contribute to weathering, especially during flood events. This result is illustrated by the relationship between δ(13)C(DIC) and the molar ratio NO(3)(-)/(Ca(2+) + Mg(2+)). Consequently, when the contribution of nitrate increases, the δ(13)C(DIC) increases towards the calcareous end-member. This new isotopic result provides evidence for the direct influence of nitrogen fertilizer inputs on weathering, CO(2) consumption and base cation leaching and confirms previous results obtained using the chemistry of the

  16. Decoding depositional sequences in carbonate systems: Concepts vs experience

    NASA Astrophysics Data System (ADS)

    Pomar, Luis; Haq, Bilal U.

    2016-11-01

    Efficacy of sequence stratigraphic concepts in siliciclastic systems has been proven by successful applications in both academia and the industry over the past four decades. However, experience has demonstrated repeatedly that the relatively simple advective transportational approach of these models is less than successful when applied to the more complex carbonate systems and can lead to erroneous interpretations. Instead, an approach that includes the use of the changes in the biotic components of carbonate deposits to infer the sea-level trajectory and thereby placing it in the proper sequence framework is deemed to be more meaningful. This is exemplified with several well-studied examples that illustrate the variety of ways in which the biotic components can build carbonate platforms, and how these have changed through the ages prompted by biological evolution. This extended review discusses carbonate production, source to sink transportation influenced by sea-level changes, surface waves, as well as the less understood and under-appreciated internal waves, and the resulting variety of platforms that can be built by the interaction of these factors, as well as the changing patterns of biotic components with time. Their effect on the carbonate reservoir is considerable, understanding of which is the ultimate objective of carbonate research for applications in the industry. Key elements in the carbonate environments that differ from the siliciclastic systems are: 1) intrabasinal conditions (nutrients, salinity, temperature, water energy, transparency) are important controls on carbonate production and therefore also control in-situ accommodation and how it may be filled; 2) depositional accommodation can be both physical (controlled by hydrodynamics) and ecological (in the building-up above the base level mode); 3) because carbonates are products of biological activity, their production modes have been changing with time as their biotic components have evolved; 4

  17. Highly selective and stable carbon dioxide uptake in polyindole-derived microporous carbon materials.

    PubMed

    Saleh, Muhammad; Tiwari, Jitendra N; Kemp, K Christain; Yousuf, Muhammad; Kim, Kwang S

    2013-05-21

    Adsorption with solid sorbents is considered to be one of the most promising methods for the capture of carbon dioxide (CO₂) from power plant flue gases. In this study, microporous carbon materials used for CO₂ capture were synthesized by the chemical activation of polyindole nanofibers (PIF) at temperatures from 500 to 800 °C using KOH, which resulted in nitrogen (N)-doped carbon materials. The N-doped carbon materials were found to be microporous with an optimal adsorption pore size for CO₂ of 0.6 nm and a maximum (Brunauer-Emmett-Teller) BET surface area of 1185 m(2) g(-1). The PIF activated at 600 °C (PIF6) has a surface area of 527 m(2) g(-1) and a maximum CO₂ storage capacity of 3.2 mmol g(-1) at 25 °C and 1 bar. This high CO₂ uptake is attributed to its highly microporous character and optimum N content. Additionally, PIF6 material displays a high CO₂ uptake at low pressure (1.81 mmol g(-1) at 0.2 bar and 25 °C), which is the best low pressure CO₂ uptake reported for carbon-based materials. The adsorption capacity of this material remained remarkably stable even after 10 cycles. The isosteric heat of adsorption was calculated to be in the range of 42.7-24.1 kJ mol(-1). Besides the excellent CO₂ uptake and stability, PIF6 also exhibits high selectivity values for CO₂ over N₂, CH₄, and H₂ of 58.9, 12.3, and 101.1 at 25 °C, respectively, and these values are significantly higher than reported values.

  18. Stable Drop Formation and Deposition Control in Ink Jet Printing of Polyvinylidene Fluoride Solution

    NASA Astrophysics Data System (ADS)

    Thorne, Nathaniel; Yang, Xin; Sun, Ying; Complex Fluids and Multiphase Transport Lab-Drexel University Team

    2013-11-01

    Using inkjet printing as an additive fabrication method is an enabling technology for low-cost, high-throughput production of flexible electronics and photonics. Polymeric materials, such as Polyvinylidene fluoride (PVDF), are widely used as dielectric materials for microelectronics, batteries, among others. However, due to its large molecular weight and incompatibility with moisture in air, the stable drop formation of PVDF solution is quite challenging. In this study, we examine the effects of solute concentration, nozzle back pressure, ejection waveform, and ambient moisture on the formation of PVDF droplets. The deposition dynamics of inkjet-printed PVDF solutions are then examined as a function of the solvent concentration. Bi-solvents of different surface tensions and vapor pressures are used to induce Marangoni flows in order to suppress the coffee-ring effect. The deposition of a single droplet and the interactions between multiple drops are examined for a better control of the deposition uniformity. Printing of lines and patterns with reduced instability is also discussed.

  19. Highly Stable and Effective Doping of Graphene by Selective Atomic Layer Deposition of Ruthenium.

    PubMed

    Kim, Minsu; Kim, Ki-Ju; Lee, Seung-Joon; Kim, Hyun-Mi; Cho, Seong-Yong; Kim, Min-Sik; Kim, Soo-Hyun; Kim, Ki-Bum

    2017-01-11

    The sheet resistance of graphene synthesized by chemical vapor deposition is found to be significantly reduced by the selective atomic layer deposition (ALD) of Ru onto defect sites such as wrinkles and grain boundaries. With 200 ALD cycles, the sheet resistance is reduced from ∼500 to <50 Ω/sq, and the p-type carrier density is drastically increased from 10(13) to 10(15) cm(-2). At the same time, the carrier mobility is reduced from ∼670 to less than 100 cm(2) V(-1) s(-1). This doping of graphene proved to be very stable, with the electrical properties remaining unchanged over eight weeks of measurement. Selective deposition of Ru on defect sites also makes it possible to obtain a graphene film that is both highly transparent and electrically conductive (e.g., a sheet resistance of 125 Ω/sq with 92% optical transmittance at 550 nm). Highly doped graphene layers achieved by Ru ALD are therefore expected to provide a viable basis for transparent conducting electrodes.

  20. Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

    NASA Technical Reports Server (NTRS)

    Boreham, C. J.; Fookes, C. J.; Popp, B. N.; Hayes, J. M.

    1990-01-01

    Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

  1. The stable carbon isotopes in enstatite chondrites and Cumberland Falls

    NASA Astrophysics Data System (ADS)

    Deines, P.; Wickman, F. E.

    1985-01-01

    The carbon-isotopic composition (CIC) of the total carbon in the enstatite chondrites Indarch, Abee, St. Marks, Pillistfer, Hvittis and Daniel's Kuil and the enstatite achondrite Cumberland Falls has been measured. The empirical relationship between CIC and total carbon content is distinct from that of carbonaceous and ordinary chondrites. Within the enstatite chondrite group the average C-13 content increases with petrographic type: E4 less than E5 less than E6. Daniel's Kuil shows the largest C-13 enrichment in the bulk carbon of any meteorite. The CIC is most clearly correlated with the abundance of the elements Zn, Cd, and In. Insofar as these elements may hold the key to the understanding of enstatite chondrites, more detailed combined CIC and trace-element studies of these meteorites will play an important role in the deciphering of their history.

  2. STABLE ISOTOPIC EVIDENCE OF CARBON AND NITROGEN USE IN CULTURED ECTOMYCORRHIZAL AND SAPROTROPHIC FUNGI

    EPA Science Inventory

    Stable isotopes in sporocarps have proven useful for inferring ectomycorrhizal or saprotrophic status and understanding carbon (C) and nitrogen (N) utilization. However, greater understanding of processes producing isotopic concentrations is needed. We measured natural abundanc...

  3. Isotope composition of carbon in the carbonates of the Gumbeykan scheelite deposits in the southern Urals

    SciTech Connect

    Korzhinskii, A.F.; Mamchur, G.P.; Yarynych, O.A.

    1980-10-01

    Through investigations of the isotope composition of carbon of various generations and carbonates from marbles, skarns, and nested and vein scheelite orebodies, the probable source of carbon of these carbonates has been established as a mixture of sedimentary carbonates, carbon dioxide with carbonic acid that was formed by oxidation of the organic matter from sedimentary terrane (..delta..C/sup 13/ - 0.05 to -0.62%). In the calcite and dolomite phenocrysts of marble and the coarse-grained dolostone, containing scheelite, the carbon was lighter (..delta..C/sup 13/ from -0.60 to -0.87%). For the dolomite and ankerite from scheelite pockets of the Balkan deposit and quartz veins of the Buranovo, ..delta..C/sup 13/ varied from -0.44 to -0.87%. The lightest carbon found in strontianite (..delta..C/sup 13/ = -1.32%), located near the coating of the organic matter (..delta..C/sup 13/ = -1.26%) in fractures of the quartz vein of the Buranovo deposit. In the section through the orebodies and near-ore diffusion-metasomatic zones of the Balkan deposit, the lessening of carbon in the carbonates was observed, with increasing distance away from the fracture. ..delta..C/sup 13/ in the altered granitoids ranged from -0.44 to -1.03%; while in the diopside-wollastonite hornfels, from -0.89 to 1.13%. The lessening in weight of the carbon is explained by diffusional fractionation of the isotopes caused apparently by the differential movement of volatile mixtures of carbon during ore-forming processes and the formation of their diffusion-metasomatic zones.

  4. Molten carbonate fuel cell reduction of nickel deposits

    DOEpatents

    Smith, James L.; Zwick, Stanley A.

    1987-01-01

    A molten carbonate fuel cell with anode and cathode electrodes and an eleolyte formed with two tile sections, one of the tile sections being adjacent the anode and limiting leakage of fuel gas into the electrolyte with the second tile section being adjacent the cathode and having pores sized to permit the presence of oxygen gas in the electrolyte thereby limiting the formation of metal deposits caused by the reduction of metal compositions migrating into the electrolyte from the cathode.

  5. Carbon Stable Isotopes as Indicators of Coastal Eutrophication

    EPA Science Inventory

    Coastal ecologists and managers have frequently used nitrogen stable isotopes (δ15N) to trace and monitor anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of δ15N data can often be challenging, if not confounding, as the isotope values fractionate su...

  6. Stable carbonous catalyst particles and method for making and utilizing same

    DOEpatents

    Ganguli, Partha S.; Comolli, Alfred G.

    2005-06-14

    Stable carbonous catalyst particles composed of an inorganic catalytic metal/metal oxide powder and a carbonaceous binder material are formed having a basic inner substantially uniform-porous carbon coating of the catalytic powder, and may include an outer porous carbon coating layer. Suitable inorganic catalytic powders include zinc-chromite (ZnO/Cr.sub.2 03) and suitable carbonaceous liquid binders having molecular weight of 200-700 include partially polymerized furfuryl alcohol, which are mixed together, shaped and carbonized and partially oxidized at elevated temperature. Such stable carbonous catalyst particles such as 0.020-0.100 inch (0.51-2.54 mm) diameter extrudates, have total carbon content of 2-25 wt. % and improved crush strength of 1.0-5 1b/mn, 50-300 m.sup.2 /g surface area, and can be advantageously utilized in fixed bed or ebullated/fluidized bed reactor operations. This invention also includes method steps for making the stable carbonous catalyst particles having improved particle strength and catalytic activity, and processes for utilizing the active stable carbonous carbon-coated catalysts such as for syn-gas reactions in ebullated/fluidized bed reactors for producing alcohol products and Fischer-Tropsch synthesis liquid products.

  7. Newly developed stepwise electroless deposition enables a remarkably facile synthesis of highly active and stable amorphous Pd nanoparticle electrocatalysts for oxygen reduction reaction.

    PubMed

    Poon, Kee Chun; Tan, Desmond C L; Vo, Thang D T; Khezri, Bahareh; Su, Haibin; Webster, Richard D; Sato, Hirotaka

    2014-04-09

    This paper reports on highly active and stable amorphous Pd nanoparticle electrocatalysts for the oxygen reduction reaction. The amorphous catalysts were synthesized by a remarkably facile and quick electroless deposition process newly developed in this study (process time <5 min). An electrode substrate (glassy carbon, carbon cloth) was sequentially dipped for 10 s into two separate solutions of a reducing agent (sodium hypophosphite (NaH2PO2)) and Pd ions to deposit amorphous Pd nanoparticles containing phosphorus (Pd-P). By repeating the deposition cycles, the specific and mass activities of the Pd nanoparticles can be actively tuned. Owing to the nanoscale amorphous nature, the obtained Pd-P nanoparticle electrocatalysts exhibited superior specific and mass activities compared with crystalline Pd nanoparticles synthesized by another reducing agent (N2H4) and commercial Pt-loaded carbon (Pt/C) and Pd-loaded carbon (Pd/C). The specific and mass activities of the amorphous Pd-P nanoparticles were over 4.5 times and 2.6 times higher than previously reported values of Pd and Pt catalysts.

  8. Raman spectroscopic studies of thin film carbon nanostructures deposited using electro deposition technique

    NASA Astrophysics Data System (ADS)

    Dayal, Saurabh; Sasi, Arshali; Jhariya, Sapna; Sasikumar, C.

    2016-05-01

    In the present work our focus is to synthesize carbon nanostructures (CNS) by electro deposition technique without using any surface pretreatment or catalyst preparation before CNS formation. The process were carried out at significantly low voltage and at low temperature as reported elsewhere. Further the samples were characterized using different characterization tools such as SEM and Raman spectroscopy. The SEM results showed the fibres or tubular like morphology. Raman spectra shows strong finger print at 1600 cm-1 (G peak), 1350 cm-1 (D peak) along with the radial breathing mode (RBM) between 150cm-1 to 300 cm-1. This confirms the formation of tubular carbon nanostructures.

  9. USE OF THE COMPOSITION AND STABLE CARBON ISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (Gamma 13C) of individual microbial phospholipid fatty acids (PLFAS) in soils and sediments as indicators of live microbial biomass levels and microbial carbon source. For studies of soil organic matter (SO...

  10. PRODUCTION AND TRANSPORT OF CARBON DIOXIDE IN A CONTAMINATED VADOSE ZONE: A STABLE AND RADIOACTIVE CARBON ISOTOPE STUDY

    EPA Science Inventory

    Analyses of soil gas compositions and stable and radioactive carbon isotopes in the vadose zone above an alluvial aquifer were conducted at an organic solvent disposal site in southeast Phoenix, AZ. The study investigated the source and movement of carbon dioxide above a plume of...

  11. Conformal atomic layer deposition of alumina on millimeter tall, vertically-aligned carbon nanotube arrays.

    PubMed

    Stano, Kelly L; Carroll, Murphy; Padbury, Richard; McCord, Marian; Jur, Jesse S; Bradford, Philip D

    2014-11-12

    Atomic layer deposition (ALD) can be used to coat high aspect ratio and high surface area substrates with conformal and precisely controlled thin films. Vertically aligned arrays of multiwalled carbon nanotubes (MWCNTs) with lengths up to 1.5 mm were conformally coated with alumina from base to tip. The nucleation and growth behaviors of Al2O3 ALD precursors on the MWCNTs were studied as a function of CNT surface chemistry. CNT surfaces were modified through a series of post-treatments including pyrolytic carbon deposition, high temperature thermal annealing, and oxygen plasma functionalization. Conformal coatings were achieved where post-treatments resulted in increased defect density as well as the extent of functionalization, as characterized by X-ray photoelectron spectroscopy and Raman spectroscopy. Using thermogravimetric analysis, it was determined that MWCNTs treated with pyrolytic carbon and plasma functionalization prior to ALD coating were more stable to thermal oxidation than pristine ALD coated samples. Functionalized and ALD coated arrays had a compressive modulus more than two times higher than a pristine array coated for the same number of cycles. Cross-sectional energy dispersive X-ray spectroscopy confirmed that Al2O3 could be uniformly deposited through the entire thickness of the vertically aligned MWCNT array by manipulating sample orientation and mounting techniques. Following the ALD coating, the MWCNT arrays demonstrated hydrophilic wetting behavior and also exhibited foam-like recovery following compressive strain.

  12. Lipid Correction for Carbon Stable Isotope Analysis of Deep-sea Fishes

    EPA Science Inventory

    Lipid extraction is used prior to stable isotope analysis of fish tissues to remove variability in the carbon stable isotope ratio (d13C) caused by varying lipid content among samples. Our objective was to evaluate an application of a mass balance correction for the effect of lip...

  13. Carbon nanowalls grown by microwave plasma enhanced chemical vapor deposition during the carbonization of polyacrylonitrile fibers

    SciTech Connect

    Li Jiangling; Su Shi; Kundrat, Vojtech; Abbot, Andrew M.; Ye, Haitao; Zhou Lei; Mushtaq, Fajer; Ouyang Defang; James, David; Roberts, Darren

    2013-01-14

    We used microwave plasma enhanced chemical vapor deposition (MPECVD) to carbonize an electrospun polyacrylonitrile (PAN) precursor to form carbon fibers. Scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy were used to characterize the fibers at different evolution stages. It was found that MPECVD-carbonized PAN fibers do not exhibit any significant change in the fiber diameter, whilst conventionally carbonized PAN fibers show a 33% reduction in the fiber diameter. An additional coating of carbon nanowalls (CNWs) was formed on the surface of the carbonized PAN fibers during the MPECVD process without the assistance of any metallic catalysts. The result presented here may have a potential to develop a novel, economical, and straightforward approach towards the mass production of carbon fibrous materials containing CNWs.

  14. Factors Controlling Black Carbon Deposition in Snow in the Arctic

    NASA Astrophysics Data System (ADS)

    Qi, L.; Li, Q.; He, C.; Li, Y.

    2015-12-01

    This study evaluates the sensitivity of black carbon (BC) concentration in snow in the Arctic to BC emissions, dry deposition and wet scavenging efficiency using a 3D global chemical transport model GEOS-Chem driven by meteorological field GEOS-5. With all improvements, simulated median BC concentration in snow agrees with observation (19.2 ng g-1) within 10%, down from -40% in the default GEOS-Chem. When the previously missed gas flaring emissions (mainly located in Russia) are included, the total BC emission in the Arctic increases by 70%. The simulated BC in snow increases by 1-7 ng g-1, with the largest improvement in Russia. The discrepancy of median BC in snow in the whole Arctic reduces from -40% to -20%. In addition, recent measurements of BC dry deposition velocity suggest that the constant deposition velocity of 0.03 cm s-1 over snow and ice used in the GEOS-Chem is too low. So we apply resistance-in-series method to calculate the dry deposition velocity over snow and ice and the resulted dry deposition velocity ranges from 0.03 to 0.24 cm s-1. However, the simulated total BC deposition flux in the Arctic and BC in snow does not change, because the increased dry deposition flux has been compensated by decreased wet deposition flux. However, the fraction of dry deposition to total deposition increases from 16% to 25%. This may affect the mixing of BC and snow particles and further affect the radative forcing of BC deposited in snow. Finally, we reduced the scavenging efficiency of BC in mixed-phase clouds to account for the effect of Wegener-Bergeron-Findeisen (WBF) process based on recent observations. The simulated BC concentration in snow increases by 10-100%, with the largest increase in Greenland (100%), Tromsø (50%), Alaska (40%), and Canadian Arctic (30%). Annual BC loading in the Arctic increases from 0.25 to 0.43 mg m-2 and the lifetime of BC increases from 9.2 to 16.3 days. This indicates that BC simulation in the Arctic is really sensitive to

  15. Carbon sequestration potential of soils in southeast Germany derived from stable soil organic carbon saturation.

    PubMed

    Wiesmeier, Martin; Hübner, Rico; Spörlein, Peter; Geuß, Uwe; Hangen, Edzard; Reischl, Arthur; Schilling, Bernd; von Lützow, Margit; Kögel-Knabner, Ingrid

    2014-02-01

    Sequestration of atmospheric carbon (C) in soils through improved management of forest and agricultural land is considered to have high potential for global CO2 mitigation. However, the potential of soils to sequester soil organic carbon (SOC) in a stable form, which is limited by the stabilization of SOC against microbial mineralization, is largely unknown. In this study, we estimated the C sequestration potential of soils in southeast Germany by calculating the potential SOC saturation of silt and clay particles according to Hassink [Plant and Soil 191 (1997) 77] on the basis of 516 soil profiles. The determination of the current SOC content of silt and clay fractions for major soil units and land uses allowed an estimation of the C saturation deficit corresponding to the long-term C sequestration potential. The results showed that cropland soils have a low level of C saturation of around 50% and could store considerable amounts of additional SOC. A relatively high C sequestration potential was also determined for grassland soils. In contrast, forest soils had a low C sequestration potential as they were almost C saturated. A high proportion of sites with a high degree of apparent oversaturation revealed that in acidic, coarse-textured soils the relation to silt and clay is not suitable to estimate the stable C saturation. A strong correlation of the C saturation deficit with temperature and precipitation allowed a spatial estimation of the C sequestration potential for Bavaria. In total, about 395 Mt CO2 -equivalents could theoretically be stored in A horizons of cultivated soils - four times the annual emission of greenhouse gases in Bavaria. Although achieving the entire estimated C storage capacity is unrealistic, improved management of cultivated land could contribute significantly to CO2 mitigation. Moreover, increasing SOC stocks have additional benefits with respect to enhanced soil fertility and agricultural productivity.

  16. Deposition And Characterization Of Ultra Thin Diamond Like Carbon Films

    NASA Astrophysics Data System (ADS)

    Tomcik, B.

    2010-07-01

    Amorphous hydrogenated and/or nitrogenated carbon films, a-C:H/a-C:N, in overall thickness up to 2 nm are materials of choice as a mechanical and corrosion protection layer of the magnetic media in modern hard disk drive disks. In order to obtain high density and void-free films the sputtering technology has been replaced by different plasma and ion beam deposition techniques. Hydrocarbon gas precursors, like C2H2 or CH4 with H2 and N2 as reactive gases are commonly used in Kaufman DC ion and RF plasma beam sources. Optimum incident energy of carbon ions, C+, is up to 100 eV while the typical ion current densities during the film formation are in the mA/cm2 range. Other carbon deposition techniques, like filtered cathodic arc, still suffer from co-deposition of fine nanosized carbon clusters (nano dust) and their improvements are moving toward arc excitation in the kHz and MHz frequency range. Non-destructive film analysis like μ-Raman optical spectroscopy, spectroscopic ellipsometry, FTIR and optical surface analysis are mainly used in the carbon film characterization. Due to extreme low film thicknesses the surface enhanced Raman spectroscopy (SERS) with pre-deposited layer of Au can reduce the signal collection time and minimize photon-induced damage during the spectra acquisition. Standard approach in the μ-Raman film evaluation is the measurement of the position (shift) and area of D and G-peaks under the deconvoluted overall carbon spectrum. Also, a slope of the carbon spectrum in the 1000-2000 cm-1 wavenumber range is used as a measure of the hydrogen intake within a film. Diamond like carbon (DLC) film should possess elasticity and self-healing properties during the occasional crash of the read-write head flying only couple of nanometers above the spinning film. Film corrosion protection capabilities are mostly evaluated by electrochemical tests, potentio-dynamic and linear polarization method and by business environmental method. Corrosion mechanism

  17. Characterization of Carbon Deposits Formed During Plasma Pyrolysis of Xinjiang Candle Coal

    NASA Astrophysics Data System (ADS)

    Zhu, Guilin; Meng, Yuedong; Shu, Xingsheng; Fang, Shidong

    2009-08-01

    Carbon deposits were formed on the reactor wall during plasma pyrolysis of the Xinjiang candle coal in our V-style plasma pyrolysis pilot-plant. The carbon deposits were studied using a scanning electronic microscope (SEM) and the X-ray diffraction (XRD) method. It was found that carbon deposits located at different parts in the reactor exhibited different microscopic patterns. The formation mechanism of the carbon deposits was deduced. The downward increase in the graphitization degree of the carbon deposits was found and interpreted.

  18. USE OF THE COMPOSITION AND STABLE CARBONIISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (*13C) of individual microbial phospholipid fatty acids (PLFAs) in soils and sediments as indicators of live microbial biomass levels and microbial carbon source. For studies of soil organic matter (SOM) cy...

  19. Mechanisms controlling soil carbon sequestration under atmospheric nitrogen deposition

    SciTech Connect

    R.L. Sinsabaugh; D.R. Zak; D.L. Moorhead

    2008-02-19

    Increased atmospheric nitrogen (N) deposition can alter the processing and storage of organic carbon in soils. In 2000, we began studying the effects of simulated atmospheric N deposition on soil carbon dynamics in three types of northern temperate forest that occur across a wide geographic range in the Upper Great Lakes region. These ecosystems range from 100% oak in the overstory (black oak-white oak ecosystem; BOWO) to 0% overstory oak (sugar maple-basswood; SMBW) and include the sugar maple-red oak ecosystem (SMRO) that has intermediate oak abundance. The leaf litter biochemistry of these ecosystems range from highly lignified litter (BOWO) to litter of low lignin content (SMBW). We selected three replicate stands of each ecosystem type and established three plots in each stand. Each plot was randomly assigned one of three levels of N deposition (0, 30 & 80 kg N ha-1 y-1) imposed by adding NaNO3 in six equal increments applied over the growing season. Through experiments ranging from the molecular to the ecosystem scales, we produced a conceptual framework that describes the biogeochemistry of soil carbon storage in N-saturated ecosystems as the product of interactions between the composition of plant litter, the composition of the soil microbial community and the expression of extracellular enzyme activities. A key finding is that atmospheric N deposition can increase or decrease the soil C storage by modifying the expression of extracellular enzymes by soil microbial communities. The critical interactions within this conceptual framework have been incorporated into a new class of simulations called guild decomposition models.

  20. Stable Gold(III) Catalysts by Oxidative Addition of a Carbon-Carbon Bond

    PubMed Central

    Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch

    2014-01-01

    Whereas low-valent late transition metal catalysis has become indispensible for chemical synthesis, homogeneous high-valent transition metal catalysis is underdeveloped, mainly due to the reactivity of high-valent transition metal complexes and the challenges associated with synthesizing them. In this manuscript, we report a mild carbon-carbon bond cleavage reaction by a Au(I) complex that generates a stable Au(III) cationic complex. Complementary to the well-established soft and carbophilic Au(I) catalyst, this Au(III) complex exhibits hard, oxophilic Lewis acidity. This is exemplified by catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(III)-activated cinnamaldehyde intermediate. The concepts revealed in this study provide a strategy for accessing high-valent transition metal catalysis from readily available precursors. PMID:25612049

  1. Stable gold(III) catalysts by oxidative addition of a carbon-carbon bond

    NASA Astrophysics Data System (ADS)

    Wu, Chung-Yeh; Horibe, Takahiro; Jacobsen, Christian Borch; Toste, F. Dean

    2015-01-01

    Low-valent late transition-metal catalysis has become indispensable to chemical synthesis, but homogeneous high-valent transition-metal catalysis is underdeveloped, mainly owing to the reactivity of high-valent transition-metal complexes and the challenges associated with synthesizing them. Here we report a carbon-carbon bond cleavage at ambient conditions by a Au(I) complex that generates a stable Au(III) cationic complex. In contrast to the well-established soft and carbophilic Au(I) catalyst, this Au(III) complex exhibits hard, oxophilic Lewis acidity. For example, we observed catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(III)-activated cinnamaldehyde intermediate. The concepts revealed suggest a strategy for accessing high-valent transition-metal catalysis from readily available precursors.

  2. Stable isotopes reveal habitat-related diet shifts in facultative deposit-feeders

    NASA Astrophysics Data System (ADS)

    Rossi, Francesca; Baeta, Alexandra; Marques, João C.

    2015-01-01

    Seagrass patches interspersed in a sediment matrix may vary environmental conditions and affect feeding habits of consumers and food-web structure. This paper investigates diet shifts between bare sediments and a Zostera noltei (Hornemann, 1832) meadow for three facultative deposit-feeding macrofaunal consumers, notably the bivalve Scrobicularia plana (da Costa, 1778), the polychaete Hediste diversicolor (O.T. Müller, 1776), and the gastropod Hydrobia ulvae (Pennant, 1778). In July 2008, one eelgrass meadow and two bare sediment locations were chosen in the Mondego estuary (40° 08″ N, 8° 50‧ W, Portugal) and sampled for stable isotope signatures (δ13C and δ15N) of macrofauna consumers and some of their potential basal food sources, such as sedimentary organic matter (SOM), microphytobenthos (MPB), seagrass shoots, leaves and seaweeds laying on the surface sediment. The δ15N of H. diversicolor was 3‰ higher in the eelgrass meadow than in bare sediment, indicating a change of trophic position, whereas the Bayesian stable-isotope mixing model showed that S. plana assimilated more macroalgal detritus than microphytobenthos in the eelgrass bed. Such habitat-related diet shifts have the potential to change structure and spatial dynamics of benthic food webs.

  3. Air-Stable flexible organic light-emitting diodes enabled by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Lin, Yuan-Yu; Chang, Yi-Neng; Tseng, Ming-Hung; Wang, Ching-Chiun; Tsai, Feng-Yu

    2015-01-01

    Organic light-emitting diodes (OLED) are an energy-efficient light source with many desirable attributes, besides being an important display of technology, but its practical application has been limited by its low air-stability. This study demonstrates air-stable flexible OLEDs by utilizing two atomic-layer-deposited (ALD) films: (1) a ZnO film as both a stable electron-injection layer (EIL) and as a gas barrier in plastics-based OLED devices, and (2) an Al2O3/ZnO (AZO) nano-laminated film for encapsulating the devices. Through analyses of the morphology and electrical/gas-permeation properties of the films, we determined that a low ALD temperature of 70 °C resulted in optimal EIL performance from the ZnO film and excellent gas-barrier properties [water vapor transmission rate (WVTR) <5 × 10-4 g m-2 day-1] from both the ZnO EIL and the AZO encapsulating film. The low-temperature ALD processes eliminated thermal damage to the OLED devices, which were severe when a 90 °C encapsulation process was used, while enabling them to achieve an air-storage lifetime of >10 000 h.

  4. Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Gibson, Everett K., Jr.; Golden, D. C.; Ming, Douglas W.; McKay, Gordon A.

    2003-01-01

    An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.

  5. Thermal stability of vapor-deposited stable glasses of an organic semiconductor

    NASA Astrophysics Data System (ADS)

    Walters, Diane M.; Richert, Ranko; Ediger, M. D.

    2015-04-01

    Vapor-deposited organic glasses can show enhanced kinetic stability relative to liquid-cooled glasses. When such stable glasses of model glassformers are annealed above the glass transition temperature Tg, they lose their thermal stability and transform into the supercooled liquid via constant velocity propagating fronts. In this work, we show that vapor-deposited glasses of an organic semiconductor, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD), also transform via propagating fronts. Using spectroscopic ellipsometry and a new high-throughput annealing protocol, we measure transformation front velocities for TPD glasses prepared with substrate temperatures (TSubstrate) from 0.63 to 0.96 Tg, at many different annealing temperatures. We observe that the front velocity varies by over an order of magnitude with TSubstrate, while the activation energy remains constant. Using dielectric spectroscopy, we measure the structural relaxation time of supercooled TPD. We find that the mobility of the liquid and the structure of the glass are independent factors in controlling the thermal stability of TPD films. In comparison to model glassformers, the transformation fronts of TPD have similar velocities and a similar dependence on TSubstrate, suggesting universal behavior. These results may aid in designing active layers in organic electronic devices with improved thermal stability.

  6. Stable Isotopes (O, H, and S) in the Muteh Gold Deposit, Golpaygan Area, Iran

    SciTech Connect

    Abdollahi, M. J. Karimpour, M. H.; Kheradmand, A.; Zarasvandi, A. R.

    2009-06-15

    The Muteh gold district with nine gold deposits is located in the Sanandaj-Sirjan metamorphic zone. Gold mineralization occurs in a pre-Permian complex which mainly consists of green schists, meta-volcanics, and gneiss rocks. Shear zones are the host of gold mineralization. Gold paragenesis minerals include pyrite, chalcopyrite, pyrrhotite, and secondary minerals. Pyrites occur as pre-, syn-, and post-metamorphism minerals. To determine the source of the ore-bearing fluids, fifty samples were selected for petrographical and stable isotope studies. The mean values of 12.4 per mille , and -42 per mille for {delta}{sup 18}O and {delta}D isotopes, respectively, and a mean value of 7.75 per mille of calculated fractionation factors for {delta}{sup 18}O H{sub 2}O, from quartz veins indicate that metamorphic host rocks are the most important source for the fluids and gold mineralization. Three generations of pyrite can be distinguished showing a wide range of {delta}{sup 34}S. Gold mineralization is closely associated with intense hydrothermal alteration along the ductile shear zones. The characteristics of the gold mineralization in the study area are similar to those of orogenic gold deposits elsewhere.

  7. Thermal stability of vapor-deposited stable glasses of an organic semiconductor

    SciTech Connect

    Walters, Diane M.; Ediger, M. D.; Richert, Ranko

    2015-04-07

    Vapor-deposited organic glasses can show enhanced kinetic stability relative to liquid-cooled glasses. When such stable glasses of model glassformers are annealed above the glass transition temperature T{sub g}, they lose their thermal stability and transform into the supercooled liquid via constant velocity propagating fronts. In this work, we show that vapor-deposited glasses of an organic semiconductor, N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), also transform via propagating fronts. Using spectroscopic ellipsometry and a new high-throughput annealing protocol, we measure transformation front velocities for TPD glasses prepared with substrate temperatures (T{sub Substrate}) from 0.63 to 0.96 T{sub g}, at many different annealing temperatures. We observe that the front velocity varies by over an order of magnitude with T{sub Substrate}, while the activation energy remains constant. Using dielectric spectroscopy, we measure the structural relaxation time of supercooled TPD. We find that the mobility of the liquid and the structure of the glass are independent factors in controlling the thermal stability of TPD films. In comparison to model glassformers, the transformation fronts of TPD have similar velocities and a similar dependence on T{sub Substrate}, suggesting universal behavior. These results may aid in designing active layers in organic electronic devices with improved thermal stability.

  8. Graphene coated with controllable N-doped carbon layer by molecular layer deposition as electrode materials for supercapacitors

    NASA Astrophysics Data System (ADS)

    Chen, Yao; Gao, Zhe; Zhang, Bin; Zhao, Shichao; Qin, Yong

    2016-05-01

    In this work, graphene is coated with nitrogen-doped carbon layer, which is produced by a carbonization process of aromatic polyimide (PI) films deposited on the surfaces of graphene by molecular layer deposition (MLD). The utilization of MLD not only allows uniform coating of PI layers on the surfaces of pristine graphene without any surface treatment, but also enables homogenous dispersion of doped nitrogen atoms in the carbonized products. The as-prepared N-doped carbon layer coated graphene (NC-G) exhibited remarkable capacitance performance as electrode materials for supercapacitor, showing a high specific capacitance of 290.2 F g-1 at current density of 1 A g-1 in 6 M KOH aqueous electrolyte, meanwhile maintaining good rate performance and stable cycle capability. The NC-G synthesized by this way represents an alternative promising candidate as electrode material for supercapacitors.

  9. Preparation of starch and other carbon fractions from higher plant leaves for stable carbon isotope analysis.

    PubMed

    Wanek, W; Heintel, S; Richter, A

    2001-01-01

    The measurement of the carbon isotope composition of starch and cellulose still relies on chemical isolation of these water-insoluble plant constituents and subsequent elemental analysis by isotope ratio mass spectrometry (EA/IRMS) of the purified fractions, while delta(13)C values of low-molecular-weight organic compounds are now routinely measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Here we report a simple and reliable method for processing milligram quantities of dried plant material for the analysis of the carbon isotope composition of lipids, soluble sugars, starch and cellulose from the same sample. We evaluated three different starch preparation methods, namely (1) enzymatic hydrolysis by alpha-amylase, (2) solubilization by dimethyl sulfoxide (DMSO) followed by precipitation with ethanol, and (3) partial hydrolysis by HCl followed by precipitation of the resulting dextrins by ethanol. Starch recovery for three commercially available native starches (from potato, rice and wheat) varied from 48 to 81% for the techniques based on precipitation, whereas the enzymatic technique exhibited yields between 99 and 105%. In addition, the DMSO and HCl techniques introduced a significant (13)C fractionation of up to 1.9 per thousand, while the carbon isotope composition of native starches analyzed after enzymatic digestion did not show any significant difference from that of untreated samples. The enzymatic starch preparation method was then incorporated into a protocol for determination of delta(13)C signatures of lipids, soluble carbohydrates, starch and crude cellulose. The procedure is based on methanol/chloroform/water extraction of dried and ground leaf material. After recovery of the chloroform phase (lipid fraction), the methanol/water phase was deionized by ion exchange (soluble carbohydrate fraction) and the pellet treated with heat-stable alpha-amylase (starch fraction). The remaining insoluble material was subjected

  10. Stable carbon isotope depth profiles and soil organic carbon dynamics in the lower Mississippi Basin

    USGS Publications Warehouse

    Wynn, J.G.; Harden, J.W.; Fries, T.L.

    2006-01-01

    Analysis of depth trends of 13C abundance in soil organic matter and of 13C abundance from soil-respired CO2 provides useful indications of the dynamics of the terrestrial carbon cycle and of paleoecological change. We measured depth trends of 13C abundance from cropland and control pairs of soils in the lower Mississippi Basin, as well as the 13C abundance of soil-respired CO2 produced during approximately 1-year soil incubation, to determine the role of several candidate processes on the 13C depth profile of soil organic matter. Depth profiles of 13C from uncultivated control soils show a strong relationship between the natural logarithm of soil organic carbon concentration and its isotopic composition, consistent with a model Rayleigh distillation of 13C in decomposing soil due to kinetic fractionation during decomposition. Laboratory incubations showed that initially respired CO 2 had a relatively constant 13C content, despite large differences in the 13C content of bulk soil organic matter. Initially respired CO2 was consistently 13C-depleted with respect to bulk soil and became increasingly 13C-depleted during 1-year, consistent with the hypothesis of accumulation of 13C in the products of microbial decomposition, but showing increasing decomposition of 13C-depleted stable organic components during decomposition without input of fresh biomass. We use the difference between 13C / 12C ratios (calculated as ??-values) between respired CO 2 and bulk soil organic carbon as an index of the degree of decomposition of soil, showing trends which are consistent with trends of 14C activity, and with results of a two-pooled kinetic decomposition rate model describing CO2 production data recorded during 1 year of incubation. We also observed inconsistencies with the Rayleigh distillation model in paired cropland soils and reasons for these inconsistencies are discussed. ?? 2005 Elsevier B.V. All rights reserved.

  11. Stable carbon isotope fractionation by sulfate-reducing bacteria

    NASA Technical Reports Server (NTRS)

    Londry, Kathleen L.; Des Marais, David J.

    2003-01-01

    Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

  12. Stable carbon and nitrogen isotope enrichment in primate tissues

    PubMed Central

    Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

    2010-01-01

    Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

  13. Stable carbon and nitrogen isotopes in vertical peat profiles of natural and drained boreal peatlands

    NASA Astrophysics Data System (ADS)

    Nykänen, Hannu; Mpamah, Promise; Rissanen, Antti; Pitkänen, Aki; Turunen, Jukka; Simola, Heikki

    2015-04-01

    Peatlands form a significant carbon pool in the global carbon cycle. Change in peat hydrology, due to global warming is projected to change microbiological processes and peat carbon pool. We tested if bulk stable carbon and nitrogen isotopes serve as indicators of severe long term drying in peatlands drained for forestry. Depth profile analysis of peat, for their carbon and nitrogen content as well as their carbon and nitrogen stable isotopic signatures, were conducted for peatlands in southern and eastern Finland, having ombrotrophic and minerotrophic natural and corresponding drained pairs or separate drained sites. The selection of sites allowed us to compare changes due to different fertility and changes due to long term artificial drying. Drainage lasting over 40 years has led to changes in hydrology, vegetation, nutrient mineralization and respiration. Furthermore, increased nutrient uptake and possible recycling of peat nitrogen and carbon trough vegetation back to the peat surface, also possibly has an effect on the stable isotopic composition of peat carbon and nitrogen. We think that drainage induced changes somehow correspond to those caused by changed hydrology due to climate change. We will present data from these measurements and discuss their implications for carbon and nitrogen flows in peatlands.

  14. Raman spectra of amorphous carbon films deposited by SWP

    NASA Astrophysics Data System (ADS)

    Xu, Junqi; Liu, Weiguo; Hang, Lingxia; Su, Junhong; Fan, Huiqing

    2010-10-01

    Amorphous carbon film is one of the most important anti-reflection protective films coated on infrared optical components. In this paper, hydrogen-free amorphous carbon films were deposited by new type surface-wave-sustained plasma (SWP) source with a graphite target at various experiment parameters. The laser Raman spectroscopy at wavelength of 514 nm was used to investigate the structure and bonding of these carbon films. The results showed consanguineous correlations between the intensity ratio ID/IG and the experiment parameters such as microwave power, target voltage and gas pressure applied to the SWP source. Raman spectra proved the structure of these carbon films prepared by SWP technique is typical diamond-like carbon (DLC). The analysis on G peak position and intensity ratio ID/IG indicated that Raman shifts moves to low wavenumber and ID/IG decreases with the increasing of microwave power from 150 W to 330 W. These results means the formation of sp3 bond prefers higher microwave power. DLC films prepared at target voltage of -200 V have higher sp3 content than that of -350 V, moreover, an increase of gas pressure during experiments yields higher sp3 content at the microwave power below 270 W, whereas the change of sp3 content is slight with the various conditions when microwave power exceeds 270 W.

  15. Dual-Carbon sources fuel the OCS deep-reef Community, a stable isotope investigation

    USGS Publications Warehouse

    Sulak, Kenneth J.; Berg, J.; Randall, Michael; Dennis, George D.; Brooks, R.A.

    2008-01-01

    The hypothesis that phytoplankton is the sole carbon source for the OCS deep-reef community (>60 m) was tested. Trophic structure for NE Gulf of Mexico deep reefs was analyzed via carbon and nitrogen stable isotopes. Carbon signatures for 114 entities (carbon sources, sediment, fishes, and invertebrates) supported surface phytoplankton as the primary fuel for the deep reef. However, a second carbon source, the macroalga Sargassum, with its epiphytic macroalgal associate, Cladophora liniformis, was also identified. Macroalgal carbon signatures were detected among 23 consumer entities. Most notably, macroalgae contributed 45 % of total carbon to the 13C isotopic spectrum of the particulate-feeding reef-crest gorgonian Nicella. The discontinuous spatial distribution of some sessile deep-reef invertebrates utilizing pelagic macroalgal carbon may be trophically tied to the contagious distribution of Sargassum biomass along major ocean surface features.

  16. Nano structured carbon nitrides prepared by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Karuppannan, Ramesh; Prashantha, M.

    2010-08-01

    Nanostructured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition(CVD). A two zone furnace with a temperature profile having a uniform temperature over a length of 20 cm length has been designed and developed. The precursor Azabenzimidazole was taken in a quartz tube and evaporated at 400 0C. The dense vapours enter the pyrolysis zone kept at a desired temperature and deposit on the quartz substrates. The FTIR spectrum of the prepared samples shows peaks at 1272 cm-1 (C.N stretching) and 1600 cm-1 (C=N) confirms the bonding of nitrogen with carbon. Raman D and G peaks, are observed at 1360 cm-1 and 1576 cm-1 respectively. XPS core level spectra of C 1s and N 1s show the formation of π bonding between carbon and nitrogen atoms. The size of the nano crystals estimated from the SEM images and XRD is ~100 nm. In some regions of the sample a maximum of 57 atom % of nitrogen has been observed.

  17. Stable isotope mass balances versus concentration differences of dissolved inorganic carbon - implications for tracing carbon turnover in reservoirs.

    PubMed

    Barth, Johannes A C; Mader, Michael; Nenning, Franziska; van Geldern, Robert; Friese, Kurt

    2017-02-13

    The aim of this study was to identify sources of carbon turnover using stable isotope mass balances. For this purpose, two pre-reservoirs in the Harz Mountains (Germany) were investigated for their dissolved and particulate carbon contents (dissolved inorganic carbon (DIC), dissolved organic carbon, particulate organic carbon) together with their stable carbon isotope ratios. DIC concentration depth profiles from March 2012 had an average of 0.33 mmol L(-1). Increases in DIC concentrations later on in the year often corresponded with decreases in its carbon isotope composition (δ(13)CDIC) with the most negative value of -18.4 ‰ in September. This led to a carbon isotope mass balance with carbon isotope inputs of -28.5 ‰ from DOC and -23.4, -31.8 and -30.7 ‰ from algae, terrestrial and sedimentary matter, respectively. Best matches between calculated and measured DIC gains were achieved when using the isotope composition of algae. This shows that this type of organic material is most likely responsible for carbon additions to the DIC pool when its concentrations and δ(13)CDIC values correlate negatively. The presented isotope mass balance is transferable to other surface water and groundwater systems for quantification of organic matter turnover.

  18. Apparatus and process for deposition of hard carbon films

    DOEpatents

    Nyaiesh, Ali R.; Garwin, Edward L.

    1989-01-01

    A process and an apparatus for depositing thin, amorphous carbon films having extreme hardness on a substrate is described. An enclosed chamber maintained at less than atmospheric pressure houses the substrate and plasma producing elements. A first electrode is comprised of a cavity enclosed within an RF coil which excites the plasma. A substrate located on a second electrode is excited by radio frequency power applied to the substrate. A magnetic field confines the plasma produced by the first electrode to the area away from the walls of the chamber and focuses the plasma onto the substrate thereby yielding film deposits having higher purity and having more rapid buildup than other methods of the prior art.

  19. Apparatus and process for deposition of hard carbon films

    DOEpatents

    Nyaiesh, Ali R.; Garwin, Edward L.

    1989-01-03

    A process and an apparatus for depositing thin, amorphous carbon films having extreme hardness on a substrate is described. An enclosed chamber maintained at less than atmospheric pressure houses the substrate and plasma producing elements. A first electrode is comprised of a cavity enclosed within an RF coil which excites the plasma. A substrate located on a second electrode is excited by radio frequency power applied to the substrate. A magnetic field confines the plasma produced by the first electrode to the area away from the walls of the chamber and focuses the plasma onto the substrate thereby yielding film deposits having higher purity and having more rapid buildup than other methods of the prior art.

  20. Sputtering deposition and characterization of ultrathin amorphous carbon films

    NASA Astrophysics Data System (ADS)

    Lu, Wei

    1999-11-01

    This dissertation focuses on experimental investigations of ultrathin, ultrasmooth amorphous carbon (a-C) films deposited on Si(100) substrates by radio frequency (RF) sputtering and characterization of the nanomechanical and nanotribological properties and thermal stability of the films. Ultrathin a-C films of thickness 5--100 nm and typical root-mean-square roughness of 0.15--1 nm were deposited on ultrasmooth Si(100) substrates using pure argon as the sputtering gas. A low-pressure RF argon discharge model was used to analyze the plasma parameters in the film growth environment. These plasma parameters correlate the deposition conditions with the film growth processes. Atomic force microscopy (AFM) and surface force microscopy (SFM) were used to characterize the nanomechanical and nanotribological properties of the a-C films. X-ray photoelectron spectroscopy (XPS) was used to investigate the compositions and microstructures of the films. Sputter-etching measurements of the a-C films by energetic argon ion bombardment were used to study the surface binding energy of carbon atoms in a-C films deposited under different conditions. The dependence of film properties on deposition conditions was studied, and relations between nanomechanical and nanotribological properties were discussed in terms of a modified deformation index. The deformation and nanotribology mechanisms of the a-C films were compared with those of other films, such as TiC and Cr films (both 100 nm thick), and bulk Si(100). Reactive RF sputtering of nitrogenated amorphous carbon (a-CNx) films was investigated by introducing nitrogen into the a-C films during film growth by using an argon-nitrogen gas mixture as the sputtering gas. The alloying effect of nitrogen on the film growth and properties, such as hardness and surface energy, was studied and interpreted in terms of the changes in the plasma environment induced due to differences in the composition of the sputtering gas mixture. The thermal

  1. Carbon deposition model for oxygen-hydrocarbon combustion

    NASA Technical Reports Server (NTRS)

    Bossard, John A.

    1988-01-01

    The objectives are to use existing hardware to verify and extend the database generated on the original test programs. The data to be obtained are the carbon deposition characteristics when methane is used at injection densities comparable to full scale values. The database will be extended to include liquid natural gas (LNG) testing at low injection densities for gas generator/preburner conditions. The testing will be performed at mixture ratios between 0.25 and 0.60, and at chamber pressures between 750 and 1500 psi.

  2. Plasma-enhanced chemical vapor deposition of multiwalled carbon nanofibers

    NASA Technical Reports Server (NTRS)

    Matthews, Kristopher; Cruden, Brett A.; Chen, Bin; Meyyappan, M.; Delzeit, Lance

    2002-01-01

    Plasma-enhanced chemical vapor deposition is used to grow vertically aligned multiwalled carbon nanofibers (MWNFs). The graphite basal planes in these nanofibers are not parallel as in nanotubes; instead they exhibit a small angle resembling a stacked cone arrangement. A parametric study with varying process parameters such as growth temperature, feedstock composition, and substrate power has been conducted, and these parameters are found to influence the growth rate, diameter, and morphology. The well-aligned MWNFs are suitable for fabricating electrode systems in sensor and device development.

  3. Are there carbonate deposits in the Valles Marineris, Mars?

    NASA Technical Reports Server (NTRS)

    Nedell, Susan S.; Mckay, Christopher P.

    1989-01-01

    The precipitation of 30 mbar of Martian atmosphere CO2 as carbonates in lakes is suggested to be the source of thick sequences of layered deposits found in the Valles Marineris. Support is adduced for this scenario from processes occurring in the perennially frozen dry valley lakes of Antarctica, where the lake water is supersaturated with atmospheric gases. Atmospheric CO2 would have accumulated in such Martian lakes as temperature fell, and the presence of an insulating ice cover would have allowed liquid water to exist.

  4. Stable and responsive fluorescent carbon nanotube silica gels

    SciTech Connect

    Dattelbaum, Andrew M; Gupta, Gautam; Doorn, Stephen K; Duque, Juan G

    2010-05-03

    Here we report a general route to prepare silica nanocomposite gels doped with fluorescent single walled carbon nanotubes (SWNT). We show that tetramethylorthosilicate (TMOS) vapors can be used to gel an aqueous suspension of surfactant-wrapped SWNT while maintaining fluorescence from the semiconducting nanotubes. The vapor phase silica process is performed at room temperature and is simple, reproducible, relatively quick, and requires no dilution of SWNT dispersions. However, exposure of aqueous SWNT suspensions to TMOS vapors resulted in an acidification of the suspension prior to gelation that caused a decrease in the emission signal from sodium dodecylsulfate (SDS) wrapped SWNT. We also show that although the SWNT are encapsulated in silica the emission signal from the encapsulated SWNT may be attenuated by exposing the nanocomposites to small aromatic molecules known to mitigate SWNT emission. These results demonstrate a new route for the preparation of highly luminescent SWNT/silica composite materials that are potentially useful for future sensing applications.

  5. Stable isotopic evidence for methane seeps in Neoproterozoic postglacial cap carbonates.

    PubMed

    Jiang, Ganqing; Kennedy, Martin J; Christie-Blick, Nicholas

    2003-12-18

    The Earth's most severe glaciations are thought to have occurred about 600 million years ago, in the late Neoproterozoic era. A puzzling feature of glacial deposits from this interval is that they are overlain by 1-5-m-thick 'cap carbonates' (particulate deep-water marine carbonate rocks) associated with a prominent negative carbon isotope excursion. Cap carbonates have been controversially ascribed to the aftermath of almost complete shutdown of the ocean ecosystems for millions of years during such ice ages--the 'snowball Earth' hypothesis. Conversely, it has also been suggested that these carbonate rocks were the result of destabilization of methane hydrates during deglaciation and concomitant flooding of continental shelves and interior basins. The most compelling criticism of the latter 'methane hydrate' hypothesis has been the apparent lack of extreme isotopic variation in cap carbonates inferred locally to be associated with methane seeps. Here we report carbon isotopic and petrographic data from a Neoproterozoic postglacial cap carbonate in south China that provide direct evidence for methane-influenced processes during deglaciation. This evidence lends strong support to the hypothesis that methane hydrate destabilization contributed to the enigmatic cap carbonate deposition and strongly negative carbon isotopic anomalies following Neoproterozoic ice ages. This explanation requires less extreme environmental disturbance than that implied by the snowball Earth hypothesis.

  6. Stable Isotope Constraints on N Deposition and Cycling in Lake Tahoe

    NASA Astrophysics Data System (ADS)

    Michalski, G.; Young, R.; Thiemens, M.

    2004-12-01

    Oligotrophic Lake Tahoe has seen a decrease in opacity over the past 5 decades, which has been attributed to particulate matter (shoreline development) and algal growth (nutrients). The lake has also seen a shift from being nitrogen limited to phosphorous limited in the same time frame. Identifying the source of the increased nitrogen loading is essential for mitigation strategies to keep Lake Tahoe Blue - a 10 billion dollar watershed restoration campaign. Atmospheric deposition of nitric acid and nitrate aerosols (NO3-atm) is thought to be a significant source of new N to the lake surface. Quantifying the flux and fate of NO3-atm is limited by modeling estimates of deposition, utilization and re nitrification of organic N. Stable isotope tracers can help resolve these limitations. Δ 17O measurements, the δ 17O enrichment over the expected .52 δ 18O enrichment, have been shown to be a sensitive tracer of NO3-atm. Oxygen isotopic analysis of NO3-atm from the basin have shown Δ17O values of ~ 22‰ . Lake water nitrate have Δ17O values of 1-4‰ depending on depth and season, indicating that up to 20% of the lake nitrate is retained from the atmosphere. The δ 18O values (-2.0 to 12‰ ) cannot be used to estimate of the NO3-atm loading because of the wide range of δ 18O values associated with nitrification. Variations of Δ 17O with season can provide estimates of the flux of the nitrification of organic N. Balancing the isotopic budget with δ 15N and δ 18O measurements further constrains the N cycling dynamic within the lake. From these data a nutrient flux/utilization model can be developed.

  7. Mercury stable isotope signatures of world coal deposits and historical coal combustion emissions.

    PubMed

    Sun, Ruoyu; Sonke, Jeroen E; Heimbürger, Lars-Eric; Belkin, Harvey E; Liu, Guijian; Shome, Debasish; Cukrowska, Ewa; Liousse, Catherine; Pokrovsky, Oleg S; Streets, David G

    2014-07-01

    Mercury (Hg) emissions from coal combustion contribute approximately half of anthropogenic Hg emissions to the atmosphere. With the implementation of the first legally binding UNEP treaty aimed at reducing anthropogenic Hg emissions, the identification and traceability of Hg emissions from different countries/regions are critically important. Here, we present a comprehensive world coal Hg stable isotope database including 108 new coal samples from major coal-producing deposits in South Africa, China, Europe, India, Indonesia, Mongolia, former USSR, and the U.S. A 4.7‰ range in δ(202)Hg (-3.9 to 0.8‰) and a 1‰ range in Δ(199)Hg (-0.6 to 0.4‰) are observed. Fourteen (p < 0.05) to 17 (p < 0.1) of the 28 pairwise comparisons between eight global regions are statistically distinguishable on the basis of δ(202)Hg, Δ(199)Hg or both, highlighting the potential application of Hg isotope signatures to coal Hg emissions tracing. A revised coal combustion Hg isotope fractionation model is presented, and suggests that gaseous elemental coal Hg emissions are enriched in the heavier Hg isotopes relative to oxidized forms of emitted Hg. The model explains to first order the published δ(202)Hg observations on near-field Hg deposition from a power plant and global scale atmospheric gaseous Hg. Yet, model uncertainties appear too large at present to permit straightforward Hg isotope source identification of atmospheric forms of Hg. Finally, global historical (1850-2008) coal Hg isotope emission curves were modeled and indicate modern-day mean δ(202)Hg and Δ(199)Hg values for bulk coal emissions of -1.2 ± 0.5‰ (1SD) and 0.05 ± 0.06‰ (1SD).

  8. Carbonate Condensates in the Chicxulub Ejecta Deposits from Belize

    NASA Astrophysics Data System (ADS)

    Pope, K. O.; Ocampo, A. C.; Fischer, A. G.; Morrison, J.; Sharp, Z.

    1996-03-01

    It has long been proposed that large amounts of CO2 released to the atmosphere by impact vaporization of carbonates could trigger greenhouse warming. Recent studies of the Cretaceous/Tertiary Chicxulub impact indicate that large amounts of both carbonate and sulfate were vaporized, although sulfates had a much more dramatic effect on climate in part due to the relatively small ambient sulfate reservoir of the Earth's atmosphere compared to the huge ambient reservoir of CO2. One process that could mitigate the climatic effects of these volatiles is the back reaction of impact generated oxides (CaO and MgO) with CO2 and SO2-SO3 in the vapor plume. Analyses of Chicxulub ejecta deposits from Belize confirm that the proximal ejecta in this locality are dominated by carbonate lithologies and sulfates are extremely rare. Much of the carbonate is in the form of dolomite and calcite spheroids and euhedral dolomite silt matrix. These spheroids and fine-grained matrix may have formed through condensation in the vapor plume, thus sequestering large amounts of impact generated CO2.

  9. Middle Ordovician carbonate ramp deposits of central Appalachians

    SciTech Connect

    Demicco, R.V.

    1986-05-01

    Middle Ordovician carbonates exposed in Maryland and Pennsylvania can be divided into six facies, each a few tens to hundreds of meters thick: (1) cyclic, meter-scale, alternating thin-bedded to massive limestones and mud-cracked, stromatolitic laminites; (2) thick-bedded to massive skeletal wackestones containing diverse fauna; (3) cross-stratified skeletal-oncoid grainstones; (4) graded, thin-bedded limestones with diverse fauna and internal planar lamination or hummocky cross-stratification; (5) nodular, thin-bedded limestones; and (6) shaly, thin-bedded to laminated limestones containing rare breccia beds. These facies are interpreted as deposits of: (1) tidal flats; (2) open, bioturbated muddy shelf; (3) lime-sand shoals; (4) below normal wave-base shelf; (5) deep ramp; and (6) basin. Palinspastic reconstructions of facies distribution in Maryland and Pennsylvania suggest that these facies developed during flooding of a carbonate ramp that deepened northeastward into a foreland basin. This northern depocenter of the Middle Ordovician Appalachian foreland basin is notably different that its southern counterpart in Virginia and Tennessee. Large skeletal bioherms did not develop on the northern carbonate ramp, where only one onlap package exists. Thus, although the record of the foundering of the passive Cambrian-Ordovician carbonate shelf is grossly similar in the southern and central Appalachians, there are several significant differences. The overlying Martinsburg Formation contains deep-water facies and taconic-style thrust sheets in the central Appalachians, which suggests that the two depocenters may have had different tectonic settings.

  10. Biogenic fish-gut calcium carbonate is a stable amorphous phase in the gilt-head seabream, Sparus aurata.

    PubMed

    Foran, Elizabeth; Weiner, Steve; Fine, Maoz

    2013-01-01

    The main source of calcium carbonate (CaCO₃) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO₃ are also produced in fish intestines. The precipitation of CaCO₃ assists fish in intestinal water absorption and aids in whole body Ca²⁺ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg²⁺, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration.

  11. Patterning and Characterization of Carbon Nanotubes Grown in a Microwave Plasma Enhanced Chemical Vapor Deposition Chamber

    DTIC Science & Technology

    2009-03-01

    determined optically through scanning electron microscope images. carbon nanotubes, field emission, microwave plasma enhanced chemical vapor deposition U U U...PECVD) 13 2.3 Carbon Nanotube Properties . . . . . . . . . . . . . . . 22 2.4 Applications of Carbon Nanotubes . . . . . . . . . . . . 24 2.4.1...Multi-walled Carbon Nanotube . . . . . . . . . . . . . . . 6 TEM Transmission Electron Microscope . . . . . . . . . . . . . 6 SWCNT Single-walled Carbon

  12. The use of carbon stable isotope ratios in drugs characterization

    SciTech Connect

    Magdas, D. A. Cristea, G. Bot, A. Mirel, V.

    2013-11-13

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ{sup 13}C between batches from −29.7 to −31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between −31.3 to −34.9% for the same type of analgesic, but from different manufactures.

  13. The use of carbon stable isotope ratios in drugs characterization

    NASA Astrophysics Data System (ADS)

    Magdas, D. A.; Cristea, G.; Bot, A.; Mirel, V.

    2013-11-01

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ13C between batches from -29.7 to -31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between -31.3 to -34.9% for the same type of analgesic, but from different manufactures.

  14. Stable carbon isotope fractionation by acetotrophic sulfur-reducing bacteria.

    PubMed

    Goevert, Dennis; Conrad, Ralf

    2010-02-01

    Acetate is the most important intermediate in anaerobic degradation of organic matter. The carbon isotope effects associated with the oxidation of acetate (epsilon(ac)) were examined for four acetotrophic sulfur reducers, Desulfuromonas acetoxidans, Desulfuromonas thiophila, Desulfurella acetivorans, and Hippea maritima. During the consumption of acetate and sulfur, acetate was enriched in (13)C by 11.5 and 11.2 per thousand in Desulfuromonas acetoxidans and Desulfuromonas thiophila, respectively. By contrast, isotope fractionation in D. acetivorans and H. maritima resulted in isotope enrichment factors of epsilon(ac)=-6.3 per thousand and -8.4 per thousand, respectively. These sulfur-reducing bacteria all metabolize acetate via the tricarboxylic acid cycle, but have different mechanisms for the initial activation of acetate. In Desulfuromonas acetoxidans, acetyl-CoA is formed by succinyl-CoA : acetate-CoA-transferase, and in D. acetivorans by acetate kinase and phosphate acetyltransferase. Hence, values of epsilon(ac) seem to be characteristic for the type of activation of acetate to acetyl-CoA in acetotrophic sulfur reducers. Summarizing epsilon(ac)-values in anaerobic acetotrophic microorganisms, it appears that isotope fractionation depends on the mechanism of acetate activation to acetyl-CoA, on the key enzyme of the acetate dissimilation pathway, and on the bioavailability of acetate, which all have to be considered when using delta(13)C of acetate in environmental samples for diagnosis of the involved microbial populations.

  15. Stable biopassive insulation synthesized by initiated chemical vapor deposition of poly(1,3,5-trivinyltrimethylcyclotrisiloxane).

    PubMed

    O'Shaughnessy, W S; Murthy, S K; Edell, D J; Gleason, K K

    2007-08-01

    The permanent implantation of electronic probes capable of recording neural activity patterns requires long-term electrical insulation of these devices by biopassive coatings. In this work, the material properties and neural cell compatibility of a novel polymeric material, poly(trivinyltrimethylcyclotrisiloxane) (poly(V3D3)), are demonstrated to be suitable for application as permanently bioimplanted electrically insulating films. The poly(V3D3) polymeric films are synthesized by initiated chemical vapor deposition (iCVD), allowing for conformal and flexible encapsulation of fine wires. The poly(V3D3) also exhibits high adhesive strength to silicon substrates, a common material of manufacture for neural probes. The poly(V3D3) films were found to be insoluble in both polar and nonpolar solvents, consistent with their highly cross-linked structure. The films are pinhole-free and extremely smooth, having a root-mean-square (rms) roughness of 0.4 nm. The material possesses a bulk resistivity of 4 x 1015 Ohm-cm exceeding that of Parylene-C, the material currently used to insulate neurally implanted devices. The iCVD poly(V3D3) films are hydrolytically stable and are demonstrated to maintain their electrical properties under physiological soak conditions, and constant electrical bias, for more than 2 years. In addition, biocompatibility studies with PC12 neurons demonstrate that this material is noncytotoxic and does not influence cell proliferation.

  16. Electrochemical Deposition of Azobenzene-Containing Network Films with High-Contrast and Stable Photoresponse.

    PubMed

    Zhao, Ruiyang; Zhan, Xuepeng; Yao, Liang; Chen, Qidai; Xie, Zengqi; Ma, Yuguang

    2016-04-01

    To fabricate stable photoresponsive films and devices, a cross-linked network that firmly fixes the position of the chromophores is an ideal structure, because aggregation and/or phase separation effects of chromophores in matrix can be effectively restrained in such robust films. Herein, the in situ electrochemical deposition (ED) of azo-based precursors containing multielectroactive carbazole units is utilized to construct highly cross-linked photoresponsive films. 2-(4-(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-2-yl)phenyl)-1-(4-(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-7-yl)phenyl)diazene (BFCzAzo) with high solvability in electrolyte solution, high electroactivity, and highly efficient photoresponsive ability is synthesized by Suzuki coupling reaction as a kind of ED precursor. A highly cross-linked photoresponsive film is fabricated by ED method using BFCzAzo as ED precursor. The film can be patterned in large area by irradiation with interfering laser beam (355 nm), and the pattern possesses excellent thermal stability and insoluble ability in both organic and inorganic solvents. Excellent reversibility of the nanostructures is demonstrated by irradiation with 550 nm laser beam.

  17. Nanocomposites from Stable Dispersions of Carbon Nanotubes in Polymeric Matrices Using Dispersion Interaction

    NASA Technical Reports Server (NTRS)

    Wise, Kristopher Eric (Inventor); Park, Cheol (Inventor); Kang, Jin Ho (Inventor); Siochi, Emilie J. (Inventor); Harrison, Joycelyn S. (Inventor)

    2016-01-01

    Stable dispersions of carbon nanotubes (CNTs) in polymeric matrices include CNTs dispersed in a host polymer or copolymer whose monomers have delocalized electron orbitals, so that a dispersion interaction results between the host polymer or copolymer and the CNTs dispersed therein. Nanocomposite products, which are presented in bulk, or when fabricated as a film, fiber, foam, coating, adhesive, paste, or molding, are prepared by standard means from the present stable dispersions of CNTs in polymeric matrices, employing dispersion interactions, as presented hereinabove.

  18. Stable carbon isotopes in tree rings: the failure of uniformitarianism

    NASA Astrophysics Data System (ADS)

    McCarroll, Danny

    2010-05-01

    When tree rings are used to reconstruct past climate we rely on the uniformitarian principle that ‘the present is the key to the past'. Relationships between measured parameters and climate that can be calibrated and verified over the instrumental period are assumed to be applicable at longer timescales. In the case of δ13C, however, the uniformitarian principle fails for two reasons. (1) The instrumental calibration period is also the period of anthropogenic increase in atmospheric CO2. δ13C is a function of the ratio of internal to ambient CO2, so maintaining constant δ13C over the industrial period requires an active plastic response, either restricting stomatal conductance or increasing assimilation rate. In some areas trees may have reached the limits of their plasticity so that over the last few decades δ13C values have been declining, independent of any changes in climate. If no correction is made, the recent response to climate will be a poor indicator of behaviour in the past. (2) Tree ring δ13C is often used to reconstruct past temperatures even though temperature rarely has a strong direct control over fractionation. The link is therefore via either sunshine or humidity, which over the calibration period may be very strongly correlated with temperature. Long isotope chronologies, when compared with independent evidence of past temperatures, however, can show periods of marked divergence. The strong covariance of temperature, sunshine and humidity over the last century may not have persisted over longer timescales with larger climatic perturbations. In the case of carbon isotopes the key to the past is not statistical inference based on recent behaviour, but a clear mechanistic understanding of the influence of climate and other factors on fractionation.

  19. Photosynthetic fractionation of the stable isotopes of oxygen and carbon

    SciTech Connect

    Guy, R.D. ); Fogel, M.L.; Berry, J.A. )

    1993-01-01

    Isotope discrimination during photosynthetic exchange of O[sub 2] and CO[sub 2] was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([triangle], where 1 + [triangle]/1000 equals the isotope effect, k[sup 16]/k[sup 18] or k[sup 12]/k[sup 13]) was determined by analysis of residual substrate (O[sub 2] or CO[sub 2]). The [triangle] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per thousand]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per thousand] and independent of enzyme source, unlike carbon isotope dicrimination: 30.3[per thousand] for spinach enzyme and 19.6 to 23[per thousand] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [triangle] for O[sub 2] consumption catalyzed by glycolate oxidase was 22.7[per thousand]. Consistent with this, when Asparagus sprengeri Regel mesopyll cells approached the compensation point within a sealed vessel, the [delta][sup 18]O of dissolved O[sub 2] came to a steady-state value of about 21.5[per thousand] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global oxygen cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. 47 refs., 8 figs., 2 tabs.

  20. Photosynthetic Fractionation of the Stable Isotopes of Oxygen and Carbon.

    PubMed Central

    Guy, R. D.; Fogel, M. L.; Berry, J. A.

    1993-01-01

    Isotope discrimination during photosynthetic exchange of O2 and CO2 was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([delta], where 1 + [delta]/1000 equals the isotope effect, k16/k18 or k12/k13) was determined by analysis of residual substrate (O2 or CO2). The [delta] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per mille (thousand) sign]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per mille (thousand) sign] and independent of enzyme source, unlike carbon isotope discrimination: 30.3[per mille (thousand) sign] for spinach enzyme and 19.6 to 23[per mille (thousand) sign] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [delta] for O2 consumption catalyzed by glycolate oxidase was 22.7[per mille (thousand) sign]. The expected overall [delta] for photorespiration is about 21.7[per mille (thousand) sign]. Consistent with this, when Asparagus sprengeri Regel mesophyll cells approached the compensation point within a sealed vessel, the [delta]18O of dissolved O2 came to a steady-state value of about 21.5[per mille (thousand) sign] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global O cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. PMID:12231663

  1. A Collection of Chemical, Mineralogical, and Stable Isotopic Compositional Data for Green River Oil Shale from Depositional Center Cores in Colorado, Utah, and Wyoming

    USGS Publications Warehouse

    Tuttle, Michele L.W.

    2009-01-01

    For over half a century, the U.S. Geological Survey and collaborators have conducted stratigraphic and geochemical studies on the Eocene Green River Formation, which is known to contain large oil shale resources. Many of the studies were undertaken in the 1970s during the last oil shale boom. One such study analyzed the chemistry, mineralogy, and stable isotopy of the Green River Formation in the three major depositional basins: Piceance basin, Colo.; Uinta basin, Utah; and the Green River basin, Wyo. One depositional-center core from each basin was sampled and analyzed for major, minor, and trace chemistry; mineral composition and sulfide-mineral morphology; sulfur, nitrogen, and carbon forms; and stable isotopic composition (delta34S, delta15N, delta13C, and delta18O). Many of these data were published and used to support interpretative papers (see references herein). Some bulk-chemical and carbonate-isotopic data were never published and may be useful to studies that are currently exploring topics such as future oil shale development and the climate, geography, and weathering in the Eocene Epoch. These unpublished data, together with most of the U.S. Geological Survey data already published on these samples, are tabulated in this report.

  2. Molecular and stable carbon isotopic characterization of PAH contaminants at McMurdo Station, Antarctica.

    PubMed

    Kim, Moonkoo; Kennicutt, Mahlon C; Qian, Yaorong

    2006-12-01

    The molecular and stable carbon isotopic compositions of contaminant polycyclic aromatic hydrocarbons (PAHs) at McMurdo Station, Antarctica were analyzed in samples collected from land and sub-tidal area. PAHs in the study areas were characterized by high amounts of naphthalene and alkylated naphthalenes from petroleum products introduced by human activities in the area. Principal component analysis (PCA) of PAH composition data identified multiple sources of PAH contamination in the study area. Compositional assignments of origins were confirmed using compound specific stable carbon isotopic analysis.

  3. Activated carbon derived from waste coffee grounds for stable methane storage.

    PubMed

    Kemp, K Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M; Kim, Kwang S

    2015-09-25

    An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m(2) g(-1) and a micropore volume of 0.574 cm(3) g(-1) and exhibits a stable CH4 adsorption capacity of ∼4.2 mmol g(-1) at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.

  4. Constraining the global bromomethane budget from carbon stable isotopes

    NASA Astrophysics Data System (ADS)

    Bahlmann, Enno; Wittmer, Julian; Greule, Markus; Zetzsch, Cornelius; Seifert, Richard; Keppler, Frank

    2016-04-01

    Despite intense research in the last two decades, the global bromomethane (CH3Br) budget remains unbalanced with the known sinks exceeding the known sources by about 25%. The reaction with OH is the largest sink for CH3Br. We have determined the kinetic isotope effects for the reactions of CH3Br with the OH and Cl radical in order to better constrain the global CH3Br budget from an isotopic perspective. The isotope fractionation experiments were performed at 20±1°C in a 3500 L Teflon smog-chamber with initial CH3Br mixing ratios of about 2 and 10 ppm and perflourohexane (25 ppb) as internal standard. Atomic chlorine (Cl) was generated via photolysis of molecular chlorine (Cl2) using a solar simulator with an actinic flux comparable to that of the sun in mid-summer in Germany. OH radicals were generated via the photolysis of ozone (O3) at 253.7 nm in the presence of water vapor (RH = 70%).The mixing ratios of CH3Br, and perflourohexane were monitored by GC-MS with a time resolution of 15 minutes throughout the experiments. From each experiment 10 to 15 sub samples were taken in regular time intervals for subsequent carbon isotope ratio determinations by GC-IRMS performed at two independent laboratories in parallel. We found a kinetic isotope effect (KIE) of 17.6±3.3‰ for the reaction of CH3Br with OH and a KIE of 9.8±1.4 ‰ for the reaction with Cl*. We used these fractionation factors along with new data on the isotopic composition of CH3Br in the troposphere (-34±7‰) and the surface ocean (-26±7‰) along with reported source signatures, to constrain the unknown source from an isotopic perspective. The largest uncertainty in estimating the isotopic composition of the unknown source arises from the soil sink. Microbial degradation in soils is the second largest sink and assigned with a large fractionation factors of about 50‰. However, field experiments revealed substantially smaller apparent fractionation factors ranging from 11 to 22‰. In addition

  5. Ti-doped hydrogenated diamond like carbon coating deposited by hybrid physical vapor deposition and plasma enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Lee, Na Rae; Sle Jun, Yee; Moon, Kyoung Il; Sunyong Lee, Caroline

    2017-03-01

    Diamond-like carbon films containing titanium and hydrogen (Ti-doped DLC:H) were synthesized using a hybrid technique based on physical vapor deposition (PVD) and plasma enhanced chemical vapor deposition (PECVD). The film was deposited under a mixture of argon (Ar) and acetylene gas (C2H2). The amount of Ti in the Ti-doped DLC:H film was controlled by varying the DC power of the Ti sputtering target ranging from 0 to 240 W. The composition, microstructure, mechanical and chemical properties of Ti-doped DLC:H films with varying Ti concentrations, were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), nano indentation, a ball-on-disk tribometer, a four-point probe system and dynamic anodic testing. As a result, the optimum composition of Ti in Ti-doped DLC:H film using our hybrid method was found to be a Ti content of 18 at. %, having superior electrical conductivity and high corrosion resistance, suitable for bipolar plates. Its hardness value was measured to be 25.6 GPa with a low friction factor.

  6. Stable isotope (C, O) and monovalent cation fractionation upon synthesis of carbonate-bearing hydroxyl apatite (CHAP) via calcite transformation

    NASA Astrophysics Data System (ADS)

    Böttcher, Michael E.; Schmiedinger, Iris; Wacker, Ulrike; Conrad, Anika C.; Grathoff, Georg; Schmidt, Burkhard; Bahlo, Rainer; Gehlken, Peer-L.; Fiebig, Jens

    2016-04-01

    Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

  7. Development of a New Generation of Stable, Tunable, and Catalytically Active Nanoparticles Produced by the Helium Nanodroplet Deposition Method

    DOE PAGES

    Wu, Qiyuan; Ridge, Claron J.; Zhao, Shen; ...

    2016-07-13

    Nanoparticles (NPs) are revolutionizing many areas of science and technology, often delivering unprecedented improvements to properties of the conventional materials. However, despite important advances in NPs synthesis and applications, numerous challenges still remain. Development of alternative synthetic method capable of producing very uniform, extremely clean and very stable NPs is urgently needed. If successful, such method can potentially transform several areas of nanoscience, including environmental and energy related catalysis. Here we present the first experimental demonstration of catalytically active NPs synthesis achieved by the helium nanodroplet isolation method. This alternative method of NPs fabrication and deposition produces narrowly distributed, clean,more » and remarkably stable NPs. The fabrication is achieved inside ultra-low temperature, superfluid helium nanodroplets, which can be subsequently deposited onto any substrate. Lastly, this technique is universal enough to be applied to nearly any element, while achieving high deposition rates for single element as well as composite core-shell NPs.« less

  8. Development of a New Generation of Stable, Tunable, and Catalytically Active Nanoparticles Produced by the Helium Nanodroplet Deposition Method

    SciTech Connect

    Wu, Qiyuan; Ridge, Claron J.; Zhao, Shen; Zakharov, Dmitri; Cen, Jiajie; Tong, Xiao; Connors, Eoghan; Su, Dong; Stach, Eric A.; Lindsay, C. Michael; Orlov, Alexander

    2016-07-13

    Nanoparticles (NPs) are revolutionizing many areas of science and technology, often delivering unprecedented improvements to properties of the conventional materials. However, despite important advances in NPs synthesis and applications, numerous challenges still remain. Development of alternative synthetic method capable of producing very uniform, extremely clean and very stable NPs is urgently needed. If successful, such method can potentially transform several areas of nanoscience, including environmental and energy related catalysis. Here we present the first experimental demonstration of catalytically active NPs synthesis achieved by the helium nanodroplet isolation method. This alternative method of NPs fabrication and deposition produces narrowly distributed, clean, and remarkably stable NPs. The fabrication is achieved inside ultra-low temperature, superfluid helium nanodroplets, which can be subsequently deposited onto any substrate. Lastly, this technique is universal enough to be applied to nearly any element, while achieving high deposition rates for single element as well as composite core-shell NPs.

  9. Unusually high stable carbon isotopic values of methane from low organic carbon Mars analog hypersaline environments

    NASA Astrophysics Data System (ADS)

    Kelley, C. A.; Poole, J. A.; Tazaz, A.; Chanton, J.; Bebout, B.

    2010-12-01

    Motivated by the Mars rovers’ findings of past hypersaline environments and the discovery of methane in the atmosphere of Mars, we examined methanogenesis in hypersaline ponds in Baja California Sur and in the Don Edwards National Wildlife Refuge in northern California. Methane-rich bubbles were observed to be released from below gypsum/halite crusts in these environments. The stable carbon isotopic composition of these bubbles ranged from about -30 to -40 ‰. Methane with these relatively high isotopic values would typically be considered non-biogenic, however incubations of crust and sediments samples over time resulted in the production of methane. We therefore undertook a series of measurements aimed at understanding the isotopic composition of methane in these environments. The concentrations and isotopic composition of the particulate organic carbon (POC) in these environments were measured. POC content was low (relative to most methane-producing sedimentary environments), generally less than 1%, and always less than 2% of the total mass. The isotopic composition of the POC ranged from -13 to -22 ‰. To determine the substrates used by the methanogens, 13C-labeled trimethylamine (TMA), monomethylamine, methanol, acetate and bicarbonate were added to incubation vials and the methane produced was monitored for 13C content. The main substrates used by the methanogens in these hypersaline environments were the non-competitive substrates, the methylamines and methanol. When unlabeled, but isotopically known, TMA was added to incubation vials in varying concentrations, the isotopic composition of the methane produced also varied. Little, if any, difference in the isotopic composition between the TMA and methane occurred at the lowest TMA concentration (10 µM final concentration). The lowest methane δ13C values (and so greatest fractionation between methane and TMA) occurred when the most TMA was added (1000 µM final concentration). This change in the

  10. Highly Selective and Stable Reduction of CO2 to CO by a Graphitic Carbon Nitride/Carbon Nanotube Composite Electrocatalyst.

    PubMed

    Lu, Xunyu; Tan, Tze Hao; Ng, Yun Hau; Amal, Rose

    2016-08-16

    A stable and selective electrocatalyst for CO2 reduction was fabricated by covalently attaching graphitic carbon nitride onto multiwall carbon nanotubes (g-C3 N4 /MWCNTs). The as-prepared composite is able to reduce CO2 exclusively to CO with a maximum Faraday efficiency of 60 %, and no decay in the catalytic activity was observed even after 50 h of reaction. The enhanced catalytic activity towards CO2 reduction is attributed to the formation of active carbon-nitrogen bonds, high specific surface area, and improved material conductivity of the g-C3 N4 /MWCNT composite.

  11. Determination of stable carbon isotopes of organic acids and carbonaceous aerosols in the atmosphere.

    PubMed

    Fisseha, R; Saurer, M; Jäggi, M; Szidat, S; Siegwolf, R T W; Baltensperger, U

    2006-01-01

    A wet oxidation method for the compound-specific determination of stable carbon isotopes (delta(13)C) of organic acids in the gas and aerosol phase, as well as of water-soluble organic carbon (WSOC), is presented. Sampling of the organic acids was done using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to an ion chromatography (IC) system. The method allows for compound-specific stable carbon isotope analysis by collecting different fractions of organic acids at the end of the IC system using a fraction collector. delta(13)C analyses of organic acids were conducted by oxidizing the organic acids with sodium persulfate at a temperature of 100 degrees C and determining the delta(13)C value of the resulting carbon dioxide (CO(2)) with an isotope ratio mass spectrometer. In addition, analysis of delta(13)C of the WSOC was performed for particulate carbon collected on aerosol filters. The WSOC was extracted from the filters using ultrapure water (MQ water), and the dissolved organic carbon was oxidized to CO(2) using the oxidation method. The wet oxidation method has an accuracy of 0.5 per thousand with a precision of +/-0.4 per thousand and provides a quantitative result for organic carbon with a detection limit of 150 ng of carbon.

  12. Carbon allocation in plants and ecosystems - insights from stable isotope studies

    NASA Astrophysics Data System (ADS)

    Gessler, Arthur

    2014-05-01

    Trees are large global stores of carbon (C) that will be impacted by increased carbon dioxide levels and climate change. However, at present we cannot properly predict the carbon balance of forests in future as we lack knowledge on how plant physiological processes, the transfer of carbon within the plant, carbon storage, and remobilization in the plant tissues as well as the release of carbon from the roots to the soil interact with environmental drivers and ecosystem-scale processes. This paper will summarise how stable isotope techniques can give new insights in the fate of newly assimilated C in plants and ecosystems on time scales from hours to seasons and it will include studies either characterizing temporal and spatial variation in the natural abundance of carbon and oxygen isotopes or applying isotopically enriched tracers. It comprises the assessment of the mechanisms of C partitioning among specific metabolic pathways, between plant organs and into various ecosystem C pools with different residence times. Moreover stable isotopes are highly suitable tools to characterise the role of the phloem, which is the central long-distance conveyer distributing C from source to sinks and thus plays a central role in linking sites and structures of storage, growth and other metabolic activities. A deeper understanding of these processes and their interaction with environmental drivers is critical for predicting how trees and ecosystems will respond to coming global environmental changes, including increased temperature, altered precipitation, and elevated carbon dioxide concentrations.

  13. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Müller, K.; Winde, V.; Escher, P.; von Geldern, R.; Böttcher, M. E.

    2012-04-01

    Processes in the carbonate system of surface waters are in particular sensitive to variations of boundary conditions as, for instance, the partial pressure of carbon dioxide in the atmosphere and the aqueous solution. Examples range from streams, rivers, to coastal marine waters. The flux of carbon dioxide from continental flowing waters was recently included into calculations of the global carbon budget (Butman & Raymond, 2011, Nature Geo.). These solutions, are often supersaturated in carbon dioxide with respect to the atmosphere. The degassing of carbon dioxide is associated with a kinetically controlled fractionation of the stable carbon isotopes, which has to be considered in balancing water-air carbon dioxide fluxes. The degassing process additionally leads to the super-saturation of the aqueous solution with respect to calcium carbonate. Stable isotope fractionation is of particular value to identify and quantify processes at the water-gas phase interface and link these non-equilibrium processes to the formation mechanisms of calcite and the hydrodynamics of surface waters. Experiments were carried out with or without inert N2 gas flow to degas carbon dioxide from initially supersaturated solutions. Natural solutions used are from different stations of the Elbe estuary, the Jade Bay, the backbarrier tidal area of Spiekeroog Island, carbonate springs of Rügen Island, and the Baltic Sea coastline. Results are compared experiments using bottled mineral waters. By following the (physico) chemical changes in the solutions (pH, TA, Ca PHREEQC modeling) it was found, that two evolutionary stages can be differentiated. Reaction progress led to the preferential liberation of carbon dioxide containing the light carbon isotope, following a Rayleigh-type process. After an induction period, where only degassing of carbon dioxide took place, a second stage was observed where calcite began to form from the highly supersaturated solutions. In this stage the carbonate

  14. High rate chemical vapor deposition of carbon films using fluorinated gases

    DOEpatents

    Stafford, Byron L.; Tracy, C. Edwin; Benson, David K.; Nelson, Arthur J.

    1993-01-01

    A high rate, low-temperature deposition of amorphous carbon films is produced by PE-CVD in the presence of a fluorinated or other halide gas. The deposition can be performed at less than 100.degree. C., including ambient room temperature, with a radio frequency plasma assisted chemical vapor deposition process. With less than 6.5 atomic percent fluorine incorporated into the amorphous carbon film, the characteristics of the carbon film, including index of refraction, mass density, optical clarity, and chemical resistance are within fifteen percent (15%) of those characteristics for pure amorphous carbon films, but the deposition rates are high.

  15. Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

    SciTech Connect

    Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; Mayer, Bernhard

    2014-12-31

    Carbon stable isotopes can be used in characterization and monitoring of CO2 sequestration sites to track the migration of the CO2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport module of TOUGHREACT was modified to include separate isotopic species of CO2 gas and dissolved inorganic carbon (CO2, CO32-, HCO3-,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.

  16. Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

    DOE PAGES

    Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; ...

    2014-12-31

    Carbon stable isotopes can be used in characterization and monitoring of CO2 sequestration sites to track the migration of the CO2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport module of TOUGHREACT was modifiedmore » to include separate isotopic species of CO2 gas and dissolved inorganic carbon (CO2, CO32-, HCO3-,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

  17. Climatic evolution and control on carbonate deposition in northeast Australia

    NASA Astrophysics Data System (ADS)

    Feary, David A.; Davies, Peter J.; Pigram, Christopher J.; Symonds, Philip A.

    1991-03-01

    The characteristics of carbonate facies deposited along continental margins are directly controlled by seawater temperature. The oxygen isotopic composition of foraminifera tests reflect seawater temperature, and accordingly isotopic and age data may be combined to derive a paleotemperature record. Paleotemperature data may be used both to account for the known distribution of carbonate facies, and also to predict facies characteristics in poorly known areas. Oxygen isotope data from Deep Sea Drilling Project holes throughout the southwest Pacific have been used to compile a paleotemperature curve for offshore northeast Australia. The accuracy of paleotemperature estimates used in this compilation is dependent on the precise estimation of global ice volumes; on the estimation of surface water isotopic ratios from near-surface planktonic foraminifera; on the accuracy of biological disequilibrium isotopic fractionation constants for benthonic foraminifera; and on the identification of recrystallization, encrustation, and selective dissolution of samples. Decreasing temperatures during much of the early Cenozoic portion of the northeast Australia paleotemperature curve reflect the global high-latitude cooling trend which persisted throughout the Tertiary following the earliest Eocence temperature maximum. Warning during the middle Oligocene to Recent part of the curve reflects northeast Australia's transition from a mid-latitude situation in a world with little climatic zonation, to a low latitude situation in a world with pronounced latitudinal temperature gradients. The carbonate buildups of northeast Australia directly reflect this climatic variation. Restricted warm temperate or subtropical buildups developed during the Eocene; carbonate buildups did not develop at all during the cool Oligocene; and subtropical buildups suceeded by tropical coral reefs first developed during the latest Oligocene or Early Miocene in the northernmost part of area, and later

  18. Equations for Lipid Normalization of Carbon Stable Isotope Ratios in Aquatic Bird Eggs

    PubMed Central

    Elliott, Kyle H.; Davis, Mikaela; Elliott, John E.

    2014-01-01

    Stable isotope ratios are biogeochemical tracers that can be used to determine the source of nutrients and contaminants in avian eggs. However, the interpretation of stable carbon ratios in lipid-rich eggs is complicated because 13C is depleted in lipids. Variation in 13C abundance can therefore be obscured by variation in percent lipids. Past attempts to establish an algebraic equation to correct carbon isotope ratios for lipid content in eggs have been unsuccessful, possibly because they relied partly on data from coastal or migratory species that may obtain egg lipids from different habitats than egg protein. We measured carbon, nitrogen and sulphur stable isotope ratios in 175 eggs from eight species of aquatic birds. Carbon, nitrogen and sulphur isotopes were enriched in lipid-extracted egg samples compared with non extracted egg samples. A logarithmic equation using the C∶N ratio and carbon isotope ratio from the non extracted egg tissue calculated 90% of the lipid-extracted carbon isotope ratios within ±0.5‰. Calculating separate equations for eggs laid by species in different habitats (pelagic, offshore and terrestrial-influenced) improved the fit. A logarithmic equation, rather than a linear equation as often used for muscle, was necessary to accurately correct for lipid content because the relatively high lipid content of eggs compared with muscle meant that a linear relationship did not accurately approximate the relationship between percent lipids and the C∶N ratio. Because lipid extraction alters sulphur and nitrogen isotope ratios (and cannot be corrected algebraically), we suggest that isotopic measurement on bulk tissue followed by algebraic lipid normalization of carbon stable isotope ratio is often a good solution for homogenated eggs, at least when it is not possible to complete separate chemical analyses for each isotope. PMID:24465384

  19. Stable carbon and nitrogen isotope analysis of TNT: two-dimensional source identification.

    PubMed

    Coffin, R B; Miyares, P H; Kelley, C A; Cifuentes, L A; Reynolds, C M

    2001-12-01

    Data from a combination of laboratory and fieldwork is presented to initiate testing of stable carbon and nitrogen isotope ratios to trace sources of TNT in contaminated soil and groundwater. Evaluation of these extraction methods resulted in 99.9 and 99.8% recovery of TNT with Soxhlet and solid-phase extraction (SPE), respectively. As a result of the high extraction efficiency, isotope fractionation did not occur, thus providing an accurate stable isotope value on TNT from laboratory and field samples. Subsequent experiments evaluated the stability of isotope signatures through incubations lasting up to four weeks with a 70% decline in the TNT concentration. During these experiments, no significant variation in stable carbon and nitrogen isotope ratios was measured. Five different sources of TNT, compared for stable carbon and nitrogen isotope ratios, showed a range of 4.2 and 15%, respectively. This large range in the isotope ratios suggests excellent potential to trace sources in a complex environment. Finally, a site was surveyed for concentrations and isotope values of TNT extracted from groundwaters. Values from this site were substantially different relative to the variation measured on standards and in laboratory incubation experiments. The data set indicates good potential to use stable isotopes to determine TNT sources and fate in the environment.

  20. Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nowak-Lovato, K.

    2014-12-01

    Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

  1. Stable Isotope Values of Nitrogen and Carbon in Particulate Matter: Data

    EPA Science Inventory

    Data set from “Patterns in stable isotope values of nitrogen and carbon in particulate matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras” by Oczkowski et al. These are the data upon which all results and conclusion are made...

  2. USE OF CARBON STABLE ISOTOPE TO INVESTIGATE CHLOROMETHANE FORMATION IN THE ELECTROLYTIC DECHLORINATION OF TRICHLOROETHYLENE

    EPA Science Inventory

    Carbon stable isotope trichloroethylene (13C TCE) was used to investigate the formation of chloromethane (CM) during the electrolytic dechlorination of trichloroethylene (TCE) at a granular-graphite packed cathode. A method was developed to use a conventional GC/MS to ...

  3. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  4. FATTY ACID STABLE ISOTOPE INDICATORS OF MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory

    The soil microbial community plays an important role in tropical ecosystem functioning because of its importance in the soil organic matter (SOM) cycle. We have measured the stable carbon isotopic ratio (delta13C) of individual phospholipid fatty acids (PLFAs) in a variety of tr...

  5. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder

    EPA Science Inventory

    Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to different...

  6. Breath carbon stable isotope ratios identify changes in energy balance and substrate utilization in humans

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool to enable individuals to lose weight. In a pilot study, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath d13C values) reflects shifts between negat...

  7. Linking mercury, carbon, and nitrogen stable isotopes in Tibetan biota: Implications for using mercury stable isotopes as source tracers

    PubMed Central

    Xu, Xiaoyu; Zhang, Qianggong; Wang, Wen-Xiong

    2016-01-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ199Hg signatures, with some highest value (8.6%) ever in living organisms. The δ202Hg and Δ199Hg in sediment and biotic samples increased with trophic positions (δ15N) and %methylmercury. Fish total length closely correlated to δ13C and Δ199Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions. PMID:27151563

  8. Linking mercury, carbon, and nitrogen stable isotopes in Tibetan biota: Implications for using mercury stable isotopes as source tracers

    NASA Astrophysics Data System (ADS)

    Xu, Xiaoyu; Zhang, Qianggong; Wang, Wen-Xiong

    2016-05-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ199Hg signatures, with some highest value (8.6%) ever in living organisms. The δ202Hg and Δ199Hg in sediment and biotic samples increased with trophic positions (δ15N) and %methylmercury. Fish total length closely correlated to δ13C and Δ199Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions.

  9. Measurement of stable carbon isotope ratios of non-methane hydrocarbons and halocarbons

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A. T.

    2012-09-01

    Within the realm of volatile organic compounds, hydrocarbons and halocarbons form a sizable proportion of carbon input to the atmosphere. Within these compound categories, the light non-methane hydrocarbons (NMHC, two to seven carbon atoms) and monocarbon halocarbons have a special place as these have strong, if not exclusive, anthropogenic (human-caused) sources. With common atmospheric molar mixing ratios in the parts-per-trillion (10-12 mole/mole) to parts-per-billion (10-9 mole/mole) range, these trace gases, though decidedly minor constituants of the atmosphere, have diverse consequences due to their atmospheric presence and their removal processes. Effects range from causing ground level air pollution and resulting hazards to health, to contributing to anthropogenic climate change and the destruction of the ozone layer in the stratosphere, among many others. The existance of stable isotopes (otherwise identical atoms with varying amounts of neutrons that do not spontaneously disintegrate) in several elements relevant to atmospheric chemistry and physics is a boon to research. Their presence in molecules is detectable by mass and cause small intra- and intermolecular property changes. These changes range from the physical (e.g. boiling point variation) to the chemical (reaction rate variation) and can influence external interactions as well. The measurement of the ratio of a minor stable isotope of an element to the major one (the stable isotope ratio) can be used to establish source fingerprints, trace the interaction dynamics, and refine the understanding of the relative contribution of sources and sinks to the atmosphere as a whole. The stable minor stable isotope of carbon, 13C, has a natural abundance of approximately 1.1 %. It has a sufficient fractional mass difference from its major isotope as to cause significant effects, making it ideal for measuring the ratios and properties of hydro- and halocarbons. In order to enable a better understanding of the

  10. High conductivity transparent carbon nanotube films deposited from superacid.

    PubMed

    Hecht, David S; Heintz, Amy M; Lee, Roland; Hu, Liangbing; Moore, Bryon; Cucksey, Chad; Risser, Steven

    2011-02-18

    Carbon nanotubes (CNTs) were deposited from a chlorosulfonic superacid solution onto PET substrates by a filtration/transfer method. The sheet resistance and transmission (at 550 nm) of the films were 60 Ω/sq and 90.9% respectively, which corresponds to a DC conductivity of 12,825 S cm(-1) and a DC/optical conductivity ratio of 64.1. This is the highest DC conductivity reported for CNT thin films to date, and attributed to both the high quality of the CNT material and the exfoliation/doping by the superacid. This work demonstrates that CNT transparent films have not reached the conductivity limit; continued improvements will enable these films to be used as the transparent electrode for applications in solid state lighting, LCD displays, touch panels, and photovoltaics.

  11. Carbonate deposition, Pyramid Lake subbasin, Nevada: 1. Sequence of formation and elevational distribution of carbonate deposits (Tufas)

    USGS Publications Warehouse

    Benson, L.

    1994-01-01

    During the late Quarternary, the elevation of terrace cutting and carbonate deposition in the Pyramid Lake subbasin were controlled by constancy of lake level imposed by spill to adjoining subbasins. Sill elevations are 1177-1183 m (Mud Lake Slough Sill), 1207 m (Emerson Pass Sill), and 1265 m (Darwin Pass Sill). Carbonate deposition was favored by: (1) hydrologic closure, (2) proximity to a source of calcium, (3) elevated water temperature, and (4) a solid substrate. The thickness and aspect of tufa are a function oflake-level dynamics. Relatively thin sheets and pendant sheets were deposited during a rising or falling lake. The upper parts of thick reef-form tufas have a horizontal aspect and were deposited in a lake which was stabilized by spill to the Carson Desert subbasin. The lower parts of the reef-form tufas are thinner and their outer surface has a vertical aspect, indicating that the lower part formed in a receding lake. The thickest and most complete sequences of tufa are mounds that border the Pyramid Lake shore. The tops of the tallest mounds reach the elevation of the Darwin Pass Sill and many mounds have been eroded to the elevations of the Mud Lake Slough Sill of the Emerson Pass Sill. The sequence of tufa formation (from oldest to youngest) displayed in these mounds is: (1) a beachrock containing carbonate-cemented volcanic cobbles, (2) broken and eroded old spheroids that contain thinolitic tufa and an outer rind of dense laminated tufa, (3) large cylindrical (tubular) tufas capped by (4) coatings of old dense tufas, and (5) several generations of old branching tufa commonly associated with thin, platy tufas and coatings of thinolitic tufa, (6) young spheroids that contain poorly oriented young thinolitic tufa in the center and several generations of radially oriented young thinolitic tufas near the outer edge, (7) a transitional thinolite-to-branching tufa, (8) two or more layers of young branching tufa, (9) a 0.5-cm-thick layer of fine

  12. El Paso Formation - a Lower Ordovician platform carbonate deposit

    SciTech Connect

    Clemons, R.E.

    1987-05-01

    The eastward-transgressive Lower Ordovician El Paso Formation conformably overlies Bliss Sandstone in southern New Mexico. Locally, lower El Paso was deposited on low hills of plutonic and volcanic rocks. The region subsided gradually throughout Canadian time, receiving the El Paso carbonate rock blanket up to 460 m thick. Lithologic and chronologic correlative rocks were deposited over most of the southwestern US as the first Paleozoic carbonate platform sequence. The El Paso Formation contains four members, listed here in ascending order: Hitt Canyon, Jose, McKelligon, and Padre. Gradually decreasing sand content upward through the Hitt Canyon indicates deepening water and/or greater distance to shore. Girvanella(.) oncolites are locally abundant. Stromatolite mounds near the top of the Hitt Canyon, combined with an influx of sand, ooids, and rounded bioclasts in the Jose Member, recorded a shoaling phase. The overlying McKelligon Member contains little or no sand, and sponge-Calathium mounds are prominent at some locales. Stromatolite mounds are interbedded with sponge-Calathium mounds in a few sections. Lower Padre Member beds are typically silty to sandy and locally contain thinly-laminated zones. The Padre contains more restricted fauna that includes traces of ostracods. Pervasive bioturbation of El Paso beds and fauna consisting of echinoderms, sponges, gastropods, trilobites, Nuia, Calathium, cephalopods, and algae plus minor brachiopods and Pulchrilamina indicate predominating shallow-subtidal environments. Low-energy platform environments, in which a large volume of micritic muds accumulated, were disturbed thousands of times by storms producing abundant thin, poorly washed biosparite, intrasparite, and intrasparrudite lenses.

  13. Pronounced carbonate deposition in the Early Triassic Dienerian substage: Who was the carbonate producer?

    NASA Astrophysics Data System (ADS)

    Horacek, Micha; Brandner, Rainer

    2014-05-01

    At the Late Permian Mass Extinction (LPME) most marine carbonate producers were heavily affected or even terminated. After the event in several sections a "boundary clay" was deposited and in the Griesbachian microbialites have been reported from many marine sections, however, without causing substantial thicknesses. The Dienerian in many Tethyan sections, though, is characterized by a huge increase in sedimentation rate due to the deposition of limestone mud with only minor amounts of siliciclastic input. This is in contrast to the still missing "usual" (skeletal) carbonate producers that have not yet re-appeared after the extinction, and also in contrast to a steeply and constantly rising marine Sr-isotope curve. To us this pattern indicates short timed intense post-extinction acidification in some areas causing a strong decrease of carbonate precipitation and thus resulting in the sedimentation of the boundary clay. Post-extinction low sedimentation rate supported the extensive growth of microbialites, thrombolites and stromatolites on seafloors in the photic zone, resulting in the photosynthetic uptake of bicarbonate ions which induced carbonate biomineralisation within the microbial mats probably during still prevailing acidic ocean condition. In the Dienerian the ocean water pH must have returned to non-acidic conditions again due to biotic and probably mainly microbial activity, resulting in a thriving and carbonate precipitating planctic microbial community producing huge amounts of microcrystalline carbonate mud. As some sections already in the Griesbachian feature substantial accumulations of carbonate mud layers, there acidification might have lasted only for a shorter period. Burial of the mainly microbial biomass probably also resulted in the positive 13C isotope curve trend from the Griesbachian to the Dienerian-Smithian boundary. Our interpretation identifies the (marine) microbial community as one of the important and THE biotic factor influencing

  14. Model for carbonate deposition in an Epicontinental Bay

    SciTech Connect

    Carney, C.; Smosna, R.

    1986-05-01

    By mapping the distribution of correlative sediments across the north-central region of the Appalachian basin, a paleogeographic model has been generated for part of the Mississippian period. During the Chesterian, the upper Greenbrier Limestone was deposited in an embayment that extended northward into parts of West Virginia, Ohio, Pennsylvanian, and Maryland. The bay, only a few hundred kilometers wide, was surrounded by lowlands to the west and north, and deltaic sediments shed from nearby highlands diluted the easternmost facies. In the bay, several different shallow-water carbonate environments are distinguished. Muddy skeletal sand was deposited in the central part, which was characterized by normal marine circulation and salinity. This open-bay facies supported a moderately diverse fauna of forams, brachiopods, and mollusks. From the central facies to the bay margins, water depth decreased, circulation became more restricted, and salinity was slightly higher. A restricted-bay facies developed closer to shore, with sediment consisting of pelletal mud and scattered skeletal grains. Diversity was lower, and the fauna was composed primarily of forams and ostracodes. A tidal mud flat surrounded the embayment on all three sides where partly to totally dolomitized mud containing cryptalgal structures formed. Oolite shoals, present on the eastern side of the bay near its mouth, mark areas where tidal currents were concentrated. Eventually, the epicontinental sea flooded the small enclosed bay, replacing the shallow-water facies with an open-marine facies. The new environment supported a highly diverse fauna including crinoids, brachiopods, mollusks, forams, and ostracods.

  15. Anthropogenic nitrogen deposition enhances carbon sequestration in boreal soils.

    PubMed

    Maaroufi, Nadia I; Nordin, Annika; Hasselquist, Niles J; Bach, Lisbet H; Palmqvist, Kristin; Gundale, Michael J

    2015-08-01

    It is proposed that carbon (C) sequestration in response to reactive nitrogen (Nr ) deposition in boreal forests accounts for a large portion of the terrestrial sink for anthropogenic CO2 emissions. While studies have helped clarify the magnitude by which Nr deposition enhances C sequestration by forest vegetation, there remains a paucity of long-term experimental studies evaluating how soil C pools respond. We conducted a long-term experiment, maintained since 1996, consisting of three N addition levels (0, 12.5, and 50 kg N ha(-1) yr(-1) ) in the boreal zone of northern Sweden to understand how atmospheric Nr deposition affects soil C accumulation, soil microbial communities, and soil respiration. We hypothesized that soil C sequestration will increase, and soil microbial biomass and soil respiration will decrease, with disproportionately large changes expected compared to low levels of N addition. Our data showed that the low N addition treatment caused a non-significant increase in the organic horizon C pool of ~15% and a significant increase of ~30% in response to the high N treatment relative to the control. The relationship between C sequestration and N addition in the organic horizon was linear, with a slope of 10 kg C kg(-1) N. We also found a concomitant decrease in total microbial and fungal biomasses and a ~11% reduction in soil respiration in response to the high N treatment. Our data complement previous data from the same study system describing aboveground C sequestration, indicating a total ecosystem sequestration rate of 26 kg C kg(-1) N. These estimates are far lower than suggested by some previous modeling studies, and thus will help improve and validate current modeling efforts aimed at separating the effect of multiple global change factors on the C balance of the boreal region.

  16. Highly stable beta-class carbonic anhydrases useful in carbon capture systems

    DOEpatents

    Alvizo, Oscar; Benoit, Mike; Novick, Scott

    2013-04-16

    The present disclosure relates to .beta.-class carbonic anhydrase polypeptides having improved properties including increased thermostability and/or stability in the presence of amine compounds, ammonia, or carbonate ion. The present disclosure also provides formulations and uses of the polypeptides for accelerating the absorption of carbon dioxide from a gas stream into a solution as well as for the release of the absorbed carbon dioxide for further treatment and/or sequestering. Also provided are polynucleotides encoding the carbonic anhydrase polypeptides and host cells capable of expressing them.

  17. Highly stable beta-class carbonic anhydrases useful in carbon capture systems

    DOEpatents

    Alvizo, Oscar; Benoit, Michael R; Novick, Scott J

    2013-08-20

    The present disclosure relates to .beta.-class carbonic anhydrase polypeptides having improved properties including increased thermostability and/or stability in the presence of amine compounds, ammonia, or carbonate ion. The present disclosure also provides formulations and uses of the polypeptides for accelerating the absorption of carbon dioxide from a gas stream into a solution as well as for the release of the absorbed carbon dioxide for further treatment and/or sequestering. Also provided are polynucleotides encoding the carbonic anhydrase polypeptides and host cells capable of expressing them.

  18. Filtered pulsed cathodic arc deposition of fullerene-like carbon and carbon nitride films

    SciTech Connect

    Tucker, Mark D. Broitman, Esteban; Näslund, Lars-Åke; Hultman, Lars; Rosen, Johanna; Czigány, Zsolt

    2014-04-14

    Carbon and carbon nitride films (CN{sub x}, 0 ≤ x ≤ 0.26) were deposited by filtered pulsed cathodic arc and were investigated using transmission electron microscopy and X-ray photoelectron spectroscopy. A “fullerene-like” (FL) structure of ordered graphitic planes, similar to that of magnetron sputtered FL-CN{sub x} films, was observed in films deposited at 175 °C and above, with N{sub 2} pressures of 0 and 0.5 mTorr. Higher substrate temperatures and significant nitrogen incorporation are required to produce similar FL structure by sputtering, which may, at least in part, be explained by the high ion charge states and ion energies characteristic of arc deposition. A gradual transition from majority sp{sup 3}-hybridized films to sp{sup 2} films was observed with increasing substrate temperature. High elastic recovery, an attractive characteristic mechanical property of FL-CN{sub x} films, is evident in arc-deposited films both with and without nitrogen content, and both with and without FL structure.

  19. Filtered pulsed cathodic arc deposition of fullerene-like carbon and carbon nitride films

    NASA Astrophysics Data System (ADS)

    Tucker, Mark D.; Czigány, Zsolt; Broitman, Esteban; Näslund, Lars-Åke; Hultman, Lars; Rosen, Johanna

    2014-04-01

    Carbon and carbon nitride films (CNx, 0 ≤ x ≤ 0.26) were deposited by filtered pulsed cathodic arc and were investigated using transmission electron microscopy and X-ray photoelectron spectroscopy. A "fullerene-like" (FL) structure of ordered graphitic planes, similar to that of magnetron sputtered FL-CNx films, was observed in films deposited at 175 °C and above, with N2 pressures of 0 and 0.5 mTorr. Higher substrate temperatures and significant nitrogen incorporation are required to produce similar FL structure by sputtering, which may, at least in part, be explained by the high ion charge states and ion energies characteristic of arc deposition. A gradual transition from majority sp3-hybridized films to sp2 films was observed with increasing substrate temperature. High elastic recovery, an attractive characteristic mechanical property of FL-CNx films, is evident in arc-deposited films both with and without nitrogen content, and both with and without FL structure.

  20. Using stable isotopes of carbon to investigate the seasonal variation of carbon transfer in a northwestern Arkansas cave

    USGS Publications Warehouse

    Knierim, Katherine J.; Pollock, Erik; Hays, Phillip D.; Khojasteh, Jam

    2015-01-01

    Stable-isotope analyses are valuable in karst settings, where characterizing biogeochemical cycling of carbon along groundwater flow paths is critical for understanding and protecting sensitive cave and karst water resources. This study quantified the seasonal changes in concentration and isotopic composition (δ13C) of aqueous and gaseous carbon species—dissolved inorganic carbon (DIC) and gaseous carbon dioxide (CO2)—to characterize sources and transfer of these species along a karst flow path, with emphasis on a cave environment. Gas and water samples were collected from the soil and a cave in northwestern Arkansas approximately once a month for one year to characterize carbon cycling along a conceptual groundwater flow path. In the soil, as the DIC concentration increased, the isotopic composition of the DIC became relatively lighter, indicating an organic carbon source for a component of the DIC and corroborating soil DIC as a proxy for soil respiration. In the cave, a positive correlation between DIC and surface temperature was due to increased soil respiration as the organic carbon signal from the soil was transferred to the cave environment via the aqueous phase. CO2 concentration was lowest in the cave during colder months and increased exponentially with increasing surface temperature, presumably due to higher rates of soil respiration during warmer periods and changing ventilation patterns between the surface and cave atmosphere. Isotopic disequilibrium between CO2 and DIC in the cave was greatest when CO2 concentration was changing during November/ December and March/April, presumably due to the rapid addition or removal of gaseous CO2. The isotopic disequilibrium between DIC and CO2 provided evidence that cave CO2 was a mixture of carbon from several sources, which was mostly constrained by mixture between atmospheric CO2 and soil CO2. The concentration and isotopic composition of gaseous and aqueous carbon species were controlled by month

  1. Carbon Availability Modifies Temperature Responses of Heterotrophic Microbial Respiration, Carbon Uptake Affinity, and Stable Carbon Isotope Discrimination

    PubMed Central

    Min, Kyungjin; Lehmeier, Christoph A.; Billings, Sharon A.

    2016-01-01

    Microbial transformations of organic carbon (OC) generate a large flux of CO2 into the atmosphere and influence the C balance of terrestrial and aquatic ecosystems. Yet, inherent heterogeneity in natural environments precludes direct quantification of multiple microbial C fluxes that underlie CO2 production. Here we used a continuous flow bioreactor coupled with a stable C isotope analyzer to determine the effects of temperature and C availability (cellobiose concentration) on C fluxes and 13C discrimination of a microbial population growing at steady-state in a homogeneous, well-mixed environment. We estimated C uptake affinity and C use efficiency (CUE) to characterize the physiological responses of microbes to changing environmental conditions. Temperature increased biomass-C specific respiration rate and C uptake affinity at lower C availability, but did not influence those parameters at higher C availability. CUE decreased non-linearly with increasing temperature. The non-linear, negative relationship between CUE and temperature was more pronounced under lower C availability than under relatively high C availability. We observed stable isotope fractionation between C substrate and microbial biomass C (7~12‰ depletion), and between microbial biomass and respired CO2 (4~10‰ depletion). Microbial discrimination against 13C-containing cellobiose during C uptake was influenced by temperature and C availability, while discrimination during respiration was only influenced by C availability. Shifts in C uptake affinity with temperature and C availability may have modified uptake-induced 13C fractionation. By stressing the importance of C availability on temperature responses of microbial C fluxes, C uptake affinity, CUE, and isotopic fractionation, this study contributes to a fundamental understanding of C flow through microbes. This will help guide parameterization of microbial responses to varying temperature and C availability within Earth-system models. PMID

  2. Carbon Availability Modifies Temperature Responses of Heterotrophic Microbial Respiration, Carbon Uptake Affinity, and Stable Carbon Isotope Discrimination.

    PubMed

    Min, Kyungjin; Lehmeier, Christoph A; Iv, Ford Ballantyne; Billings, Sharon A

    2016-01-01

    Microbial transformations of organic carbon (OC) generate a large flux of CO2 into the atmosphere and influence the C balance of terrestrial and aquatic ecosystems. Yet, inherent heterogeneity in natural environments precludes direct quantification of multiple microbial C fluxes that underlie CO2 production. Here we used a continuous flow bioreactor coupled with a stable C isotope analyzer to determine the effects of temperature and C availability (cellobiose concentration) on C fluxes and (13)C discrimination of a microbial population growing at steady-state in a homogeneous, well-mixed environment. We estimated C uptake affinity and C use efficiency (CUE) to characterize the physiological responses of microbes to changing environmental conditions. Temperature increased biomass-C specific respiration rate and C uptake affinity at lower C availability, but did not influence those parameters at higher C availability. CUE decreased non-linearly with increasing temperature. The non-linear, negative relationship between CUE and temperature was more pronounced under lower C availability than under relatively high C availability. We observed stable isotope fractionation between C substrate and microbial biomass C (7~12‰ depletion), and between microbial biomass and respired CO2 (4~10‰ depletion). Microbial discrimination against (13)C-containing cellobiose during C uptake was influenced by temperature and C availability, while discrimination during respiration was only influenced by C availability. Shifts in C uptake affinity with temperature and C availability may have modified uptake-induced (13)C fractionation. By stressing the importance of C availability on temperature responses of microbial C fluxes, C uptake affinity, CUE, and isotopic fractionation, this study contributes to a fundamental understanding of C flow through microbes. This will help guide parameterization of microbial responses to varying temperature and C availability within Earth-system models.

  3. Dual ion beam deposition of carbon films with diamondlike properties

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J.; Swec, D. M.; Angus, J. C.

    1984-01-01

    A single and dual ion beam system was used to generate amorphous carbon films with diamond like properties. A methane/argon mixture at a molar ratio of 0.28 was ionized in the low pressure discharge chamber of a 30-cm-diameter ion source. A second ion source, 8 cm in diameter was used to direct a beam of 600 eV Argon ions on the substrates (fused silica or silicon) while the deposition from the 30-cm ion source was taking place. Nuclear reaction and combustion analysis indicate H/C ratios for the films to be 1.00. This high value of H/C, it is felt, allowed the films to have good transmittance. The films were impervious to reagents which dissolve graphitic and polymeric carbon structures. Although the measured density of the films was approximately 1.8 gm/cu cm, a value lower than diamond, the films exhibited other properties that were relatively close to diamond. These films were compared with diamondlike films generated by sputtering a graphite target.

  4. Examining the Role of Multiple Carbon Sources in Isoprene Synthesis in Plants Using Stable Isotope Techniques

    NASA Astrophysics Data System (ADS)

    Funk, J. L.; Mak, J. E.; Lerdau, M. T.

    2001-12-01

    The carbon source for phytogenc isoprene is an issue with important ramifications for both atmospheric and biological science because of its impact on the isotopic signature of isoprene and its oxidation products and because it lends insight into the function that isoprene serves within leaves. Although recently assimilated carbon is believed to be the primary carbon source for isoprene production in plants, variation in diurnal and seasonal isoprene fluxes that cannot be explained by temperature, light, and leaf development have led to the suggestion that alternative carbon sources may contribute. Stable isotopes of carbon can be used to identify changes in carbon partitioning into isoprene synthesis, and mixing models can assess the relative importance of each source. In preliminary studies, we document an additional 8-10 \\permil discrimination in isoprene emitted in the absence of photosynthesis. This change in signature suggests that the carbon source is switched from recently obtained photosynthate to a source more depleted in 13C. We propose that intermediates from carbohydrate degradation and/or re-fixation of CO2 from mitichondrial respiration and photorespiration can contribute to isoprene production. In addition, we expect alternative carbon sources to be most important when photosynthate is limiting (e.g. during water stress events). Photosynthesis, respiration, and isoprene emission measurements are used to calculate the isotopic signatures of the three potential carbon pools: photosynthate derived from ambient CO2, photosynthate derived from respired CO2, and carbohydrate-derived intermediates.

  5. Soil carbon dynamics beneath switchgrass as indicated by stable isotope analysis

    SciTech Connect

    Garten Jr, Charles T; Wullschleger, Stan D

    2000-04-01

    Surface (0-40 cm) soil organic carbon (SOC) dynamics were studied beneath four switchgrass (Panicum virgatum L.) field trials in the southeastern United States. Soil organic carbon was partitioned into particulate organic matter (POM) and mineral-associated organic matter (MOM). Most (75-90%) of the SOC at each study site was affiliated with MOM (<0.053 mm). Changes in stable carbon isotope ratios were used to derive carbon inputs to and losses from POM and MOM at each site. Inventories of existing SOC and new C4-derived SOC beneath switchgrass decreased with increasing soil depth. Approximately 5 yr after establishment, 19 to 31% of the existing SOC inventories beneath switchgrass had been derived from new C{sub 4}-carbon inputs. Calculated turnover times of POM and MOM ranged from 2.4 to 4.3 yr and 26 to 40 yr, respectively. The turnover time of SOC in the POM fraction increased with decreasing mean annual temperature. A simple, two-compartment model was parameterized to predict the potential for soil carbon sequestration under switchgrass. An example calculation with the model indicated a measurable and verifiable recovery of soil carbon ({approx}12% increase) on degraded lands through one decade of switchgrass production. The potential to sequester carbon through switchgrass cultivation will depend on initial soil carbon inventories, prevailing climate, soil type, and site management.

  6. Soil carbon dynamics beneath switchgrass as indicated by stable isotope analysis

    SciTech Connect

    Garten, C.T. Jr.; Wullschleger, S.D.

    2000-04-01

    Surface (0--40 cm) soil organic carbon (SOC) dynamics were studied beneath four switchgrass (Panicum virgatum L.) field trails in the southeastern US. Soil organic carbon was partitioned into particulate organic matter (POM) and mineral-associated organic matter (MOM). Most (75--90%) of the SOC at each study site was affiliated with MOM (<0.053 mm). Changes in stable carbon isotope ratios were used to derive carbon inputs to and losses from POM and MOM at each site. Inventories of existing SOC and new C{sub 4}-derived SOC beneath switchgrass decreased with increasing soil depth. Approximately 5 yr after establishment, 19 to 31% of the existing SOC inventories beneath switchgrass had been derived from new C{sub 4}-carbon inputs. Calculated turnover times of POM and MOM ranged from 2.4 to 4.3 yr and 26 to 40 yr, respectively. The turnover time of SOC in the POM fraction increased with decreasing mean annual temperature. A simple, two-compartment model was parameterized to predict the potential for soil carbon sequestration under switchgrass. An example calculation with the model indicated a measurable and verifiable recovery of soil carbon (=12% increase) on degraded lands through one decade of switchgrass production. The potential to sequester carbon through switchgrass cultivation will depend on initial soil carbon inventories, prevailing climate, soil types and site management.

  7. Carbonate clumped isotope paleothermometry and stable isotope results from the Eocene Fenghuo Shan Group, Hoh Xil Basin, Central Tibet

    NASA Astrophysics Data System (ADS)

    Snell, K. E.; Lippert, P. C.; Eiler, J. M.

    2009-12-01

    reconstructed soil water δ18O values range from 1.7 to 3.3‰ and have a trend of 0.3‰/°C. The reconstructed spar water δ18O value, in contrast, falls on the trend of the reconstructed cement waters, which suggests the spar calcite formed in equilibrium with the same water from which the cement precipitated. These data present strong evidence that the stable isotope record of carbonate in this section reflects a combination of primary (i.e., depositional) and secondary (i.e., diagenetic and burial metamorphic) processes. At maximum, these data suggest surface temperature during development of the paleosols was ~40°C or less during some part of the year, and ~25°C or less at the surface some time after deposition, during precipitation of the cement. At minimum, these preliminary data suggest that constrained surface temperatures require more detailed information regarding the burial history of the section and timing of cementation. Therefore attempts to determine the paleoelevation of this region from δ18O of carbonate will require careful documentation of extents of burial over-printing to identify and characterize the best-preserved materials.

  8. Dissolved inorganic carbon and stable carbon isotopic evolution of neutral mine drainage interacting with atmospheric CO2(g).

    PubMed

    Abongwa, Pride Tamasang; Atekwana, Eliot Anong; Puckette, James

    2016-03-01

    We investigated the spatial variations in the concentrations of dissolved inorganic carbon (DIC), the stable carbon isotopic composition (δ(13)C) of DIC and the δ(13)C of carbonate precipitated from neutral mine drainage interacting with the atmospheric CO2(g). We assessed the chemical, DIC and δ(13)CDIC evolution of the mine drainage and the δ(13)C evolution of carbonate precipitates for a distance of 562 m from the end of an 8 km tunnel that drains a mine. Our results show that as the mine drainage interacts with atmospheric CO2(g) the outgassing of CO2 due to the high initial partial pressure of CO2 (pCO2) causes the DIC to evolve under kinetic conditions followed by equilibration and then under equilibrium conditions. The carbonate evolution was characterized by spatial increases in pH, decreasing concentrations of Ca(2+) and DIC and by the precipitation of carbonate. The δ(13)CDIC showed a larger enrichment from the tunnel exit to 38 m, moderate continuous enrichment to 318 m and almost no enrichment to 562 m. On the other hand, the δ(13)C of the carbonate precipitates also showed large enrichment from the tunnel exit to 38 m, moderate enrichment to 318 m after which the δ(13)C remained nearly constant. The enrichment in the δ(13)C of the DIC and the carbonate precipitates from 0 to 38 m from kinetic fractionation caused by CO2(g) outgassing was followed by a mix of kinetic fractionation and equilibrium fractionation controlled by carbon exchange between DIC and atmospheric CO2(g) to 318 m and then by equilibrium fractionation from 318 to 562 m. From the carbonate evolution in this neutral mine drainage, we estimated that 20% of the carbon was lost via CO2 outgassing, 12% was sequestered in sediments in the drainage ponds from calcite precipitation and the remainder 68% was exported to the local stream.

  9. A high-resolution palaeoenvironmental record from carbonate deposits in the Roman aqueduct of Patara, SW Turkey, from the time of Nero

    NASA Astrophysics Data System (ADS)

    Passchier, Cornelis; Sürmelihindi, Gül; Spötl, Christoph

    2016-06-01

    An inscription on the supporting wall of the inverted siphon of the aqueduct of the ancient Roman city of Patara, SW Turkey, explains how the wall collapsed during an earthquake and was subsequently restored. Carbonate deposits formed inside the aqueduct channel show cyclic stable isotope changes representing 17 years of deposition. This sequence, together with the text of the inscription, allows dating the earthquake to 68 AD and the original inauguration of the aqueduct to the winter of 51/52 AD. Thus, the carbonate deposits represent a high-resolution record of palaeotemperature and precipitation for SW Turkey covering the complete reign of the Emperor Nero. The period shows a cooling and drying trend after an initial warm and more humid period, interrupted by a few anomalous years. These 2 cm of calcite highlight the significance of carbonate deposits in ancient water supply systems as a high-resolution archive for palaeoclimate, palaeoseismology and archaeology.

  10. A high-resolution palaeoenvironmental record from carbonate deposits in the Roman aqueduct of Patara, SW Turkey, from the time of Nero.

    PubMed

    Passchier, Cornelis; Sürmelihindi, Gül; Spötl, Christoph

    2016-06-30

    An inscription on the supporting wall of the inverted siphon of the aqueduct of the ancient Roman city of Patara, SW Turkey, explains how the wall collapsed during an earthquake and was subsequently restored. Carbonate deposits formed inside the aqueduct channel show cyclic stable isotope changes representing 17 years of deposition. This sequence, together with the text of the inscription, allows dating the earthquake to 68 AD and the original inauguration of the aqueduct to the winter of 51/52 AD. Thus, the carbonate deposits represent a high-resolution record of palaeotemperature and precipitation for SW Turkey covering the complete reign of the Emperor Nero. The period shows a cooling and drying trend after an initial warm and more humid period, interrupted by a few anomalous years. These 2 cm of calcite highlight the significance of carbonate deposits in ancient water supply systems as a high-resolution archive for palaeoclimate, palaeoseismology and archaeology.

  11. A high-resolution palaeoenvironmental record from carbonate deposits in the Roman aqueduct of Patara, SW Turkey, from the time of Nero

    PubMed Central

    Passchier, Cornelis; Sürmelihindi, Gül; Spötl, Christoph

    2016-01-01

    An inscription on the supporting wall of the inverted siphon of the aqueduct of the ancient Roman city of Patara, SW Turkey, explains how the wall collapsed during an earthquake and was subsequently restored. Carbonate deposits formed inside the aqueduct channel show cyclic stable isotope changes representing 17 years of deposition. This sequence, together with the text of the inscription, allows dating the earthquake to 68 AD and the original inauguration of the aqueduct to the winter of 51/52 AD. Thus, the carbonate deposits represent a high-resolution record of palaeotemperature and precipitation for SW Turkey covering the complete reign of the Emperor Nero. The period shows a cooling and drying trend after an initial warm and more humid period, interrupted by a few anomalous years. These 2 cm of calcite highlight the significance of carbonate deposits in ancient water supply systems as a high-resolution archive for palaeoclimate, palaeoseismology and archaeology. PMID:27357129

  12. Stable carbon isotope fractionation during trichloroethene degradation in magnetite-catalyzed Fenton-like reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Liu, Cunfu; Yu, Tingting; Li, Xiaoqian

    2013-02-01

    Mineral-catalyzed Fenton-like oxidation of chlorinated ethylenes is an attractive technique for in situ soil and groundwater remediation. Stable carbon isotope enrichment factors associated with magnetite-catalyzed Fenton-like oxidation of trichloroethylene (TCE) have been determined, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by Fenton-like oxidation. The carbon enrichment factors (ɛ values) ranged from - 2.7‰ to - 3.6‰ with a mean value of - 3.3 ± 0.3‰, and only small differences were observed for different initial reactive conditions. The ɛ values were robust and reproducible, and were relatively insensitive to a number of environmental factors such as ratios of reactants and PCE co-contamination, which can reduce the uncertainty associated with application of isotope enrichment factors for quantification of in situ remediation by Fenton-like reaction. ɛ values for Fenton-like oxidation of TCE were intermediate in those previously reported for aerobic biological processes (ɛ = - 1.1 to - 20.7‰). Thus, field-derived ɛ values that are more negative than those for Fenton-like oxidation, may indicate the occurrence of aerobic biodegradation at contaminated sites undergoing in situ remediation with Fenton-like reaction. However, stable carbon isotope analysis is unable to determine whether there is the occurrence of biodegradation processes if field-derived ɛ values are less negative than those for Fenton-like oxidation.

  13. Reading carbonate deposits from ancient water installations: why are they useful for geoarchaeology?

    NASA Astrophysics Data System (ADS)

    Sürmelihindi, Gül; Passchier, Cees

    2016-04-01

    applications, but little is known about their use. For example, did Roman water-powered flour mills operate continuously, or was their use interrupted because of water scarcity or decline in the Roman economy? Carbonate was deposited in the water channels that fed and drained these machines, and on the wood of the machines themselves. Theoretically, it should therefore be possible to see the frequency of use of the machines from the stable isotope cyclicity and other data stored in carbonate deposits. We are presently applying this technique to incrustations from the Barbegal watermill complex near Arles, France. Carbonate deposits can therefore act as archives that provide us an understanding of palaeo-environmental and economic changes over the last two thousand years and provide information on the use, distribution and age of water structures by means of annual lamina counting. With this great potential, we aim to generate new tools and techniques to study the history of science in the framework of geo-archaeology.

  14. Canopy photosynthesis estimated from sapflux and stable carbon isotope ratios in northern Idaho

    NASA Astrophysics Data System (ADS)

    Marshall, J. D.; Ubierna, N.; Kavanagh, K.; Pangle, R.; Powers, E.

    2008-12-01

    Canopy-scale estimates of photosynthesis have traditionally required either scaling up from a sample of leaf measurements or scaling down from eddy flux measurements contaminated by opposing carbon dioxide fluxes. We propose an alternative based on transpiration estimates using the well established Granier sapflux sensor and scaled by modifications of standard measurements of forest structure. The resulting sapflux estimates are converted to carbon uptake measurements by first estimating canopy conductance and then using stable carbon isotope ratios to estimate the ratio of carbon to water exchange. Carbon isotope ratios were measured on leaf bulk material, phloem contents, and the highly concentrated stem CO2 pool. As found elsewhere, leaves were highly depleted and did not provide adequate estimates. We used transfer conductances estimated in other work to adjust the carbon isotope ratios prior to estimating carbon-water exchange ratios. The resulting estimates were 11 Mg C ha-1 yr-1, well within the range to be expected based on net primar production (3.6 Mg C ha-1 yr-1) in these stands. We observed seasonal variation caused by both canopy conductance and changes in \\d13C. This method of estimating canopy photosynthesis provides an important test of one of the key, and hitherto poorly constrained, components of carbon budget analyses.

  15. The stable carbon isotope ratios in benthic food webs of the gulf of Calvi, Corsica

    NASA Astrophysics Data System (ADS)

    Dauby, Patrick

    1989-02-01

    The Gulf of Calvi, Corsica, presents a wide diversity of biocoenoses, amongst which the seagrass Posidonia meadow is prevalent. More than 100 plant, animal and sediment samples from various biotopes were analysed for their stable carbon isotope ratios, to assess carbon flows within the food chains. Marine plants display a wide range of δ 13C values, from -6 to -32‰ but with three relatively well distinct peaks for Posidonia, brown algae and phytoplankton (-9, -19 and -23‰, respectively), which are the main carbon sources. The range of isotopic values of animals is narrower, from -14 to -24‰, suggesting that they feed mainly on algae and plankton. Computations based on simple equations show the proportion of each carbon source in the diet of the animals. Posidonia, notwithstanding their important biomass, appear to be a minor food source; this is possibly because of the transfer of their dead leaves, towards the shorelines, in winter.

  16. Stable nitrogen isotope ratios in wet and dry nitrate deposition collected with an artificial tree

    SciTech Connect

    Garten Jr, Charles T

    1996-02-01

    Amounts of dry NO{sub 3}-N deposition and N isotope ratios in wet and dry NO{sub 3}-N deposition have been simultaneously determined by examining differences between precipitation collected by open funnels and throughfall collected beneath an artificial Christmas tree. Samples were collected in a forest clearing on Walker Branch Watershed, near Oak Ridge, Tennessee. From mid-summer to early autumn, NO{sub 3}-N fluxes beneath the artificial tree were always greater than those measured in precipitation indicating the tree's effectiveness as a passive collector of dry NO{sub 3}-N deposition. Dry NO{sub 3}-N deposition averaged 60 {+-} 9% of total (wet and dry) deposition. The mean ({+-} SD) calculated {delta}{sup 15}N value for NO{sub 3}-N in dry deposition was + 5.6 {+-} 2.1{per_thousand} (n = 6 sampling periods ranging from 4 to 15 days). On average, this was {approx} 6{per_thousand} heavier than measured {delta}{sup 15}N values for NO{sub 3}-N in precipitation. The calculated {delta}{sup 15}N value for NO{sub 3}-N in dry deposition was consistent with that expected if NO{sub x} precursors to HNO{sub 3} vapor (the major constituent of dry deposition at this site) originated principally from coal combustion.

  17. Stable nitrogen isotope ratios in wet and dry nitrate deposition collected with an artificial tree

    NASA Astrophysics Data System (ADS)

    Garten, Charles T., Jr.

    1996-02-01

    Amounts of dry NO3-N deposition and N isotope ratios in wet and dry NO3-N deposition have been simultaneously determined by examining differences between precipitation collected by open funnels and throughfall collected beneath an artificial Christmas tree. Samples were collected in a forest clearing on Walker Branch Watershed, near Oak Ridge, Tennessee. From mid-summer to early autumn, NO3-N fluxes beneath the artificial tree were always greater than those measured in precipitation indicating the tree's effectiveness as a passive collector of dry NO3-N deposition. Dry NO3-N deposition averaged 60±9% of total (wet and dry) deposition. The mean (±SD) calculated δ15N value for NO3-N in dry deposition was+5.6±2.1‰ (n= 6 sampling periods ranging from 4 to 15days). On average, this was ≈ 6‰ heavier than measured δ15N values for NO3-N in precipitation. The calculated δ15N value for NO3-N in dry deposition was consistent with that expected if NOx precursors to HNO3 vapor (the major constituent of dry deposition at this site) originated principally from coal combustion.

  18. Reactivity of deposited carbon on Co-Al/sub 2/O/sub 3/ catalyst

    SciTech Connect

    Nakamura, J.; Tanaka, K.; Toyoshima, I.

    1987-11-01

    Reactivity and characteristics of the carbon deposited on Co-Al/sub 2/O/sub 3/ by disproportionation of CO (the Boudouard reaction) were studied by pulse experiments using /sup 13/C or D isotopes. Three types of deposited carbon were identified by the reaction with hydrogen: highly reactive CH and/or CH/sub 2/ species, reactive carbidic carbon, and less reactive graphitic carbon. The existence of CH and CH/sub 2/ species was proved by the reaction with D/sub 2/ pulse at 80/sup 0/C, but the predominant species was carbidic carbon when the disproportionation of CO was performed on cobalt catalyst at 230/sup 0/C. Carbidic carbon was decomposed to graphitic carbon by raising the temperature. However, a certain amount of carbidic carbon was found to remain on the surface even at 430/sup 0/C. This phenomenon may suggest reversible formation of carbidic carbon from graphitic carbon on the catalyst.

  19. [Relationship between Fe, Al oxides and stable organic carbon, nitrogen in the yellow-brown soils].

    PubMed

    Heng, Li-Sha; Wang, Dai-Zhang; Jiang, Xin; Rao, Wei; Zhang, Wen-Hao; Guo, Chun-Yan; Li, Teng

    2010-11-01

    The stable organic carbon and nitrogen of the different particles were gained by oxidation of 6% NaOCl in the yellow-brown soils. The relationships between the contents of selective extractable Fe/Al and the stable organic carbon/nitrogen were investigated. It shown that amounts of dithionite-citrate-(Fe(d)) and oxalate-(Fe(o)) and pyrophosphate extractable (Fe(p)) were 6-60.8 g x kg(-1) and 0.13-4.8 g x kg(-1) and 0.03-0.47 g x kg(-1) in 2-250 microm particles, respectively; 43.1-170 g x kg(-1) and 5.9-14.0 g x kg(-1) and 0.28-0.78 g x kg(-1) in < 2 microm particles, respectively. The contents of oxalate-(Al(o)) and pyrophosphate extractable (Al(p)) were 0.08-1.34 g x kg(-10 and 0.11-0.47 g x kg(-1) in 2-250 microm particles, respectively; 2.96-6.20 g x kg(-1) and 0.38-0.78 g x kg(-1) in < 2 microm particles, respectively. And amounts of selective extractable Fe are generally higher in paddy yellow-brown soils than in arid yellow-brown soils, and that of selective extractable Al are lower in the former than in the latter. Amounts of the stable organic carbon and nitrogen, higher in paddy yellow-brown soils than in arid yellow-brown soils, were 0.93-6.0 g x kg(-1) and 0.05-0.36 g x kg(-1) in 2-250 microm particles, respectively; 6.05-19.3 g x kg(-1) and 0.61-2.1 g x kg(-1) in < 2 microm particles, respectively. The ratio of the stable organic carbon and nitrogen (C(stable)/N(stable)) were 9.50-22.0 in 2-250 microm particles and 7.43-11.54 in < 2 microm particles, respectively. The stabilization index (SI(C) and SI(N)) of the organic carbon and nitrogen were 14.3-50.0 and 11.9-55.6 in 2-250 microm particles, respectively; 53.72-88.80 and 40.64-70.0 in < 2 microm particles, respectively. According to SI, it is lower in arid yellow-brown soils than in paddy yellow-brown soils. The organic carbon and nitrogen are advantageously conserved in paddy yellow-brown soil. An extremely significant positive correlation of the stable organic carbon and nitrogen with selective

  20. Development of SOFC anodes resistant to sulfur poisoning and carbon deposition

    NASA Astrophysics Data System (ADS)

    Choi, Song Ho

    The advantages of solid oxide fuel cells (SOFCs) over other types of fuel cells include high energy efficiency and excellent fuel flexibility. In particular, the possibility of direct utilization of fossil fuels and renewable fuels (e.g., bio-fuels) may significantly reduce the cost of SOFC technologies. However, it is known that these types of fuels contain many contaminants that may be detrimental to SOFC performance. Among the contaminants commonly encountered in readily available fuels, sulfur-containing compounds could dramatically reduce the catalytic activity of Ni-based anodes under SOFC operating conditions. While various desulphurization processes have been developed for the removal of sulfur species to different levels, the process becomes another source of high cost and system complexity in order to achieve low concentration of sulfur species. Thus, the design of sulfur tolerant anode materials is essential to durability and commercialization of SOFCs. Another technical challenge to overcome for direct utilization of hydrocarbon fuels is carbon deposition. Carbon formation on Ni significantly degrades fuel cell performance by covering the electrochemically active sites at the anode. Therefore, the prevention of the carbon deposition is a key technical issue for the direct use of hydrocarbon fuels in a SOFC. In this research, the surface of a dense Ni-YSZ anode was modified with a thin-film coating of niobium oxide (Nb2O5) in order to understand the mechanism of sulfur tolerance and the behavior of carbon deposition. Results suggest that the niobium oxide was reduced to NbO 2 under operating conditions, which has high electrical conductivity. The NbOx coated dense Ni-YSZ showed sulfur tolerance when exposed to 50 ppm H2S at 700°C over 12 h. Raman spectroscopy and XRD analysis suggest that different phases of NbSx formed on the surface. Further, the DOS (density of state) analysis of NbO2, NbS, and NbS2 indicates that niobium sulfides can be considered

  1. The mangazeya Ag-Pb-Zn vein deposit hosted in sedimentary rocks, Sakha-Yakutia, Russia: Mineral assemblages, fluid inclusions, stable isotopes (C, O, S), and origin

    NASA Astrophysics Data System (ADS)

    Anikina, E. Yu.; Bortnikov, N. S.; Klubnikin, G. K.; Gamyanin, G. N.; Prokof'ev, V. Yu.

    2016-05-01

    The succession of mineral assemblages, chemistry of gangue and ore minerals, fluid inclusions, and stable isotopes (C, O, S) in minerals have been studied in the Mangazeya silver-base-metal deposit hosted in terrigenous rocks of the Verkhoyansk Fold-Thrust Belt. The deposit is localized in the junction zone of the Kuranakh Anticlinorium and the Sartanga Synclinorium at the steep eastern limb of the Endybal Anticline. The deposit is situated at the intersection of the regional Nyuektame and North Tirekhtyakh faults. Igneous rocks are represented by the Endybal massif of granodiorite porphyry 97.8 ± 0.9 Ma in age and dikes varying in composition. One preore and three types of ore mineralization separated in space are distinguished: quartz-pyrite-arsenopyrite (I), quartz-carbonate-sulfide (II), and silver-base-metal (III). Quartz and carbonate (siderite) are predominant in ore veins. Ore minerals are represented by arsenopyrite, pyrite, sphalerite, galena, fahlore, and less frequent sulfosalts. Three types of fluid inclusions in quartz differ in phase compositions: two- or three-phase aqueous-carbon dioxide (FI I), carbon dioxide gas (FI II), and two-phase (FI III) containing liquid and a gas bubble. The homogenization temperature and salinity fall within the ranges of 367-217°C and 13.8-2.6 wt % NaCl equiv in FI I; 336-126°C and 15.4-0.8 wt % NaCl equiv in FI III. Carbon dioxide in FI II was homogenized in gas at +30.2 to +15.3°C and at +27.2 to 29.0°C in liquid. The δ34S values for minerals of type I range from-1.8 to +4.7‰ (V-CDT); of type II, from-7.4 to +6.6‰; and of type III, from-5.6 to +7.1‰. δ13C and δ18O vary from-7.0 to-6.7‰ (V-PDB) and from +16.6 to +17.1 (V-SMOW) in siderite-I; from-9.1 to-6.9‰ (V-PDB) and from +14.6 to +18.9 (V-SMOW) in siderite-II; from-5.4 to-3.1‰ (V-PDB) and from +14.6 to +19.5 (V-SMOW) in ankerite; and from-4.2 to-2.9‰ (V-PDB) and from +13.5 to +16.8 (V-SMOW) in calcite. The data on mineral assemblages, fluid

  2. Carbon Nanotubes/Nanofibers by Plasma Enhanced Chemical Vapour Deposition

    NASA Technical Reports Server (NTRS)

    Teo, K. B. K.; Hash, D. B.; Bell, M. S.; Chhowalla, M.; Cruden, B. A.; Amaratunga, G. A. J.; Meyyappan, M.; Milne, W. I.

    2005-01-01

    Plasma enhanced chemical vapour deposition (PECVD) has been recently used for the production of vertically aligned carbon nanotubedfibers (CN) directly on substrates. These structures are potentially important technologically as electron field emitters (e.g. microguns, microwave amplifiers, displays), nanoelectrodes for sensors, filter media, superhydrophobic surfaces and thermal interface materials for microelectronics. A parametric study on the growth of CN grown by glow discharge dc-PECVD is presented. In this technique, a substrate containing thin film Ni catalyst is exposed to C2H2 and NH3 gases at 700 C. Without plasma, this process is essentially thermal CVD which produces curly spaghetti-like CN as seen in Fig. 1 (a). With the plasma generated by biasing the substrate at -6OOV, we observed that the CN align vertically during growth as shown in Fig. l(b), and that the magnitude of the applied substrate bias affects the degree of alignment. The thickness of the thin film Ni catalyst was found to determine the average diameter and inversely the length of the CN. The yield and density of the CN were controlled by the use of different diffusion barrier materials under the Ni catalyst. Patterned CN growth [Fig. l(c)], with la variation in CN diameter of 4.1% and 6.3% respectively, is achieved by lithographically defining the Ni thin film prior to growth. The shape of the structures could be varied from very straight nanotube-like to conical tip-like nanofibers by increasing the ratio of C2H2 in the gas flow. Due to the plasma decomposition of C2H2, amorphous carbon (a-C) is an undesirable byproduct which could coat the substrate during CN growth. Using a combination of depth profiled Auger electron spectroscopy to study the substrate and in-situ mass spectroscopy to examine gas phase neutrals and ions, the optimal conditions for a-C free growth of CN is determined.

  3. Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

    NASA Technical Reports Server (NTRS)

    Martens, C. S.; Green, C. D.; Blair, N. E.; Des Marais, D. J.

    1986-01-01

    Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95 percent. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

  4. Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

    SciTech Connect

    Martens, C.S.; Blair, N.E.; Green, C.D.; Des Marais, D.J.

    1986-09-19

    Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio (delta /sup 13/C) of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95%. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites. 17 references, 2 figures, 2 tables.

  5. Watershed Scale Stable Isotope Distribution and Implications on Soil Organic Carbon Loss Monitoring under Hydrologic Uncertainty

    NASA Astrophysics Data System (ADS)

    Ahmed, I.; Karim, A.; Boutton, T. W.; Strom, K.; Fox, J.

    2013-12-01

    The thematic focus of this 3-year period multidisciplinary USDA-CBG collaborative applied research is integrated monitoring of soil organic carbon (SOC) loss from multi-use lands using state-of-the-art stable isotope science under uncertain hydrologic influences. In this study, SOC loss and water runoff are being monitored on a 150 square kilometer watershed in Houston, Texas, using natural rainfall events, and total organic carbon/nitrogen concentration (TOC/TN) and stable isotope ratio (δ13C, δ15N) measurements with different land-use types. The work presents the interdisciplinary research results to uncover statistically valid and scientifically sound ways to monitor SOC loss by (i) application of Bayesian Markov Chain Monte Carlo statistical models to assess the relationship between rainfall-runoff and SOC release during soil erosion in space and time, (ii) capturing the episodic nature of rainfall events and its role in the spatial distribution of SOC loss from water erosion, (iii) stable isotope composition guided fingerprinting (source and quantity) of SOC by considering various types of erosion processes common in a heterogeneous watershed, to be able to tell what percentage of SOC is lost from various land-use types (Fox and Papanicolaou, 2008), (iv) creating an integrated watershed scale statistical soil loss monitoring model driven by spatial and temporal correlation of flow and stable isotope composition (Ahmed et. al., 2013a,b), and (v) creation of an integrated decision support system (DSS) for sustainable management of SOC under hydrologic uncertainty to assist the end users. References: Ahmed, I., Karim, A., Boutton, T.W., and Strom, K.B. (2013a). 'Monitoring Soil Organic Carbon Loss from Erosion Using Stable Isotopes.' Proc., Soil Carbon Sequestration, International Conference, May 26-29, Reykjavik, Iceland. Ahmed, I, Bouttom, T.W., Strom, K. B., Karim, A., and Irvin-Smith, N. (2013b). 'Soil carbon distribution and loss monitoring in the

  6. Stable carbon isotope fractionation in the search for life on early Mars

    NASA Technical Reports Server (NTRS)

    Rothschild, L. J.; Desmarais, D.

    1989-01-01

    The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

  7. Engineering of Hollow Core-Shell Interlinked Carbon Spheres for Highly Stable Lithium-Sulfur Batteries.

    PubMed

    Sun, Qiang; He, Bin; Zhang, Xiang-Qian; Lu, An-Hui

    2015-08-25

    We report engineered hollow core-shell interlinked carbon spheres that consist of a mesoporous shell, a hollow void, and an anchored carbon core and are expected to be ideal sulfur hosts for overcoming the shortage of Li-S batteries. The hollow core-shell interlinked carbon spheres were obtained through solution synthesis of polymer spheres followed by a pyrolysis process that occurred in the hermetical silica shell. During the pyrolysis, the polymer sphere was transformed into the carbon core and the carbonaceous volatiles were self-deposited on the silica shell due to the blocking effect of the hermetical silica shell. The gravitational force and the natural driving force of lowering the surface energy tend to interlink the carbon core and carbon/silica shell, resulting in a core-shell interlinked structure. After the SiO2 shell was etched, the mesoporous carbon shell was generated. When used as the sulfur host for Li-S batteries, such a hierarchical structure provides access to Li(+) ingress/egress for reactivity with the sulfur and, meanwhile, can overcome the limitations of low sulfur loading and a severe shuttle effect in solid carbon-supported sulfur cathodes. Transmission electron microscopy and scanning transmission electron microscopy images provide visible evidence that sulfur is well-encapsulated in the hollow void. Importantly, such anchored-core carbon nanostructures can simultaneously serve as a physical buffer and an electronically connecting matrix, which helps to realize the full potential of the active materials. Based on the many merits, carbon-sulfur cathodes show a high utilization of sulfur with a sulfur loading of 70 wt % and exhibit excellent cycling stability (i.e., 960 mA h g(-1) after 200 cycles at a current density of 0.5 C).

  8. Detection of lead ions in picomolar concentration range using underpotential deposition on silver nanoparticles-deposited glassy carbon electrodes.

    PubMed

    Sivasubramanian, R; Sangaranarayanan, M V

    2011-09-30

    The efficacy of silver-deposited glassy carbon electrode for the determination of lead ions at the sub-nanomolar concentration ranges is investigated. The silver nanoparticles are electrodeposited on glassy carbon electrode using chronoamperometry and the electrode surface is characterized using SEM. Lead ions are detected in the region of underpotential deposition. The analysis is performed in square wave mode in the stripping voltammetry without the removal of oxygen. The detection limit of 10 pM has been obtained with a constant potential of -0.7 V during the electrodeposition step for a period of 50s. The interference of surfactants in the detection of lead ions is also studied.

  9. Urea-stabilized air-stable Pt nanoparticles for thin film deposition.

    PubMed

    Latour, Virginie; Maisonnat, André; Coppel, Yannick; Collière, Vincent; Fau, Pierre; Chaudret, Bruno

    2010-04-21

    The reduction of [Pt(COD)(CH3)2] with CO in the presence of hexadecylamine (HDA) and oleic acid (OlAc) leads to amine carbonylation and formation of an air-stable colloidal solution of N,N'-bis(hexadecyl)urea-stabilized Pt(0) nanoparticles. These air-stable colloidal solutions can be used to form thin films of Pt nanoparticles on a silicon substrate.

  10. Electrostatic Force Microscopic Characterization of Early Stage Carbon Deposition on Nickel Anodes in Solid Oxide Fuel Cells.

    PubMed

    Park, Hyungmin; Li, Xiaxi; Lai, Samson Y; Chen, Dongchang; Blinn, Kevin S; Liu, Mingfei; Choi, Sinho; Liu, Meilin; Park, Soojin; Bottomley, Lawrence A

    2015-09-09

    Carbon deposition on nickel anodes degrades the performance of solid oxide fuel cells that utilize hydrocarbon fuels. Nickel anodes with BaO nanoclusters deposited on the surface exhibit improved performance by delaying carbon deposition (i.e., coking). The goal of this research was to visualize early stage deposition of carbon on nickel surface and to identify the role BaO nanoclusters play in coking resistance. Electrostatic force microscopy was employed to spatially map carbon deposition on nickel foils patterned with BaO nanoclusters. Image analysis reveals that upon propane exposure initial carbon deposition occurs on the Ni surface at a distance from the BaO features. With continued exposure, carbon deposits penetrate into the BaO-modified regions. After extended exposure, carbon accumulates on and covers BaO. The morphology and spatial distribution of deposited carbon was found to be sensitive to experimental conditions.

  11. Parameterization of gaseous dry deposition in atmospheric chemistry models: Sensitivity to aerodynamic resistance formulations under statically stable conditions

    NASA Astrophysics Data System (ADS)

    Toyota, Kenjiro; Dastoor, Ashu P.; Ryzhkov, Andrei

    2016-12-01

    Turbulence controls the vertical transfer of momentum, heat and trace constituents in the atmospheric boundary layer. In the lowest 10% of this layer lies the surface boundary layer (SBL) where the vertical fluxes of transferred quantities have been successfully parameterized using the Monin-Obukhov similarity theory in weather forecast, climate and atmospheric chemistry models. However, there is a large degree of empiricism in the stability-correction parameterizations used to formulate eddy diffusivity and aerodynamic resistance particularly under strongly stable ambient conditions. Although the influence of uncertainties in stability-correction parameterizations on eddy diffusivity is actively studied in boundary-layer meteorological modeling, its impact on dry deposition in atmospheric chemistry modeling is not well characterized. In this study, we address this gap by providing the mathematical basis for the relationship between the formulations of vertical surface flux used in meteorological and atmospheric chemistry modeling communities, and by examining the sensitivity of the modeled dry deposition velocities in statically stable SBL to the choice of stability-correction parameterizations used in three operational and/or research environmental models (GEM/GEM-MACH, ECMWF IFS and CMAQ-MM5). Aerodynamic resistances (ra) calculated by the three sets of parameterizations are notably different from each other and are also different from those calculated by a "z-less" scaling formulation under strongly stable conditions (the bulk Richardson number > 0.2). Furthermore, we show that many atmospheric chemistry models calculate ra using formulations which are inconsistent with the derivation of micro-meteorological parameters. Finally, practical implications of the differences in stability-correction algorithms are discussed for the computations of dry deposition velocities of SO2, O3 and reactive bromine compounds for specific cases of stable SBL.

  12. Method of depositing a carbon film on a substrate and products obtained thereby

    SciTech Connect

    Lewin, G.; Nir, D.

    1984-12-04

    There is disclosed a method for depositing a diamond or diamond-like carbon film on at least one substrate employing a hydrocarbon gas and at least one gas which preferentially removes by chemical sputtering other forms of carbon, especially graphite from said film to thereby obtain useful carbon film coated products.

  13. [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.

  14. Site-specific carbon deposition for hierarchically ordered core/shell-structured graphitic carbon with remarkable electrochemical performance.

    PubMed

    Lv, Yingying; Wu, Zhangxiong; Qian, Xufang; Fang, Yin; Feng, Dan; Xia, Yongyao; Tu, Bo; Zhao, Dongyuan

    2013-10-01

    A fascinating core-shell-structured graphitic carbon material composed of ordered microporous core and uniform mesoporous shell is fabricated for the first time through a site-specific chemical vapor deposition process by using a nanozeolite@mesostructured silica composite molecular sieve as the template. The mesostructure-directing agent cetyltrimethylammonium bromide in the shell of the template can be either burned off or carbonized so that it is successfully utilized as a pore switch to turn the shell of the template "on" or "off" to allow selective carbon deposition. The preferred carbon deposition process can be performed only in the inner microporous zeolite cores or just within the outer mesoporous shells, resulting in a zeolite-like ordered microporous carbon or a hollow mesoporous carbon. Full carbon deposition in the template leads to the new core-shell-structured microporous@mesoporous carbon with a nanographene-constructed framework for fast electron transport, a microporous nanocore with large surface area for high-capacity storage of lithium ions, a mesoporous shell with highly opened mesopores as a transport layer for lithium ions and electron channels to access inner cores. The ordered micropores are protected by the mesoporous shell, avoiding pore blockage as the formation of solid electrolyte interphase layers. Such a unique core-shell-structured microporous@mesoporous carbon material represents a newly established lithium ion storage model, demonstrating high reversible energy storage, excellent rate capability, and long cyclic stability.

  15. Electrophoretic deposition of iron catalyst on C-fiber textiles for the growth of carbon nanofibers.

    PubMed

    Lee, Sang-Won; Lee, Chang-Seop

    2014-11-01

    In this study, carbon nanofibers synthesis has been conducted by chemical vapor deposition on C-fiber textiles coated with an iron catalyst via electrophoretic deposition. C-fiber textiles were oxidized with nitric acid before the iron catalyst was plated by electrophoretic deposition. Due to oxidation, the hydroxyl group was created on the C-fiber textiles and was used as an active site for iron catalyst deposition. It was verified that the iron catalyst was deposited on the C-fiber textiles, while current, voltage, and deposition time varied and the concentration of electrolyte was kept constant in electrophoretic deposition. After being deposited, the iron particles were dried in oven for 24 hours and reduced by hydrogen gas in a furnace. Ethylene gas was introduced for the growth of carbon nanofibers and the growth temperature was then varied to find the optimal growth temperature of the carbon nanofibers. Thus, the characteristics of carbon nanofibers were analyzed by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), N2-sorption (BET), X-Ray Diffraction (XRD), and X-ray Photoelectron Spectroscopy (XPS). It is verified that the iron particles were most evenly deposited at 0.1 A for 3 minutes. Carbon nanofibers grew to 150-200 nm most evenly at 600 degrees C via temperature variations in CVD.

  16. Effect of molecular weight on the electrophoretic deposition of carbon black nanoparticles in moderately viscous systems.

    PubMed

    Modi, Satyam; Panwar, Artee; Mead, Joey L; Barry, Carol M F

    2013-08-06

    Electrophoretic deposition from viscous media has the potential to produce in-mold assembly of nanoparticles onto three-dimensional parts in high-rate, polymer melt-based processes like injection molding. The effects of the media's molecular weight on deposition behavior were investigated using a model system of carbon black and polystyrene in tetrahydrofuran. Increases in molecular weight reduced the electrophoretic deposition of the carbon black particles due to increases in suspension viscosity and preferential adsorption of the longer polystyrene chains on the carbon black particles. At low deposition times (≤5 s), only carbon black deposited onto the electrodes, but the deposition decreased with increasing molecular weight and the resultant increases in suspension viscosity. For longer deposition times, polystyrene codeposited with the carbon black, with the amount of polystyrene increasing with molecular weight and decreasing with greater charge on the polystyrene molecules. This deposition behavior suggests that use of lower molecular polymers and control of electrical properties will permit electrophoretic deposition of nanoparticles from polymer melts for high-rate, one-step fabrication of nano-optical devices, biochemical sensors, and nanoelectronics.

  17. Measurements of CO2 Carbon Stable Isotopes at Artificial and Natural Analog Sites

    NASA Astrophysics Data System (ADS)

    Humphries, S. D.; Clegg, S. M.; Rahn, T.; Fessenden, J. E.; Dobeck, L.; Spangler, L.; McLing, T. L.

    2010-12-01

    Carbon storage in geologic formations is one method to prevent carbon dioxide (CO2), produced by fossil fuel combustion, from entering the Earth's atmosphere. The monitoring, verification and accounting (MVA) of geologically sequestered CO2 is critical to the operation of a geologic storage site. Surface MVA techniques need to identify seepage from the sequestration reservoir at or below ambient CO2 concentrations. The CO2 carbon stable isotope ratio of is a sensitive diagnostic signature that can distinguish between anthropogenic and natural sources of CO2. Frequency Modulated spectroscopy (FMS) is an ultra-sensitive version of absorption spectroscopy that is capable of detecting the CO2 carbon stable isotope ratios. The technique involves phase modulation of the laser such that two side bands, spaced wider than the absorption feature of interest (in this case +/-2 GHz) are created. The signal is mixed with the local oscillator yielding a signal proportional to the species concentration. This FMS signature is recorded at multiple wavelengths to obtain the CO2 carbon isotope ratio.Two instruments using the FMS technique have been built and tested at LANL. One instrument draws ambient air into a multi-pass cell for a measurement, point source measurements. The other instrument uses an open-air path, tested up to 160 m (round trip), to measure the CO2 carbon isotopic ratio along the beam path, column average measurements. In this paper, results from multiple field deployments of one or both of the instruments will be presented. The Zero Emissions Research & Technology (ZERT) group at Montana State University established a field test site where controlled amounts of CO2 are released to test the performance of CO2 detection instruments and measurement techniques. The field site allows a controlled flow rate of CO2 to be released into the near surface through a 100 m long horizontal pipe. In July of 2009, a release was conducted, with a uniform flow rate of 0.2 tons per

  18. Stable isotope evidence for carbon transformations in the water column and the sediments of the tropical Beibu Gulf, South China Sea

    NASA Astrophysics Data System (ADS)

    Wu, Zijun; Kowalski, Nicole; Dellwig, Olaf; Escher, Peter; Endler, Michael; Böttcher, Michael E.

    2013-04-01

    The depositional environment of the Beibu Gulf is highly complex, and sediments are formed under dynamic changes in hydrodynamics and sediment sources. It is an ideal natural laboratory to study biogeochemical transformation processes and its responses to changes in hydrography and depositional conditions in a tropical shelf environment. In the present study, several water column profiles and a number of short (MUC) and long (GC) sediment cores were taken during a joint German-Chinese expedition with R/V Sonne (Cruise 219; December 2011) in the Beibu Gulf. The sampling stations may be separated into three different depositional zones, namely Northern Coastal Beibu Gulf with sandy sediment, Delta Deposits in Vicinity to Qiongzhou Strait affected by strong currents, and Central Beibu Gulf with stable depositional environments. We measured the geochemical composition and carbon isotope composition of DIC in the water column and pore waters. In the sediments, the TOC, TIC, TN and TS contents, the C isotope composition of organic matter (OM), and the C and O isotope composition of carbonates were analyzed to follow the fate of organic matter during pelagic and benthic transformations. Pelagic OM transformations are already demonstrated by stable isotopes in the water column. The carbon isotopic composition of pore water DIC give further evidence for the mineralization of mainly marine OM with minor or no contributions from methane at most sites. The coupled pore water profiles indicate that sulfate reduction is the most important source for the DIC added to the pore waters. No correlation was observed between TOC contents and net sulfate reduction rates for the investigated sites. Lithostratigraphic marker and 14C age in different depositional zones indicated sedimentation rate plays an important role in determining the preservation and pathway of organic decomposition. In the central Beibu Gulf, where higher sedimentation rates dominate, pore water profiles exhibit the

  19. In situ oligonucleotide synthesis on carbon materials: stable substrates for microarray fabrication

    PubMed Central

    Phillips, Margaret F.; Lockett, Matthew R.; Rodesch, Matthew J.; Shortreed, Michael R.; Cerrina, Franco; Smith, Lloyd M.

    2008-01-01

    Glass has become the standard substrate for the preparation of DNA arrays. Typically, glass is modified using silane chemistries to provide an appropriate functional group for nucleic acid synthesis or oligonucleotide immobilization. We have found substantial issues with the stability of these surfaces as manifested in the unwanted release of oligomers from the surface when incubated in aqueous buffers at moderate temperatures. To address this issue, we have explored the use of carbon-based substrates. Here, we demonstrate in situ synthesis of oligonucleotide probes on carbon-based substrates using light-directed photolithographic phosphoramidite chemistry and evaluate the stabilities of the resultant DNA arrays compared to those fabricated on silanized glass slides. DNA arrays on carbon-based substrates are substantially more stable than arrays prepared on glass. This superior stability enables the use of high-density DNA arrays for applications involving high temperatures, basic conditions, or where serial hybridization and dehybridization is desired. PMID:18084027

  20. Carbon allocation belowground in Pinus pinaster using stable carbon isotope pulse labeling technique

    NASA Astrophysics Data System (ADS)

    Dannoura, M.; Bosc, A.; Chipeaux, C.; Sartore, M.; Lambrot, C.; Trichet, P.; Bakker, M.; Loustau, D.; Epron, D.

    2010-12-01

    Carbon allocation belowground competes with aboveground growth and biomass production. In the other hand, it contributes to resource acquisition such as nutrient, water and carbon sequestration in soil. Thus, a better characterization of carbon flow from plant to soil and its residence time within each compartment is an important issue for understanding and modeling forest ecosystem carbon budget. 13C pulse labeling of whole crown was conducted at 4 seasons to study the fate of assimilated carbon by photosynthesis into the root on 12 year old Pinus pinaster planted in the INRA domain of Pierroton. Maritime pine is the most widely planted species in South-West Europe. Stem, root and soil CO2 effluxes and their isotope composition were measured continuously by tunable diode laser absorption spectroscopy with a trace gas analyzer (TGA 100A; Campbell Scientific) coupled to flow-through chambers. 13CO2 recovery and peak were observed in respiration of each compartment after labeling. It appeared sequentially from top of stem to bottom, and to coarse root. The maximum velocity of carbon transfer was calculated as the difference in time lag of recovery between two positions on the trunk or on the root. It ranged between 0.08-0.2 m h-1 in stem and between 0.04-0.12 m h-1 in coarse root. This velocity was higher in warmer season, and the difference between time lag of recovery and peak increased after first frost. Photosynthates arrived underground 1.5 to 5 days after labeling, at similar time in soil CO2 effluxes and coarse root respiration. 0.08-1.4 g of carbon was respired per tree during first 20 days following labeling. It presented 0.6 -10% of 13C used for labeling and it is strongly related to seasons. The isotope signal was detected in fine root organs and microbial biomass by periodical core sampling. The peak was observed 6 days after labeling in early summer while it was delayed more than 10 days in autumn and winter with less amount of carbon allocated

  1. Stable carbon isotope analysis of coprocessing materials: Quarterly technical progress report, October 1--December 31, 1988

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Lancet, M.S.

    1989-03-01

    Consol R and D will develop and demonstrate stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken will be to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation will be determined and, if necessary, corrections will be applied to account for it. Precision, accuracy and range of applicability will be defined. The value of accessory analytical techniques will also be assessed. Results achieved this quarter include: feed and product fractions from hydroprocessing bench unit runs at the Kentucky Center for Applied Energy Research (CAER) were received, and samples from a Kentucky tar sand bitumen-only run were analyzed for carbon isotope ratios. Repeat carbon isotope analyses of seven samples from HRI Coprocessing Run 227-53 resulted in improved carbon balances for one run period. Athabasca ASB, Cold Lake ASB and Maya ASB were fractionated by distillation and solubility fractionation to determine the homogeneity of each petroleum with respect to carbon isotope ratios. 9 figs., 2 tabs.

  2. Nitrogen deposition: how important is it for global terrestrial carbon uptake?

    NASA Astrophysics Data System (ADS)

    Bala, G.; Devaraju, N.; Chaturvedi, R. K.; Caldeira, K.; Nemani, R.

    2013-11-01

    Global carbon budget studies indicate that the terrestrial ecosystems have remained a large sink for carbon despite widespread deforestation activities. CO2 fertilization, N deposition and re-growth of mid-latitude forests are believed to be key drivers for land carbon uptake. In this study, we assess the importance of N deposition by performing idealized near-equilibrium simulations using the Community Land Model 4.0 (CLM4). In our equilibrium simulations, only 12-17% of the deposited nitrogen is assimilated into the ecosystem and the corresponding carbon uptake can be inferred from a C : N ratio of 20 : 1. We calculate the sensitivity of the terrestrial biosphere for CO2 fertilization, climate warming and N deposition as changes in total ecosystem carbon for unit changes in global mean atmospheric CO2 concentration, global mean temperature and Tera grams of nitrogen deposition per year, respectively. Based on these sensitivities, it is estimated that about 242 PgC could have been taken up by land due to the CO2 fertilization effect and an additional 175 PgC taken up as a result of the increased N deposition since the pre-industrial period. Because of climate warming, the terrestrial ecosystem could have lost about 152 PgC during the same period. Therefore, since pre-industrial times terrestrial carbon losses due to warming may have been more or less compensated by effects of increased N deposition, whereas the effect of CO2 fertilization is approximately indicative of the current increase in terrestrial carbon stock. Our simulations also suggest that the sensitivity of carbon storage to increased N deposition decreases beyond current levels, indicating that climate warming effects on carbon storage may overwhelm N deposition effects in the future.

  3. Nitrogen deposition: how important is it for global terrestrial carbon uptake?

    NASA Astrophysics Data System (ADS)

    Bala, G.; Devaraju, N.; Chaturvedi, R. K.; Caldeira, K.; Nemani, R.

    2013-07-01

    Global carbon budget studies indicate that the terrestrial ecosystems have remained a~large sink for carbon despite widespread deforestation activities. CO2-fertilization, N deposition and re-growth of mid-latitude forests are believed to be key drivers for land carbon uptake. In this study, we assess the importance of N deposition by performing idealized near-equilibrium simulations using the Community Land Model 4.0 (CLM4). In our equilibrium simulations, only 12-17% of the deposited Nitrogen is assimilated into the ecosystem and the corresponding carbon uptake can be inferred from a C : N ratio of 20:1. We calculate the sensitivity of the terrestrial biosphere for CO2-fertilization, climate warming and N deposition as changes in total ecosystem carbon for unit changes in global mean atmospheric CO2 concentration, global mean temperature and Tera grams of Nitrogen deposition per year, respectively. Based on these sensitivities, it is estimated that about 242 PgC could have been taken up by land due to the CO2 fertilization effect and an additional 175 PgC taken up as a result of the increased N deposition since the pre-industrial period. Because of climate warming, terrestrial ecosystem could have lost about 152 PgC during the same period. Therefore, since preindustrial times terrestrial carbon losses due to warming may have been approximately compensated by effects of increased N deposition, whereas the effect of CO2-fertilization is approximately indicative of the current increase in terrestrial carbon stock. Our simulations also suggest that the sensitivity of carbon storage to increased N deposition decreases beyond current levels, indicating climate warming effects on carbon storage may overwhelm N deposition effects in the future.

  4. Martian Cryogenic Carbonate Formation: Stable Isotope Variations Observed in Laboratory Studies

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K. Jr.

    2014-01-01

    The history of water on Mars is tied to the formation of carbonates through atmospheric CO2 and its control of the climate history of the planet. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms easily from freezing solutions when carbon dioxide degasses quickly from Ca-bicarbonate-rich water, a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lake beds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. A series of laboratory experiments were conducted that simulated cryogenic carbonate formation on Mars in order to understand their isotopic systematics. The results indicate that carbonates grown under martian conditions show variable enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values.

  5. Stable carbon and oxygen isotope fractionation processes during speleothem growth: systematic investigation in novel laboratory experiments

    NASA Astrophysics Data System (ADS)

    Scholz, D.; Hansen, M.; Dreybrodt, W.

    2012-04-01

    The most widely applied climate proxies in speleothems are stable carbon and oxygen isotopes (δ13C and δ18O). The interpretation of the stable isotope signals in terms of past temperature and/or precipitation variability is complex because both δ18O and δ13C depend on a complex interplay of various processes occurring in the atmosphere, the soil and karst above the cave and inside the cave. Quantitative reconstruction of climate parameters such as temperature and precipitation has, thus, remained impossible so far. Here we present several novel laboratory experiments aiming to understand the basic physical and chemical processes affecting the δ18O and δ13C signals during precipitation of calcium carbonate on the stalagmite surface. In particular, we aim to quantify the influence of kinetic isotope fractionation and verify recently published modelling studies (Dreybrodt, 2008; Scholz et al., 2009, Dreybrodt and Scholz, 2011). Several experiments are conducted: Degassing of CO2 from a thin film of water sparged with CO2 flowing down an inclined glass plate. pH and electric conductivity are systematically documented in order to monitor degassing of CO2. The results show that degassing of CO2 is fast, and the pCO2 of the solution is in equilibrium with the atmosphere after a short distance of flow. Carbon isotope exchange between atmospheric CO2 and dissolved bicarbonate. The results show that carbon isotope exchange may have a significant effect on the δ13C value of the dissolved bicarbonate and, thus, speleothem calcite, in particular for slow drip rates. Degassing of CO2 and calcite precipitation from a thin film of water supersaturated with respect to calcite flowing down an inclined calcium carbonate plate. Drip water is sampled after different lengths of flow path and, thus, different residence times on the plate, and pH, electrical conductivity and the stable isotope composition of the water are determined. Decreasing conductivity with increasing distance

  6. Modeling carbon dynamics in vegetation and soil under the impact of soil erosion and deposition

    USGS Publications Warehouse

    Liu, S.; Bliss, N.; Sundquist, E.; Huntington, T.G.

    2003-01-01

    Soil erosion and deposition may play important roles in balancing the global atmospheric carbon budget through their impacts on the net exchange of carbon between terrestrial ecosystem and the atmosphere. Few models and studies have been designed to assess these impacts. In this study, we developed a general ecosystem model, Erosion-Deposition-Carbon-Model (EDCM), to dynamically simulate the influences of rainfall-induced soil erosion and deposition on soil organic carbon (SOC) dynamics in soil profiles. EDCM was applied to several landscape positions in the Nelson Farm watershed in Mississippi, including ridge top (without erosion or deposition), eroding hillslopes, and depositional sites that had been converted from native forests to croplands in 1870. Erosion reduced the SOC storage at the eroding sites and deposition increased the SOC storage at the depositional areas compared with the site without erosion or deposition. Results indicated that soils were consistently carbon sources to the atmosphere at all landscape positions from 1870 to 1950, with lowest source strength at the eroding sites (13 to 24 gC m-2 yr-1), intermediate at the ridge top (34 gC m-2 yr-1), and highest at the depositional sites (42 to 49 gC m-2 yr-1). During this period, erosion reduced carbon emissions via dynamically replacing surface soil with subsurface soil that had lower SOC contents (quantity change) and higher passive SOC fractions (quality change). Soils at all landscape positions became carbon sinks from 1950 to 1997 due to changes in management practices (e.g., intensification of fertilization and crop genetic improvement). The sink strengths were highest at the eroding sites (42 to 44 gC m-2 yr-1 , intermediate at the ridge top (35 gC m-2 yr-1), and lowest at the depositional sites (26 to 29 gC m-2 yr-1). During this period, erosion enhanced carbon uptake at the eroding sites by continuously taking away a fraction of SOC that can be replenished with enhanced plant residue

  7. Uplift and submarine formation of some Melanesian porphyry copper deposits: Stable isotope evidence

    USGS Publications Warehouse

    Chivas, A.R.; O'Neil, J.R.; Katchan, G.

    1984-01-01

    Hydrogen and oxygen isotope analyses of sericites and kaolinites from four young porphyry copper deposits (Ok Tedi (1.2 Ma) and Yandera (6.5 Ma), Papua New Guinea; Koloula (1.5 Ma), Solomon Islands; and Waisoi (<5 Ma), Fiji) indicate that the fluids from which these minerals precipitated were of mixed magmatic and non-magmatic sources. The non-magmatic component of the fluid from the island arc deposits (Koloula, Waisoi) was ocean water. For Ok Tedi, the non-magmatic component was a meteoric water with an isotopic composition different from that of the present meteoric water in the region. The isotopic signature of the former meteoric water is consistent with a surface elevation of 200 m a.s.l. or less at the time of mineralization. The deposit was later exposed and supergene kaolinitization commenced at approximately 1200 m a.s.l. Uplift and erosion has continued to the present at which time the elevation of the exposed deposit is 1800 m a.s.l. This rate of uplift is consistent with that known from other geological evidence. If the rate of uplift were approximately constant during the last 1.2 Ma, the age of supergene enrichment can be dated at approximately 0.4 Ma B.P. Similarly, influx of meteoric water at Yandera occurred when the ground surface above the deposit was at an elevation of approximately 600 m a.s.l. The deposit's present elevation is 1600 m a.s.l. In this case a total uplift of approximately 2.2 km is indicated, with removal of 1.2 km of overburden by erosion. ?? 1984.

  8. Carbonate deposition on tail feathers of ruddy ducks using evaporation ponds

    USGS Publications Warehouse

    Euliss, N.H.; Jarvis, R.L.; Gilmer, D.S.

    1989-01-01

    Substantial carbonate deposits were observed on rectrices of Ruddy Ducks (Oxyura jamaicensis) collected during 1982-1984 on evaporation ponds in the San Joaquin Valley, California. Carbonate deposits were composed of about 75% aragonite and 25% calcite, both polymorphous forms of CaCO3. Significantly more carbonate deposits were observed on Ruddy Ducks as length of exposure to agricultural drain water increased, during the 1983-1984 field season when salt concentrations in the ponds were higher, and in certain evaporation-pond systems.

  9. A Carbon Source Apportionment Shift in Mexico City Atmospheric Particles During 2003-2004 as Determined with Stable Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Lopez-Veneroni, D. G.; Vega, E.

    2013-05-01

    The stable carbon isotope composition of atmospheric particles (PM2.5) was measured at La Merced (MER), a commercial site in the eastern sector, and at Xalostoc (XAL) an industrial site in the NE sector of Mexico City, during three sampling periods in autumn 2003, and spring and autumn 2004. At each site and sampling campaign particle samples were collected daily with minivol samplers during two week periods. Ancillary data included organic and elemental carbon, trace elements and ionic species. This data base was complement with air quality data from the RAMA (Automatic Atmospheric Monitoring Network). In general, particle concentrations, ionic species and some air quality species showed higher concentrations in autumn and lowest values in spring. Moreover, the concentrations of these chemical species were highest at XAL compared to MER. The stable carbon isotope composition of PM2.5 during autumn 2003 and spring 2004 had and average value of -26.04 (± 1.54) ‰ vs. PDB. Differences in the isotopic composition between the two sites were non significant. The average δ13C during these seasons were 1 ‰ lighter relative to data collected previously at these sites during 2000 and 2001, and is consistent with a predominant source of hydrocarbon combustion. In autumn 2004, however, average δ13C at XAL and MER increased to -22.8 (± 0.9) and -20.6 (± 3.1) ‰, respectively. Organic carbon concentrations during this period increased concomitantly at these sites. The shift in the isotopic composition in ambient particles suggests a predominance of soil-derived carbon during this period. The possible causes and implications of this are discussed.

  10. Effects of Land Use on Stable Carbon Isotopic Composition and Concentration of Dissolved Organic Carbon (DOC) and Dissolved Inorganic Carbon (DIC) in Southeastern US Piedmont Headwater Streams

    EPA Science Inventory

    Stable carbon isotopic composition (delta 13C) and concentrations of DOC and DIC were measured in stream water samples collected monthly in 15 headwater streams from an area with extensive poultry and cattle production and a rapidly growing human population. Linear regression te...

  11. Thin film growth rate effects for primary ion beam deposited diamondlike carbon films

    NASA Technical Reports Server (NTRS)

    Nir, D.; Mirtich, M.

    1986-01-01

    Diamondlike carbon (DLC) films were grown by primary ion beam deposition and the growth rates were measured for various beam energies, types of hydrocarbon gases and their ratio to Ar, and substrate materials. The growth rate had a linear dependence upon hydrocarbon content in the discharge chamber, and only small dependence on other parameters. For given deposition conditions a threshold in the atomic ratio of carbon to argon gas was identified below which films did not grow on fused silica substrate, but grew on Si substrate and on existing DLC films. Ion source deposition parameters and substrate material were found to affect the deposition threshold and film growth rates.

  12. Co-sputter deposited nickel-copper bimetallic nanoalloy embedded carbon films for electrocatalytic biomarker detection

    NASA Astrophysics Data System (ADS)

    Shiba, Shunsuke; Kato, Dai; Kamata, Tomoyuki; Niwa, Osamu

    2016-06-01

    We report the fabrication of a nickel (Ni)-copper (Cu) bimetallic nanoalloy (~3 nm) embedded carbon film electrode with the unbalanced magnetron (UBM) co-sputtering technique, which requires only a one-step process at room temperature. Most of each nanoalloy body was firmly embedded in a chemically stable carbon matrix with an atomically flat surface (Ra: 0.21 nm), suppressing the aggregation and/or detachment of the nanoalloy from the electrode surface. The nanoalloy size and composition can be controlled simply by individually controlling the target powers of carbon, Ni and Cu, which also makes it possible to localize the nanoalloys near the electrode surface. This electrode exhibited excellent electrocatalytic activity for d-mannitol, which should be detected with a low detection limit in urine samples for the diagnosis of severe intestinal diseases. With a Ni/Cu ratio of around 64/36, the electrocatalytic current per metal area was 3.4 times larger than that of an alloy film electrode with a similar composition (~70/30). This improved electrocatalytic activity realized higher stability (n = 60, relative standard deviation (RSD): 4.6%) than the alloy film (RSD: 32.2%) as demonstrated by continuous measurements of d-mannitol.We report the fabrication of a nickel (Ni)-copper (Cu) bimetallic nanoalloy (~3 nm) embedded carbon film electrode with the unbalanced magnetron (UBM) co-sputtering technique, which requires only a one-step process at room temperature. Most of each nanoalloy body was firmly embedded in a chemically stable carbon matrix with an atomically flat surface (Ra: 0.21 nm), suppressing the aggregation and/or detachment of the nanoalloy from the electrode surface. The nanoalloy size and composition can be controlled simply by individually controlling the target powers of carbon, Ni and Cu, which also makes it possible to localize the nanoalloys near the electrode surface. This electrode exhibited excellent electrocatalytic activity for d

  13. Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

    USGS Publications Warehouse

    Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

    2014-01-01

    The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3

  14. Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

    NASA Astrophysics Data System (ADS)

    Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

    2014-08-01

    The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2-5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2-5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>-10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and

  15. Stable carbon isotope analysis in a South Texas cave: Investigating sources of CO2 production

    NASA Astrophysics Data System (ADS)

    Thompson, Reece

    Studies of interactions between modern local climate, cave atmosphere, and ?13C ratios are needed to determine sources of CO2 in caves, and the cycles of seasonal variations that alter karst geochemistry. A seasonal study, focusing on the analysis of stable isotopes collected from a modern cave system, was conducted in Robber Baron Cave (RBC) in order to identify sources of CO2 in its atmosphere. Determining what conditions affect cave morphology and the transfer path of carbon through a cave system is necessary in order to assess the role of caves in the carbon cycle and correctly interpret past ecological changes. This study investigates the extent that stable isotopic values of carbon in CO2 are affected by CO2 sourced from soils, bedrock, atmospheric air, and vegetation, and how ?13C signals are transmitted in a modern cave system. This study also measures how ventilation affects CO2 concentration and ?13C on seasonal scales. In-cave air grab samples were collected monthly at various transects located in RBC in order to measure CO2 composition in addition to factors such as temperature, and barometric pressure. Soil gas and limestone bedrock were also collected and tested for ?13C composition. Air samples were analyzed using an Ambient Air-Model G2101-I Picarro Cavity Ring-Down Spectroscopy Analyzer for both the concentration and ?13C isotopic value of CO2. These values were then compared to isotopic values of known sources of CO2 in order to determine possible sources of CO2 that result in high CO2 concentrations found in RBC. The background stable isotopic value of carbon from CO2 measured in RBC is -19.1‰ VPDB.

  16. Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

    NASA Technical Reports Server (NTRS)

    Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.

    2013-01-01

    The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the

  17. Nitrogen deposition enhances carbon sequestration by plantations in northern China.

    PubMed

    Du, Zhihong; Wang, Wei; Zeng, Wenjing; Zeng, Hui

    2014-01-01

    Nitrogen (N) deposition and its ecological effects on forest ecosystems have received global attention. Plantations play an important role in mitigating climate change through assimilating atmospheric CO2. However, the mechanisms by which increasing N additions affect net ecosystem production (NEP) of plantations remain poorly understood. A field experiment was initialized in May 2009, which incorporated additions of four rates of N (control (no N addition), low-N (5 g N m⁻² yr⁻¹), medium-N (10 g N m⁻² yr⁻¹), and high-N (15 g N m⁻² yr⁻¹) at the Saihanba Forestry Center, Hebei Province, northern China, a locality that contains the largest area of plantations in China. Net primary production (NPP), soil respiration, and its autotrophic and heterotrophic components were measured. Plant tissue carbon (C) and N concentrations (including foliage, litter, and fine roots), microbial biomass, microbial community composition, extracellular enzyme activities, and soil pH were also measured. N addition significantly increased NPP, which was associated with increased litter N concentrations. Autotrophic respiration (AR) increased but heterotrophic respiration (HR) decreased in the high N compared with the medium N plots, although the HR in high and medium N plots did not significantly differ from that in the control. The increased AR may derive from mycorrhizal respiration and rhizospheric microbial respiration, not live root respiration, because fine root biomass and N concentrations showed no significant differences. Although the HR was significantly suppressed in the high-N plots, soil microbial biomass, composition, or activity of extracellular enzymes were not significantly changed. Reduced pH with fertilization also could not explain the pattern of HR. The reduction of HR may be related to altered microbial C use efficiency. NEP was significantly enhanced by N addition, from 149 to 426.6 g C m⁻² yr⁻¹. Short-term N addition may significantly enhance

  18. Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

    NASA Astrophysics Data System (ADS)

    Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

    2003-12-01

    Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

  19. Cryogenic Carbonate Formation on Mars: Clues from Stable Isotope Variations Seen in Experimental Studies

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Niles, Paul B.; Fu, Qi; Gibson, Everett K., Jr.

    2010-01-01

    Discoveries of large deposits of sedimentary materials on the planet Mars by landers and orbiters have confirmed the widely held hypothesis that water has played a crucial role in the development of the martian surface. Recent studies have indicated that both water ice and liquid water may have been present and in the case of water ice perhaps is still present on or near the surface of Mars. However, there remains much controversy about the prevailing atmospheric conditions and climate of Mars during its history and whether liquid water existed on the martian surface simply during discrete geological events or whether this water was present over relatively much longer geologic time periods. The recent identification of Ca-rich carbonate by the Phoenix lander as well as its measurement of the isotopic composition of atmospheric CO2 has shown the importance of understanding the carbonates on Mars as an important sink of atmospheric carbon. This work compliments that of our past experiments where we produced cryogenic calcite in open containers, as analogs for terrestrial aufeis formation, and as a means for evaluating the fractionation of C-13 in CO2 during bicarbonate freezing [13]. Unlike our previous experiments in which carbonates were grown in ambient laboratory condition in open containers (atmospheric pressure and composition), this work attempts to quantify the amount of delta C-13 enrichment possible in both fluids and secondary carbonates formed from freezing of bicarbonate fluids under martian-like atmospheric conditions. Morphologic textures of produced carbonates in these experiments are also examined under SEM in order to identify the effect that the cryogenic freezing process has on the mineral's mineralogy. Understanding the role of kinetic isotope fractionation during formation of carbonates under martian-like conditions will aid in our ability to quantify the isotopic composition of the carbonate sink furthering our ability to model the climate

  20. Atomic Layer Deposition on Carbon Nanotubes and their Assemblies

    NASA Astrophysics Data System (ADS)

    Stano, Kelly Lynn

    Global issues related to energy and the environment have motivated development of advanced material solutions outside of traditional metals ceramics, and polymers. Taking inspiration from composites, where the combination of two or more materials often yields superior properties, the field of organic-inorganic hybrids has recently emerged. Carbon nanotube (CNT)-inorganic hybrids have drawn widespread and increasing interest in recent years due to their multifunctionality and potential impact across several technologically important application areas. Before the impacts of CNT-inorganic hybrids can be realized however, processing techniques must be developed for their scalable production. Optimization in chemical vapor deposition (CVD) methods for synthesis of CNTs and vertically aligned CNT arrays has created production routes both high throughput and economically feasible. Additionally, control of CVD parameters has allowed for growth of CNT arrays that are able to be drawn into aligned sheets and further processed to form a variety of aligned 1, 2, and 3-dimensional bulk assemblies including ribbons, yarns, and foams. To date, there have only been a few studies on utilizing these bulk assemblies for the production of CNT-inorganic hybrids. Wet chemical methods traditionally used for fabricating CNT-inorganic hybrids are largely incompatible with CNT assemblies, since wetting and drying the delicate structures with solvents can destroy their structure. It is therefore necessary to investigate alternative processing strategies in order to advance the field of CNT-inorganic hybrids. In this dissertation, atomic layer deposition (ALD) is evaluated as a synthetic route for the production of large-scale CNT-metal oxide hybrids as well as pure metal oxide architectures utilizing CNT arrays, ribbons, and ultralow density foams as deposition templates. Nucleation and growth behavior of alumina was evaluated as a function of CNT surface chemistry. While highly graphitic

  1. Determination of the origin of dissolved inorganic carbon in groundwater around a reclaimed landfill in Otwock using stable carbon isotopes.

    PubMed

    Porowska, Dorota

    2015-05-01

    Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC) in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ(13)CDIC) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ(13)CDIC values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4-54% of the DIC pool is derived from organic matter degradation and 96-46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20-53% of the DIC is derived from organic matter degradation of natural origin and 80-47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO2 (P CO2) was generally above the atmospheric, hence atmospheric CO2 as a source of carbon in DIC pool was negligible in the aquifer. P CO2 values in the aquifer in Otwock were always one to two orders of magnitude above the atmospheric P CO2, and thus CO2 escaped directly into the vadose zone.

  2. Use of stable carbon and nitrogen isotope ratios in size segregated aerosol particles for the O/I penetration evaluation

    NASA Astrophysics Data System (ADS)

    Garbaras, Andrius; Garbariene, Inga; Masalaite, Agne; Ceburnis, Darius; Krugly, Edvinas; Kvietkus, Kestutis; Remeikis, Vidmantas; Martuzevicius, Dainius

    2015-04-01

    Stable carbon and nitrogen isotope ratio are successfully used in the atmospheric aerosol particle source identification [1, 2], transformation, pollution [3] research. The main purpose of this study was to evaluate the penetration of atmospheric aerosol particles from outdoor to indoor using stable carbon and nitrogen isotope ratios. Six houses in Kaunas (Lithuania) were investigated during February and March 2013. Electrical low pressure impactor was used to measure in real time concentration and size distribution of outdoor aerosol particles. ELPI+ includes 15 channels covering the size range from 0.017 to 10.0 µm. The 25 mm diameter aluminium foils were used to collect aerosol particles. Gravimetric analysis of samples was made using microbalance. In parallel, indoor aerosol samples were collected with a micro-orifice uniform deposition impactor (MOUDI model 110), where the aerosol particles were separated with the nominal D50 cut-off sizes of 0.056, 0.1, 0.18,0.32,0.56, 1.0, 1.8, 3.2, 5.6, 10, 18 μm for impactor stages 1-11, respectively. The impactor was run at a flow rate of 30 L/min. Air quality meters were used to record meteorological conditions (temperature, relative humidity) during the investigated period. All aerosol samples were analyzed for total carbon (TC) and total nitrogen (TN) contents and their isotopic compositions using elemental analyzer (EA) connected to the stable isotope ratio mass spectrometer (IRMS). TC concentration in indoors ranged from 1.5 to 247.5 µg/m3. During the sampling period outdoors TN levels ranged from 0.1 to 10.9 µg/m3. The obtained outdoor δ13C(PM2.5) values varied from -24.21 to -26.3‰, while the δ15N values varied from 2.4 to 11.1 ‰ (average 7.2±2.5 ‰). Indoors carbonaceous aerosol particles were depleted in 13C compared to outdoors in all sampling sites. This depletion in δ13C varied from 0.1 to 3.2 ‰. We think that this depletion occurs due ongoing chemical reactions (oxidation) when aerosol

  3. Hierarchical composite structures prepared by electrophoretic deposition of carbon nanotubes onto glass fibers.

    PubMed

    An, Qi; Rider, Andrew N; Thostenson, Erik T

    2013-03-01

    Carbon nanotube/glass fiber hierarchical composite structures have been produced using an electrophoretic deposition (EPD) approach for integrating the carbon nanotubes (CNTs) into unidirectional E-glass fabric, followed by infusion of an epoxy polymer matrix. The resulting composites show a hierarchical structure, where the structural glass fibers, which have diameters in micrometer range, are coated with CNTs having diameters around 10-20 nm. The stable aqueous dispersions of CNTs were produced using a novel ozonolysis and ultrasonication technique that results in dispersion and functionalization in a single step. Ozone-oxidized CNTs were then chemically reacted with a polyethyleneimine (PEI) dendrimer to enable cathodic EPD and promote adhesion between the CNTs and the glass-fiber substrate. Deposition onto the fabric was accomplished by placing the fabric in front of the cathode and applying a direct current (DC) field. Microscopic characterization shows the integration of CNTs throughout the thickness of the glass fabric, where individual fibers are coated with CNTs and a thin film of CNTs also forms on the fabric surfaces. Within the composite, networks of CNTs span between adjacent fibers, and the resulting composites exhibit good electrical conductivity and considerable increases in the interlaminar shear strength, relative to fiber composites without integrated CNTs. Mechanical, chemical and morphological characterization of the coated fiber surfaces reveal interface/interphase modification resulting from the coating is responsible for the improved mechanical and electrical properties. The CNT-coated glass-fiber laminates also exhibited clear changes in electrical resistance as a function of applied shear strain and enables self-sensing of the transition between elastic and plastic load regions.

  4. After the Storm: Assessing the carbon and nitrogen leaching potential from sediments deposited in aquatic ecosystems

    NASA Astrophysics Data System (ADS)

    Johnson, E. R.; Krieg, C.; Canning, C.; Inamdar, S. P.; Rowland, R. D.

    2015-12-01

    The erosive energy of large storms can mobilize, and subsequently deposit large amounts of sediment in receiving aquatic ecosystems. Depending on the character of the sediments there is potential for leaching or sequestration of carbon (C) and nitrogen (N) from the sediments. This could have significant implications for water quality, aquatic metabolism, and global cycling of C and N. This study examines the fate of these sediments by: (1) determining the amount and quality of organic matter that can be leached into the surrounding water from coarse, medium and fine particle classes (2) assessing the C and N contents of various particles classes and the sources of the sediment through isotopic composition. Bed sediment samples were collected along a 1-2nd order stream (eight locations) in a forested catchment in the Piedmont region of Maryland following a large storm event. Samples were sieved into three particle classes - coarse (2mm-1mm), medium (1mm-250µm) and fine (<250µm). Extractions were performed for each of three particle class sizes by leaching with DI water. Organic matter composition for the extracts was characterized using fluorescence. Stable isotopes of 13C and 15N were determined for bed sediment classes and upland source sediments to identify the origins of the eroded sediments. Extracts with low C:N ratios that also exhibit a higher percent protein and lower percent humic carbon content are considered most labile. Within the bed sediment deposits, differences were found in the distribution of labile compounds between each particle class size. Generally, course particle size exhibited the most labile characteristics, closely followed by medium particle size. Fine particle size exhibited the most refractory characteristics in all locations. These results are critical since climate-change predictions reveal more intense and large storms for the northeast US, with potentially greater impacts on aquatic ecosystems from eroded upland sediments.

  5. Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

    USGS Publications Warehouse

    Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

    2016-01-01

    Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

  6. Carbon deposition in an SOFC fueled by tar-laden biomass gas: a thermodynamic analysis

    NASA Astrophysics Data System (ADS)

    Singh, Devinder; Hernández-Pacheco, Eduardo; Hutton, Phillip N.; Patel, Nikhil; Mann, Michael D.

    This work presents a thermodynamic analysis of the carbon deposition in a solid oxide fuel cell (SOFC) fueled by a biomass gasifier. Integrated biomass-SOFC units offer considerable benefits in terms of efficiency and fewer emissions. SOFC-based power plants can achieve a system efficiency of 70-80% (including heat utilization) as compared to 30-37% for conventional systems. The fuel from the biomass gasifier can contain considerable amounts of tars depending on the type of gasifier used. These tars can lead to the deposition of carbon at the anode side of SOFCs and affect the performance of the fuel cells. This paper thermodynamically studies the risk of carbon deposition due to the tars present in the feed stream and the effect various parameters like current density, steam, and temperature have on carbon deposition. Since tar is a complex mixture of aromatics, it is represented by a mixture of toluene, naphthalene, phenol, and pyrene. A total of 32 species are considered for the thermodynamic analysis, which is done by the Gibbs energy minimization technique. The carbon deposition is shown to decrease with an increase in current density and becomes zero after a critical current density. Steam in the feed stream also decreases the amount of carbon deposition. With the increase in temperature the amount of carbon first decreases and then increases.

  7. Efficient, air-stable colloidal quantum dot solar cells encapsulated using atomic layer deposition of a nanolaminate barrier

    SciTech Connect

    Ip, Alexander H.; Labelle, André J.; Sargent, Edward H.

    2013-12-23

    Atomic layer deposition was used to encapsulate colloidal quantum dot solar cells. A nanolaminate layer consisting of alternating alumina and zirconia films provided a robust gas permeation barrier which prevented device performance degradation over a period of multiple weeks. Unencapsulated cells stored in ambient and nitrogen environments demonstrated significant performance losses over the same period. The encapsulated cell also exhibited stable performance under constant simulated solar illumination without filtration of harsh ultraviolet photons. This monolithically integrated thin film encapsulation method is promising for roll-to-roll processed high efficiency nanocrystal solar cells.

  8. Surface treatment effect on Si (111) substrate for carbon deposition using DC unbalanced magnetron sputtering

    SciTech Connect

    Aji, A. S. Sahdan, M. F.; Hendra, I. B.; Dinari, P.; Darma, Y.

    2015-04-16

    In this work, we studied the effect of HF treatment in silicon (111) substrate surface for depositing thin layer carbon. We performed the deposition of carbon by using DC Unbalanced Magnetron Sputtering with carbon pallet (5% Fe) as target. From SEM characterization results it can be concluded that the carbon layer on HF treated substrate is more uniform than on substrate without treated. Carbon deposition rate is higher as confirmed by AFM results if the silicon substrate is treated by HF solution. EDAX characterization results tell that silicon (111) substrate with HF treatment have more carbon fraction than substrate without treatment. These results confirmed that HF treatment on silicon Si (111) substrates could enhance the carbon deposition by using DC sputtering. Afterward, the carbon atomic arrangement on silicon (111) surface is studied by performing thermal annealing process to 900 °C. From Raman spectroscopy results, thin film carbon is not changing until 600 °C thermal budged. But, when temperature increase to 900 °C, thin film carbon is starting to diffuse to silicon (111) substrates.

  9. Tracing the source of sedimentary organic carbon in the Loess Plateau of China: An integrated elemental ratio, stable carbon signatures, and radioactive isotopes approach.

    PubMed

    Liu, Chun; Dong, Yuting; Li, Zhongwu; Chang, Xiaofeng; Nie, Xiaodong; Liu, Lin; Xiao, Haibing; Bashir, Hassan

    2017-02-01

    Soil erosion, which will induce the redistribution of soil and associated soil organic carbon (SOC) on the Earth's surface, is of critically importance for biogeochemical cycling of essential elements and terrestrial carbon sequestration. Despite the importance of soil erosion, surprisingly few studies have evaluated the sources of eroded carbon (C). This study used natural abundance levels of the stable isotope signature ((13)C) and radioactive isotopes ((137)Cs and (210)Pbex), along with elements ratio (C/N) based on a two end member mixing model to qualitatively and quantitatively identify the sources of sedimentary OC retained by check dam in the Qiaozigou small watershed in the Loess Plateau, China. Sediment profiles (0-200 cm) captured at natural depositional area of the basin was compared to possible source materials, which included: superficial Loess mineral soils (0-20 cm) from three land use types [i.e., grassland (Medicago sativa), forestland (Robinia pseudoacacia.), shrubland (Prunus sibirica), and gully land (Loess parent material.)]. The results demonstrated that SOC in sediments showed significantly negative correlation with pH (P < 0.01), and positive correlation with soil water content (SWC) (P < 0.05). The sedimentary OC was not derived from grasslands or gullies. Forestland and shrubland were two main sources of eroded organic carbon within the surface sediment (0-60 cm deep), except for that in the 20-40 cm soil layer. Radionuclides analyses also implied that the surface sediments retained by check-dams mainly originated from soils of forestland and shrubland. Results of the two end-member mixing model demonstrated that more than 50% SOC (mean probability estimate (MPE) 50.13% via (13)C and 60.53% via C/N) in surface sediment (0-20 cm deep) derived from forestland, whereas subsurface sedimentary SOC (20-200 cm) mainly resulted from shrubland (MPE > 50%). Although uncertainties on the sources of SOC in deep soils exist, the soil

  10. Inorganic markers, carbonaceous components and stable carbon isotope from biomass burning aerosols in Northeast China.

    PubMed

    Cao, Fang; Zhang, Shi-Chun; Kawamura, Kimitaka; Zhang, Yan-Lin

    2016-12-01

    To better characterize the chemical compositions and sources of fine particulate matter (i.e. PM2.5) in Sanjiang Plain, Northeast China, total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions as well as stable carbon isotopic composition (δ(13)C) were measured in this study. Intensively open biomass burning episodes are identified from late September to early October by satellite fire and aerosol optical depth maps. During the biomass-burning episode, concentrations of PM2.5, OC, EC, and WSOC are increased by a factor of 4-12 compared to those during the non-biomass-burning period. Non-sea-salt potassium is strongly correlated with PM2.5, OC, EC and WSOC, demonstrating an important contribution from biomass-burning emissions. The enrichment in both the non-sea-salt potassium and chlorine is significantly larger than other inorganic species, suggesting that biomass-burning aerosols in Sanjiang Plain are mostly fresh and less aged. In addition, the WSOC-to-OC ratio is lower than that reported in biomass-burning aerosols in tropical regions, further supporting that biomass-burning aerosols in Sanjiang Plain are mostly primary and secondary organic aerosols may be not significant. A lower average δ(13)C value (-26.2‰) is observed during the biomass-burning period, indicating a dominant contribution from combustion of C3 plants in the studied region.

  11. Microbial Utilization of Estuarine Dissolved Organic Carbon: a Stable Isotope Tracer Approach Tested by Mass Balance

    PubMed Central

    Hullar, M.; Fry, B.; Peterson, B. J.; Wright, R. T.

    1996-01-01

    The natural stable isotope values of different plants have been used to trace the fate of organic carbon that enters estuarine ecosystems. Experiments were designed to determine the magnitude of (delta) (sup13)C changes of dissolved organic carbon (DOC) derived from tidal marsh vegetation that occurred during bacterial decomposition. Bacteria were grown on DOC leached from estuarine Spartina alterniflora and Typhus angustifolia plants. In four experiments, 25 to 80% of the initial carbon (2.6 to 9.1 mM organic C) was converted to bacterial biomass and CO(inf2). Mass balance calculations showed good recovery of total C and (sup13)C at the end of these experiments (100% (plusmn) 14% total C; (plusmn) 1(permil) (delta) (sup13)C). The (delta) (sup13)C values of DOC, bacterial biomass, and respired CO(inf2) changed only slightly in the four experiments by average values of -0.6, +1.4, and +0.5(permil), respectively. These changes are small relative to the range of (delta) (sup13)C values represented by different organic carbon sources to estuaries. Thus, microbial (delta) (sup13)C values determined in the field helped to identify the source of the carbon assimilated by bacteria. PMID:16535358

  12. Constraining Rates of Biodegradation of Chlorinated Ethenes at Steep Concentration Gradients Using Stable Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Morrill, P. L.; Seepersad, D. J.; Lacrampe-Couloume, G.; Edwards, E. A.; Sleep, B. E.; McMaster, M. L.; Major, D. W.; Sherwood Lollar, B.

    2005-12-01

    Enhanced biodegradation of emplaced dense non-aqueous phase liquid (DNAPL) sources of tetrachloroethene (PCE) was monitored in a 2-dimensional model aquifer and in a Dover Air Force Base pilot field study. The stable carbon isotope values of PCE and its biodegradation products were monitored along steep concentration gradients near the PCE source zones to quantify first order biodegradation rate constants during a study that assessed the potential for biological enhancement of PCE DNAPL dissolution . Stable carbon isotope measurements are an ideal tool to assess the relative rate of biodegradation versus dissolution since while biodegradation of chlorinated ethenes involves a substantial carbon isotope fractionation, dissolution of chlorinated ethenes is a largely non-fractionating process. Within the dissolved plumes that developed down gradient from the emplaced sources, the isotopic fractionation of PCE and its degradation products in both the model aquifer and field study were consistent with those previously observed in batch laboratory studies. A maximum isotope fractionation of 2.3 permil was observed in the dissolved PCE downgradient, while close to the source zone the carbon isotopic signature of the dissolved PCE remained largely unchanged, due to the continuing dissolution of unfractionated PCE DNAPL. Significant carbon isotopic fractionation was observed adjacent to and/or downstream from the source in the degradation products trichloroethene (TCE), 1,2-dichloroethene (cDCE), and vinyl chloride (VC). Therefore, close to the source zone, confirmation of PCE degradation is based primarily on the appearance of the lesser chlorinated ethene degradation products and isotopic signatures of those products consistent with biodegradation. This trend was observed on a small scale in the model aquifer and similar trends were observed in the field at a larger scale. In both cases biodegradation was correlated with enhanced rates of DNAPL dissolution compared to non

  13. Aligned carbon nanotube, graphene and graphite oxide thin films via substrate-directed rapid interfacial deposition.

    PubMed

    D'Arcy, Julio M; Tran, Henry D; Stieg, Adam Z; Gimzewski, James K; Kaner, Richard B

    2012-05-21

    A procedure for depositing thin films of carbon nanostructures is described that overcomes the limitations typically associated with solution based methods. Transparent and conductively continuous carbon coatings can be grown on virtually any type of substrate within seconds. Interfacial surface tension gradients result in directional fluid flow and film spreading at the water/oil interface. Transparent films of carbon nanostructures are produced including aligned ropes of single-walled carbon nanotubes and assemblies of single sheets of chemically converted graphene and graphite oxide. Process scale-up, layer-by-layer deposition, and a simple method for coating non-activated hydrophobic surfaces are demonstrated.

  14. Surface modification of carbon post arrays by atomic layer deposition of ZnO film.

    PubMed

    Lee, Hyun Ae; Byun, Young-Chul; Singh, Umesh; Cho, Hyoung J; Kim, Hyoungsub

    2011-08-01

    The applicability of atomic layer deposition (ALD) process to the carbon microelectromechanical system technology was studied for a surface modification method of the carbon post electrodes. A conformal coating of the ALD-ZnO film was successfully demonstrated on the carbon post arrays which were fabricated by the traditional photolithography and subsequent two-step pyrolysis. A significant Zn diffusion into the underlying carbon posts was observed during the ALD process. The addition of a sputter-deposited ZnO interfacial layer efficiently blocked the Zn diffusion without altering the microstructure and surface morphology of the ALD-ZnO film.

  15. Determination of the origin of dissolved inorganic carbon in groundwater around a reclaimed landfill in Otwock using stable carbon isotopes

    SciTech Connect

    Porowska, Dorota

    2015-05-15

    Highlights: • Research showed the origin of DIC in the groundwater around a reclaimed landfill. • Carbon isotope was used to evaluate the contributions of carbon from different sources. • The leachate-contaminated water was isotopically distinct from the natural groundwater. • DIC in the natural groundwater comes from organic matter and dissolution of carbonates. • In the contaminated water, DIC comes from organic matter in the aquifer and landfill. - Abstract: Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC) in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ{sup 13}C{sub DIC}) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ{sup 13}C{sub DIC} values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4–54% of the DIC pool is derived from organic matter degradation and 96–46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20–53% of the DIC is derived from organic matter degradation of natural origin and 80–47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO{sub 2} (P CO{sub 2}) was generally above the atmospheric, hence atmospheric CO{sub 2} as a source of carbon in DIC pool was negligible in the

  16. Ultrathin diamond-like carbon films deposited by filtered carbon vacuum arcs

    SciTech Connect

    Anders, Andre; Fong, Walton; Kulkarni, Ashok; Ryan, Francis W.; Bhatia, C. Singh

    2001-07-13

    Ultrathin (< 5 nm) hard carbon films are of great interest to the magnetic storage industry as the areal density approaches 100 Gbit/in{sup 2}. These films are used as overcoats to protect the magnetic layers on disk media and the active elements of the read-write slider. Tetrahedral amorphous carbon films can be produced by filtered cathodic arc deposition, but the films will only be accepted by the storage industry only if the ''macroparticle'' issue has been solved. Better plasma filters have been developed over recent years. Emphasis is put on the promising twist filter system - a compact, open structure that operates with pulsed arcs and high magnetic field. Based on corrosion tests it is shown that the macroparticle reduction by the twist filter is satisfactory for this demanding application, while plasma throughput is very high. Ultrathin hard carbon films have been synthesized using S-filter and twist filter systems. Film properties such as hardness, elastic modulus, wear, and corrosion resistance have been tested.

  17. Friction and Wear of Ion-Beam-Deposited Diamondlike Carbon on Chemical-Vapor-Deposited, Fine-Grain Diamond

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Wu, Richard L. C.; Lanter, William C.

    1996-01-01

    Friction and wear behavior of ion-beam-deposited diamondlike carbon (DLC) films coated on chemical-vapor-deposited (CVD), fine-grain diamond coatings were examined in ultrahigh vacuum, dry nitrogen, and humid air environments. The DLC films were produced by the direct impact of an ion beam (composed of a 3:17 mixture of Ar and CH4) at ion energies of 1500 and 700 eV and an RF power of 99 W. Sliding friction experiments were conducted with hemispherical CVD diamond pins sliding on four different carbon-base coating systems: DLC films on CVD diamond; DLC films on silicon; as-deposited, fine-grain CVD diamond; and carbon-ion-implanted, fine-grain CVD diamond on silicon. Results indicate that in ultrahigh vacuum the ion-beam-deposited DLC films on fine-grain CVD diamond (similar to the ion-implanted CVD diamond) greatly decrease both the friction and wear of fine-grain CVD diamond films and provide solid lubrication. In dry nitrogen and in humid air, ion-beam-deposited DLC films on fine-grain CVD diamond films also had a low steady-state coefficient of friction and a low wear rate. These tribological performance benefits, coupled with a wider range of coating thicknesses, led to longer endurance life and improved wear resistance for the DLC deposited on fine-grain CVD diamond in comparison to the ion-implanted diamond films. Thus, DLC deposited on fine-grain CVD diamond films can be an effective wear-resistant, lubricating coating regardless of environment.

  18. Depositional history of upper Triassic carbonate platforms on Wrangellia terrane, western British Columbia, Canada

    SciTech Connect

    Desrochers, A.

    1989-03-01

    Upper Triassic (Karnian-Norian) limestones of the Quatsino Formation, Vancouver Island, and the Kunga Formation, Queen Charlotte Island, were deposited within a complex rifted island arc system, which was accreted to the western margin of North America as Wrangellia during the mid-Cretaceous. Carbonates sedimentation began after a transgressive event submerged the subaerially exposed Karmutsen volcanics. In both Vancouver and Queen Charlotte Islands, the lower part of the carbonate sequence records the widespread development of a shallow, subtidal platform composed mainly of two facies: open-platform deposits (bioturbated fossiliferous wackestones) and platform sand-shoal deposits (oolitic-bioclastic grainstones). This early depositional stage evolved gradually into a second stage characterized by the fragmentation of the platform and development of a carbonate bank/basin topography controlled by extensional tectonics within Wrangellia. The interior facies of these carbonate banks consist of cyclic subtidal lagoonal and tidal-flat limestones, each cycle commonly capped by a vadose diagenetic layer. The bank margin facies comprises exclusively high-energy, oolitic sandshoal deposits. The adjacent basin facies include (1) pelagic/hemipelagic limestones, (2) platform-derived and slope-derived carbonate breccia, and (3) proximal to distal carbonate turbidites. In both island systems, carbonate sedimentation ended abruptly when the isolated carbonate banks were drowned and covered by basinal clastics in response to rapid subsidence probably caused by tectonic activity within Wrangellia.

  19. N-type thermoelectric recycled carbon fibre sheet with electrochemically deposited Bi2Te3

    NASA Astrophysics Data System (ADS)

    Pang, E. J. X.; Pickering, S. J.; Chan, A.; Wong, K. H.; Lau, P. L.

    2012-09-01

    An N-type thermoelectric recycled carbon fibre sheet with bismuth telluride coating has been successfully synthesised through an electro-deposition technique. The Seebeck coefficient and electrical properties of the combined recycled carbon fibre sheet and bismuth telluride films are reported. Classification of the crystal structure, surface morphology and the elemental composition of the resulting deposits are methodically characterised by XRD, SEM and EDX. Cyclic voltammetry is also carried out in nitric acid solutions to investigate the right range of deposition potential. The synthesis N-type thermoelectric sheet has a highest attainable Seebeck coefficient of -54 μV K-1 and an electrical resistivity of 8.9×10-5 Ω m. The results show slight differences in morphologies and thermoelectric properties for the films deposited at varying deposition potential. The increase in thermoelectrical properties of the recycled carbon fibre is in line with the development of using coated recycled fibre for thermoelectrical applications.

  20. Fe stable isotope fractionation in modern and ancient hydrothermal Fe-Si deposits

    NASA Astrophysics Data System (ADS)

    Moeller, K.; Schoenberg, R.; Thorseth, I. H.; Øvreås, L.; Pedersen, R.

    2010-12-01

    Modern iron-silica deposits of small yellow to rust coloured mounds and chimney-like structures were found in a low-temperature venting area distal to a white smoker type hydrothermal vent site at the south-western part of the Mohns Ridge, North Atlantic. Individual stratified mm to cm thick laminated layers within these structures are largely composed of branching, twisted filaments resembling encrusted stalks of Fe-oxidising bacteria. DNA analyses have confirmed the presence of both Fe-oxidising (Mariprofundus ferrooxidans and other ζ-Proteobacteria) and Fe-reducing bacteria (Shewanellaceae). Similar morphologic features, such as several mm thick red hematite-rich laminae and micron-scale filamentous structures concentrated in discrete laminae, have also been found in Early Ordovician volcanogenic massive sulphide (VMS) hosted jasper deposits in the Løkken-Høydal area, Norway [1]. These filamentous structures are believed to be formed by Fe-oxidising bacteria similar to Mariprofundus ferrooxidans [2]. Here, we compare the Fe isotope composition of these two different types of Fe-Si deposits with the aim to gain further information about deposition mechanisms and the role of microorganisms in Fe redox cycling of deep-sea hydrothermal systems. Fe isotope compositions of the modern biogenic Fe-Si deposit vary between -2.09 and -0.66 ‰ in δ56Fe values, a range that is comparable to late Archaean to early Proterozoic banded iron formations. The ~490 Ma old Løkken jaspers show a similar variation, but with significantly higher δ56Fe values ranging from -0.39 to +0.89 ‰. The Fe isotopic composition of the Løkken jaspers clearly correlates with morphological features with the lowest δ56Fe values in layered and the highest ones in brecciform jaspers. Our data demonstrate that variations in Fe isotope compositions of the modern Fe-Si deposit cannot be explained by a single process, but rather reflect the full complexity of Fe redox cycling within deep

  1. Heat-stable phytases in transgenic wheat (Triticum aestivum L.): deposition pattern, thermostability, and phytate hydrolysis.

    PubMed

    Brinch-Pedersen, Henrik; Hatzack, Frank; Stöger, Eva; Arcalis, Elsa; Pontopidan, Katrine; Holm, Preben B

    2006-06-28

    The present paper addresses the question of thermotolerance of in planta synthesized heterologous enzymes using phytase as a model. Two individual transgenic wheat materials expressing an Aspergillus fumigatus phytase with a low denaturation temperature (62.5 degrees C) but a high refolding capacity, and a rationally designed consensus phytase engineered to a high denaturation temperature (89.3 degrees C), were evaluated. High levels of endosperm specific expression were ensured by the wheat high molecular weight glutenin 1DX5 promoter. Immunodetection at the light and electron microscopical level shows unequivocally that the heterologous phytase is deposited in the vacuole, albeit that the transformation constructs were designed for secretion to the apoplast. Evaluation of heat stability properties and kinetic properties unraveled that, under these deposition conditions, heat stability based on high unfolding temperature is superior to high refolding capacity and represents a realistic strategy for improving phosphate and mineral bioavailability in cereal-based feed and food.

  2. Stable isotopes of carbon and nitrogen in the study of organochlorine contaminants in albatrosses and petrels.

    PubMed

    Colabuono, Fernanda I; Barquete, Viviane; Taniguchi, Satie; Ryan, Peter G; Montone, Rosalinda C

    2014-06-15

    Carbon and nitrogen stable isotopes in albatrosses and petrels collected off southern Brazil were compared with concentrations of organochlorine contaminants (OCs). δ(13)C and δ(15)N values, as well as OCs concentrations, exhibited a high degree of variability among individuals and overlap among species. δ(13)C values reflected latitudinal differences among species, with lower values found in Wandering and Tristan Albatrosses and higher values found in Black-browed and Atlantic Yellow-nosed Albatrosses and White-chinned Petrels. Some relationships were found between OCs and stable isotopes, but in general a partial 'uncoupling' was observed between OCs concentrations and stable isotopes ratios (especially for δ(15)N). δ(13)C and δ(15)N values in Procellariiformes tissues during the non-breeding season appear to be a better indicator of foraging habitats than of trophic relationships, which may partially explain the high degree of variability between concentrations of OCs and stable isotopes ratios in birds with a diversified diet and wide foraging range.

  3. Investigations of Oxidation Protection Systems for Carbon-Carbon Composites Formed by Chemical Vapor Deposition and Plasma-Assisted Chemical Vapor Deposition Techniques

    DTIC Science & Technology

    1991-01-21

    the coating oxidizes to form a protective seal. ZrO2 may react with the SiO 2 film to form zirconium silicate, which offers reasonable oxidation...oxidation behavior of coated carbon-carbon (C-C) composites is studied. Silicon carbide and zirconium diboride ceramic coating are deposited on pack...cementation process were a weight percent mixture of silicon (Si), silicon carbide (SiC), zirconium carbide (ZrC), Boron (B), and Alumina (A1203). The

  4. A new designed π conjugated molecule for stable single walled carbon nanotube dispersion in aqueous medium.

    PubMed

    Nogueira, S L; Sahoo, S K; Jarrosson, T; Serein-Spirau, F; Lère-Porte, J-P; Moujaes, E A; Marletta, A; Santos, A P; Fantini, C; Furtado, C A; Silva, R A

    2016-02-15

    A molecule with a π conjugated backbone built from aromatic thiophene and dialkoxyphenylene units and substituted imidazolium groups (TPO) is designed to obtain ultra-stable single walled carbon nanotube (SWCNT) dispersion in aqueous medium. The proposed mechanism of non-covalent interaction is accompanied by individualization of SWCNT and comprises of dominant nondisruptive π-π and cation-π interaction between them and the TPO conjugated oligomer. The individualization of SWCNT and dispersibility and stability of the ultra-stable suspensions were estimated using high resolution transmission electron microscopy, UV-Visible-NIR absorption spectroscopy, Raman spectroscopy, photoluminescence and zeta potential measurement. Nuclear magnetic resonance data provides direct evidence toward possible cation-π interaction.

  5. Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

    SciTech Connect

    Kruzer, Helen W; Horita, Juske; Moran, James J; Tomkins, Bruce A; Janszen, Derek B; Carman, April

    2012-01-01

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.

  6. Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

    SciTech Connect

    Kreuzer, Helen W.; Horita, Juske; Moran, James J.; Tomkins, Bruce; Janszen, Derek B.; Carman, April J.

    2012-01-03

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.

  7. Stable superhydrophobic surface of hierarchical carbon nanotubes on Si micropillar arrays.

    PubMed

    He, Shaoqing; Wei, Jinquan; Wang, Haifan; Sun, Deshun; Yao, Zhaohui; Fu, Chengsong; Xu, Ruiqiao; Jia, Yi; Zhu, Hongwei; Wang, Kunlin; Wu, Dehai

    2013-10-07

    It is of great importance to construct a stable superhydrophobic surface with low sliding angle (SA) for various applications. We used hydrophobic carbon nanotubes (CNTs) to construct the superhydrophobic hierarchical architecture of CNTs on silicon micropillar array (CNTs/Si-μp), which have a large contact angle of 153° to 155° and an ultralow SA of 3° to 5°. Small water droplets with a volume larger than 0.3 μL can slide on the CNTs/Si-μp with a tilted angle of approximately 5°. The CNTs growing on planar Si wafer lose their superhydrophobic properties after exposing to tiny water droplets. However, the CNTs/Si-μp still show superhydrophobic properties even after wetting using tiny water droplets. The CNTs/Si-μp still have a hierarchical structure after wetting, resulting in a stable superhydrophobic surface.

  8. Preliminary Study: Application of Off-Axis ICOS to Determine Stable Carbon Isotope in Dissolved Inorganic Carbon

    NASA Astrophysics Data System (ADS)

    Kim, Y. T.; Lee, J. M.; Hwang, J. H.; Piao, J.; Woo, N. C.

    2015-12-01

    CO2 is one of the major causes for global climate change. Because stable carbon isotope ratio is used to trace carbon source, several analytical techniques likes IRMS (Isotope Ratio Mass Spectrometry) and LAS (Laser Absorption Spectrometry) were extensively used. Off-axis ICOS, a kind of LAS, has merits on long-term stability and field application, therefore it is widely being used in CCS (Carbon Capture and Storage) field. The aim of this study is to extend the application scope of OA-ICOS to determine dissolved inorganic carbon (DIC). Because OA-ICOS showed dependence of δ13C on CO2 concentration, data processing is required. We tested CO2 Carbon Isotope Analyzer (CCIA-36-EP, Los Gatos Research) with both reference gas (δ13C= -28.28‰) and aqueous solutions prepared by dissolving sodium bicarbonate standards (δ13C= -12.26‰ and +3.96‰). The differences of δ13C between reference and measurement values are plotted by CO2 concentrations, then compared. At first, we checked the similarity between our curve pattern for reference gas and Guillon's research (δ13C= -43.99‰) by other Analyzer. To analyze aqueous samples, more errors can be caused than gas analysis. The carbon isotope fractionation occurs during dissolving standard reagents and extracting DIC as CO2 gas form. This effect is mixed with CO2 concentration dependence effect, therefore the curve patterns are different with that for reference gas. Our experiments are done for various δ13C values. It could be an important point to use OA-ICOS to analyze DIC, too.

  9. Molecular marker and stable carbon isotope analyses of carbonaceous Ambassador uranium ores of Mulga Rock in Western Australia

    NASA Astrophysics Data System (ADS)

    Jaraula, C.; Schwark, L.; Moreau, X.; Grice, K.; Bagas, L.

    2013-12-01

    Mulga Rock is a multi-element deposit containing uranium hosted by Eocene peats and lignites deposited in inset valleys incised into Permian rocks of the Gunbarrel Basin and Precambrian rocks of the Yilgarn Craton and Albany-Fraser Orogen. Uranium readily adsorbs onto minerals or phytoclasts to form organo-uranyl complexes. This is important in pre-concentrating uranium in this relatively young ore deposit with rare uraninite [UO2] and coffinite [U(SiO4)1-x(OH)4x], more commonly amorphous and sub-micron uranium-bearing particulates. Organic geochemical and compound-specific stable carbon isotope analyses were conducted to identify possible associations of molecular markers with uranium accumulation and to recognize effect(s) of ionizing radiation on molecular markers. Samples were collected from the Ambassador deposit containing low (<200 ppm) to high (>2000 ppm) uranium concentrations. The bulk rock C/N ratios of 82 to 153, Rock-Eval pyrolysis yields of 316 to 577 mg hydrocarbon/g TOC (Hydrogen Index, HI) and 70 to 102 mg CO2/g TOC (Oxygen Index, OI) are consistent with a terrigenous and predominantly vascular plant OM source deposited in a complex shallow water system, ranging from lacustrine to deltaic, swampy wetland and even shallow lake settings as proposed by previous workers. Organic solvent extracts were separated into saturated hydrocarbon, aromatic hydrocarbon, ketone, and a combined free fatty acid and alcohol fraction. The molecular profiles appear to vary with uranium concentration. In samples with relatively low uranium concentrations, long-chain n-alkanes, alcohols and fatty acids derived from epicuticular plant waxes dominate. The n-alkane distributions (C27 to C31) reveal an odd/even preference (Carbon Preference Index, CPI=1.5) indicative of extant lipids. Average δ13C of -27 to -29 ‰ for long-chain n-alkanes is consistent with a predominant C3 plant source. Samples with relatively higher uranium concentrations contain mostly intermediate

  10. A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations.

    PubMed

    Archbold, Marie E; Redeker, Kelly R; Davis, Simon; Elliot, Trevor; Kalin, Robert M

    2005-01-01

    A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air (13)C/(12)C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl(2)F(2)) and CFC-113 (C(2)Cl(3)F(3)). Significant, but consistent, isotopic shifts of -27.5 per thousand to -25.6 per thousand do occur within the system for CFC-11 (CCl(3)F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (carbon isotope results similar to published values for (13)C/(12)C analysis of MeCl (-39.1 per thousand) and CFC-113 (-28.1 per thousand). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4 per thousand) and CFC-12 (-37.0 per thousand).

  11. Fatty acid and stable carbon isotope characterization of Camelina sativa oil: implications for authentication.

    PubMed

    Hrastar, Robert; Petrisic, Marinka G; Ogrinc, Nives; Kosir, Iztok Joze

    2009-01-28

    The importance of authenticity characterization is an increasing and pressing requirement for all foods. Vegetable oil is one of the most studied foods because of its nutritional and medicinal properties in a correct diet. In this study, a total of 53 Camelina sativa samples, from all known growing areas, were chemically and isotopically characterized. The fatty acid content of camelina oil was determined by gas chromatography (GC), and the ratios of stable carbon isotopes ((13)C/(12)C) of individual fatty acids and seed/bulk oil were determined by gas chromatography-combustion-stable isotope ratio mass spectrometry (GC/C/IRMS) and elemental analysis-stable isotope ratio mass spectrometry (IRMS). A total of 17 different fatty acids were detected by GC, with omega3 R-linolenic acid (C(18:3n3)) being the most abundant (29.7-40.0 wt %). Oleic acid (C(18:1n9)), linoleic acid (C(18:2n6)) and eicosenoic acid (C(20:1n9)) all belong to the second group of major fatty acids. The stable carbon isotopic values (delta(13)C) fell into a range typical for C(3) plants. The use of delta(13)C(18:2n6) vs delta(13)C(18:3n3) correlation could show cases where impurity or adulteration is suspected, whereas principal component analysis clearly separates oil samples from different continents. Preliminary results on the camelina oil authentication procedure provide a basis for the investigation of geographical origin and the further distinction between camelina and camelina refined or other, less expensive oils.

  12. Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

    NASA Technical Reports Server (NTRS)

    Rau, G. H.; Desmarais, David J.

    1985-01-01

    Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

  13. Method of preparing a dimensionally stable electrode for use in a molten carbonate fuel cell

    DOEpatents

    Swarr, T.E.; Wnuck, W.G.

    1986-01-29

    A method is disclosed for preparing a dimensionally stable electrode structure, particularly nickel-chromium anodes, for use in a molten carbonate fuel cell stack. A low-chromium to nickel alloy is provided and oxidized in a mildly oxidizing gas of sufficient oxidation potential to oxidize chromium in the alloy structure. Typically, a steam/H/sub 2/ gas mixture in a ratio of about 100/1 and at a temperature below 800/sup 0/C is used as the oxidizing medium. This method permits the use of less than 5 wt % chromium in nickel alloy electrodes while obtaining good resistance to creep in the electrodes of a fuel cell stack.

  14. Using variances in hydrocarbon concentration and carbon stable isotope to determine the important influence of irrigated water on petroleum accumulation in surface soil.

    PubMed

    Zhang, Juan; Wang, Renqing; Yang, Juncheng; Hou, Hong; Du, Xiaoming; Dai, Jiulan

    2013-05-01

    Hunpu is a wastewater-irrigated area southwest of Shenyang. To evaluate petroleum contamination and identify its sources at the area, the aliphatic hydrocarbons and compound-specific carbon stable isotopes of n-alkanes in the soil, irrigation water, and atmospheric deposition were analyzed. The analyses of hydrocarbon concentrations and geochemical characteristics reveal that the water is moderately contaminated by degraded heavy oil. According to the isotope analysis, inputs of modern C3 plants and degraded petroleum are present in the water, air, and soil. The similarities and dissimilarities among the water, air, and soil samples were determined by concentration, isotope, and multivariate statistical analyses. Hydrocarbons from various sources, as well as the water/atmospheric deposition samples, are more effectively differentiated through principal component analysis of carbon stable isotope ratios (δ(13)C) relative to hydrocarbon concentrations. Redundancy analysis indicates that 57.1 % of the variance in the δ(13)C of the soil can be explained by the δ(13)C of both the water and air, and 35.5 % of the variance in the hydrocarbon concentrations of the soil can be explained by hydrocarbon concentrations of both the water and the air. The δ(13)C in the atmospheric deposition accounts for 28.2 % of the δ(13)C variance in the soil, which is considerably higher than the variance in hydrocarbon concentrations of the soil explained by hydrocarbon concentrations of the atmospheric deposition (7.7 %). In contrast to δ(13)C analysis, the analysis of hydrocarbon concentrations underestimates the effect of petroleum contamination in the irrigated water and air on the surface soil. Overall, the irrigated water exerts a larger effect on the surface soil than does the atmospheric deposition.

  15. Hall measurements on carbon nanotube paper modified with electroless deposited platinum.

    PubMed

    Petrik, Leslie; Ndungu, Patrick; Iwuoha, Emmanuel

    2009-09-18

    Carbon nanotube paper, sometimes referred to as bucky paper, is a random arrangement of carbon nanotubes meshed into a single robust structure, which can be manipulated with relative ease. Multi-walled carbon nanotubes were used to make the nanotube paper, and were subsequently modified with platinum using an electroless deposition method based on substrate enhanced electroless deposition. This involves the use of a sacrificial metal substrate that undergoes electro-dissolution while the platinum metal deposits out of solution onto the nanotube paper via a galvanic displacement reaction. The samples were characterized using SEM/EDS, and Hall-effect measurements. The SEM/EDS analysis clearly revealed deposits of platinum (Pt) distributed over the nanotube paper surface, and the qualitative elemental analysis revealed co-deposition of other elements from the metal substrates used. When stainless steel was used as sacrificial metal a large degree of Pt contamination with various other metals was observed. Whereas when pure sacrificial metals were used bimetallic Pt clusters resulted. The co-deposition of a bimetallic system upon carbon nanotubes was a function of the metal type and the time of exposure. Hall-effect measurements revealed some interesting fluctuations in sheet carrier density and the dominant carrier switched from N- to P-type when Pt was deposited onto the nanotube paper. Perspectives on the use of the nanotube paper as a replacement to traditional carbon cloth in water electrolysis systems are also discussed.

  16. Stable single helical C- and I-chains inside single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Yao, Z.; Liu, C. J.; Li, Y.; Jing, X. D.; Meng, F. S.; Zheng, S. P.; Zhao, X.; Li, J. H.; Qiu, Z. Y.; Yuan, Q.; Wang, W. X.; Bi, L.; Liu, H.; Zhang, Y. P.; Liu, B. B.

    2016-09-01

    The helicity of stable single helical carbon chains and iodine chains inside single-walled carbon nanotubes (SWCNTs) is studied by calculating the systematic van der Waals interaction energy. The results show that the optimal helical radius increases linearly with increasing tube radius, which produces a constant separation between the chain structure and the tube wall. The helical angle exhibits a ladder-like decrease with increasing tube radius, indicating that a large tube can produce a small helicity in the helical structures. Project supported by the National Basic Research Program of China (Grant No. 2011CB808200), the National Natural Science Foundation of China (Grant Nos. 11504150 and 51320105007), and the Cheung Kong Scholars Program of China.

  17. Stable configurations of C20 and C28 encapsulated in single wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zhou, L.; Pan, Z. Y.; Wang, Y. X.; Zhu, J.; Liu, T. J.; Jiang, X. M.

    2006-04-01

    The stable configurations of small fullerenes (C20 and C28) encapsulated inside single wall carbon nanotubes (SWNTs) of different diameters were investigated by molecular dynamics simulations. The interactions between carbon atoms were described by a combination of the many-body Brenner potential with the Lennard-Jones (LJ) potential. We observed that the filling of small fullerenes into nanotubes with diameters larger than 10.85 Å ((8, 8) SWNT) is an exothermic process. During the annealing process the fullerenes arrange themselves into complex phases, which may be one-(chain), two-(zigzag) or three-dimensional, depending on the tube diameter. This tube size dependence is very similar to that of C60, which has been experimentally observed. A comparison with the prediction of the hard-sphere model also finds a satisfactory level of consistency, indicating the dense packing nature of fullerene configurations in SWNTs.

  18. Depositional model for carbonate-evaporite cyclicity: Middle Pennsylvanian of Paradox basin

    SciTech Connect

    Kendall, A.C.

    1987-05-01

    The Paradox basin is a classic area for the study of relations between carbonates and evaporites. Previous depositional models assume carbonates and evaporites are coeval, implying that the evaporites were deep water deposits. Stratigraphic relationships are, however, complicated by previously unrecognized salt dissolution. Restoration of the missing salts indicates that evaporites entirely postdate marine carbonates in each cycle. Anhydrites and silty dolomites that succeed halites are reinterpreted as shallow hypersaline to subaerial deposits. These playa-like sediments are abruptly overlain by organic-rich shales that represent anoxic and the deepest-water deposits in the sequence. Paradox basin salts and succeeding playa deposits formed in a deep but desiccated basin. Sea level rises drowned the formerly exposed basin rims, causing sudden complete floodings of the basin and the abrupt contacts between playa deposits and deep-water shales. The shale-carbonate-evaporite sequences that form lower parts of cycles resulted from sea level falls. These ultimately exposed basin rims, isolating the basin, and allowed evaporative draw down and the deposition of basin-central evaporites. In contrast, the halite-anhydrite-silty dolomite sequences of the upper parts of cycles arose when sediment aggradation caused expansion of the evaporite depositional area onto basin flanks. There brine reflux became more significant. This reduced residence times of brines in the basin so that, progressively, salinities decreased and only less-saline sediments were able to persist in the playa environment. Cycles end (or begin) when renewed sea level rises drowned the basin-central playas.

  19. A free-air system for long-term stable carbon isotope labeling of adult forest trees

    EPA Science Inventory

    Stable carbon (C) isotopes, in particular employed in labeling experiments, are an ideal tool to broaden our understanding of C dynamics in trees and forest ecosystems. Here, we present a free-air exposure system, named isoFACE, designed for long-term stable C isotope labeling in...

  20. Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff

    USGS Publications Warehouse

    Babiarz, C.L.; Hurley, J.P.; Krabbenhoft, D.P.; Gilmour, C.; Branfireun, B.A.

    2003-01-01

    Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (HgT), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 ??m). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms. ?? 2002 Elsevier Science B.V. All rights reserved.

  1. Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff.

    PubMed

    Babiarz, Christopher L; Hurley, James P; Krabbenhoft, David P; Gilmour, Cynthia; Branfireun, Brian A

    2003-03-20

    Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (Hg(T)), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 microm). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms.

  2. Deuterium Retention in the Co-Deposition Carbon Layers Deposited by Radio-Frequency Magnetron Sputtering in D2 Atmosphere

    NASA Astrophysics Data System (ADS)

    Zhang, Wei-Yuan; Shi, Li-Qun; Zhang, Bin; Hu, Jian-Sheng

    2014-05-01

    Carbon is deposited on C and Si substrates by rf magnetron plasma sputtering in a D2 atmosphere. The deposited layers are examined with ion beam analysis and thermal desorption spectroscopy (TDS). The growth rates of the layers deposited on Si decrease with increasing substrate temperature, while increase significantly with the increase of D2 pressure. Meanwhile, the deuterium concentrations in the layers deposited on the Si substrates decrease from 30% to 2% and from 31% to 1% on the C substrates, respectively, when the substrate temperature varies from 350K to 900 K. Similarly, the D concentration in the layer on the Si substrates increases from 3.4% to 47%, and from 8% to 35% on the C substrates when the D2 pressure increases from 0.3Pa to 8.0Pa. D desorption characterized by TDS is mainly in the forms of D2, HD, HDO, CD4, and C2D4, and a similar release peak occurs at 645 K. The release peak of D2 molecules at 960K can be attributed to the escaped gas from the thin co-deposited deuterium-rich carbon layer in the form of C-D bonding.

  3. Stable Te isotope fractionation in tellurium-bearing minerals from precious metal hydrothermal ore deposits

    NASA Astrophysics Data System (ADS)

    Fornadel, Andrew P.; Spry, Paul G.; Haghnegahdar, Mojhgan A.; Schauble, Edwin A.; Jackson, Simon E.; Mills, Stuart J.

    2017-04-01

    The tellurium isotope compositions of naturally-occurring tellurides, native tellurium, and tellurites were measured by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) and compared to theoretical values for equilibrium mass-dependent isotopic fractionation of representative Te-bearing species estimated with first-principles thermodynamic calculations. Calculated fractionation models suggest that 130/125Te fractionations as large as 4‰ occur at 100 °C between coexisting tellurates (Te VI) and tellurides (Te -II) or or native tellurium Te(0), and smaller, typically <1‰, fractionations occur between coexisting Te(-I) or Te(-II) (Au,Ag)Te2 minerals (i.e., calaverite, krennerite) and (Au,Ag)2Te minerals (i.e., petzite, hessite). In general, heavyTe/lightTe is predicted to be higher for more oxidized species, and lower for reduced species. Tellurides in the system Au-Ag-Te and native tellurium analyzed in this study have values of δ130/125Te = -1.54‰ to 0.44‰ and δ130/125Te = -0.74‰ to 0.16‰, respectively, whereas those for tellurites (tellurite, paratellurite, emmonsite and poughite) range from δ130/125Te = -1.58‰ to 0.59‰. Thus, the isotopic composition for both oxidized and reduced species are broadly coincident. Calculations of per mil isotopic variation per amu for each sample suggest that mass-dependent processes are responsible for fractionation. In one sample of coexisting primary native tellurium and secondary emmonsite, δ130/125Te compositions were identical. The coincidence of δ130/125Te between all oxidized and reduced species in this study and the apparent lack of isotopic fractionation between native tellurium and emmonsite in one sample suggest that oxidation processes cause little to no fractionation. Because Te is predominantly transported as an oxidized aqueous phase or as a reduced vapor phase under hydrothermal conditions, either a reduction of oxidized Te in hydrothermal liquids or deposition of Te from a

  4. Rapid synthesis of inherently robust and stable superhydrophobic carbon soot coatings

    NASA Astrophysics Data System (ADS)

    Esmeryan, Karekin D.; Castano, Carlos E.; Bressler, Ashton H.; Abolghasemibizaki, Mehran; Mohammadi, Reza

    2016-04-01

    The fabrication of superhydrophobic coatings using a candle flame or rapeseed oil has become very attractive as a novel approach for synthesis of water repellent surfaces. Here, we report an improved, simplified and time-efficient method for the preparation of robust superhydrophobic carbon soot that does not require any additional stabilizers or chemical treatment. The soot's inherent stabilization is achieved using a specially-designed cone-shaped aluminum chimney, mounted over an ignited paper-based wick immersed in a rapeseed oil. Such configuration decreases the level of oxygen during the process of combustion; altering the ratio of chemical bonds in the soot. As a result, the fractal-like network of the carbon nanoparticles is converted into dense and fused carbon chains, rigidly coupled to the substrate surface. The modified carbon coating shows thermal sustainability and retains superhydrophobicity up to ∼300 °C. Furthermore, it demonstrates a low contact angle hysteresis of 0.7-1.2° accompanied by enhanced surface adhesion and mechanical durability under random water flows. In addition, the soot's deposition rate of ∼1.5 μm/s reduces the exposure time of the substrate to heat and consequently minimizes the thermal effects, allowing the creation of superhydrophobic coatings on materials with low thermal stability (e.g. wood or polyethylene).

  5. Stable isotope analysis of dissolved carbon species of Hot Lake, WA

    NASA Astrophysics Data System (ADS)

    Courtney, S.; Moran, J.; Cory, A. B.; Lindemann, S. R.; Fredrickson, J.

    2013-12-01

    Hot Lake is a hypersaline, meromictic lake in north-central Washington. The lake is epsomitic, with seasonably-variable salinity (.2 to 2 M magnesium sulfate) and produces carbonates and salt precipitates. The maximum depth of the lake is around 2.5 m, and below a thermocline there is intense solar heat retention in the monolimnion, often exceeding 50°C. Despite these extreme and variable conditions, a microbial mat of up to 1.5 cm thick thrives annually in Hot Lake. The mat is widespread throughout the lake at water depths (during our experiments) ranging from 60cm-140cm. It is comprised of a variety of cyanobacteria along with other autotrophic and heterotrophic bacteria. These populations are visibly stratified with four consistent laminae displaying differences in bacterial pigmentation. Many of the layers contain carbonate species, but the full relationship between the mat and the carbonate crystallization is not known. We are studying the microbial interactions and carbon cycling of the mat communities, using stable isotope analysis of the mat and the lake water, both in situ and ex situ. We are exploring the incorporation and movement of carbon in the mat, spatially and temporally, to understand the fixation mechanisms and metabolic processes at play in this environment. This was done primarily using stable isotope ratio mass spectrometry. The focus of this work is on the study and measurement of dissolved organic and inorganic carbon using a GasBench and IRMS setup, following methods adapted from Lang et al. (2012). To account for the unique chemistry of Hot Lake, trials on the effects of oxidation conditions and salinity were done on lab-synthesized samples to compare to Hot Lake results. The majority of lake water analyses were done in conjunction with a stable isotope probing (SIP) experiment, completed during two 24-hour periods at Hot Lake in June and July of 2013. The SIP experiments included ex situ incubations (in separate glass containers on the

  6. Use of Stable Isotopes to Investigate Keratin Deposition in the Claw Tips of Ducks

    PubMed Central

    Hopkins, John B.; Cutting, Kyle A.; Warren, Jeffrey M.

    2013-01-01

    Stable isotopes derived from the claws of birds could be used to determine the migratory origins of birds if the time periods represented in excised sections of claws were known. We investigated new keratin growth in the claws of adult female Lesser Scaup (Aythya affinis) by estimating the equilibration rates of stable isotopes (δ13C, δ15N, and δ2H) from the breeding grounds into 1 mm claw tips. We sampled birds on their breeding ground through time and found that it took approximately 3–3.5 months for isotope values in most claw tips to equilibrate to isotope values that reflected those present in the environment on their breeding grounds. Results from this study suggest that isotopes equilibrate slowly into claw tips of Lesser Scaup, suggesting isotopes could potentially be used to determine the wintering grounds of birds. We suggest using controlled feeding experiments or longitudinal field investigations to understand claw growth and isotopic equilibration in claw tips. Such information would be valuable in ascertaining whether claw tips can be used in future studies to identify the migratory origins of birds. PMID:24282563

  7. Superior Stable and Long Life Sodium Metal Anodes Achieved by Atomic Layer Deposition.

    PubMed

    Zhao, Yang; Goncharova, Lyudmila V; Lushington, Andrew; Sun, Qian; Yadegari, Hossein; Wang, Biqiong; Xiao, Wei; Li, Ruying; Sun, Xueliang

    2017-03-03

    Na-metal batteries are considered as the promising alternative candidate for Li-ion battery beneficial from the wide availability and low cost of sodium, high theoretical specific capacity, and high energy density based on the plating/stripping processes and lowest electrochemical potential. For Na-metal batteries, the crucial problem on metallic Na is one of the biggest challenges. Mossy or dendritic growth of Na occurs in the repetitive Na stripping/plating process with an unstable solid electrolyte interphase layer of nonuniform ionic flux, which can not only lead to the low Coulombic efficiency, but also can create short circuit risks, resulting in possible burning or explosion. In this communication, the atomic layer deposition of Al2 O3 coating is first demonstrated for the protection of metallic Na anode for Na-metal batteries. By protecting Na foil with ultrathin Al2 O3 layer, the dendrites and mossy Na formation have been effectively suppressed and lifetime has been significantly improved. Furthermore, the thickness of protective layer has been further optimized with 25 cycles of Al2 O3 layer presenting the best performance over 500 cycles. The novel design of atomic layer deposition protected metal Na anode may bring in new opportunities to the realization of the next-generation high energy-density Na metal batteries.

  8. Evaluating North Sea carbon sources using radiogenic (224Ra and 228Ra) and stable carbon isotope (DI13C) tracers

    NASA Astrophysics Data System (ADS)

    Burt, William; Thomas, Helmuth; Hagens, Mathilde; Brenner, Heiko; Paetsch, Johannes; Clargo, Nikki

    2015-04-01

    In the North Sea, much uncertainty still exists regarding the role of boundary fluxes (e.g. benthic input from sediments or lateral inputs from the coastline) in the overall biogeochemical cycling of the system. The stable carbon isotope signature of dissolved inorganic carbon (δ13C-DIC) is a common tool for following transformations of carbon in the water column and identifying carbon sources and sinks. Here, analyses of the first basin-wide observations of δ13C-DIC reveal that a balance between biological production and respiration, as well as a freshwater input near the European continental coast, predominantly control surface distributions in the North Sea. A strong relationship between the biological component of DIC (DICbio) and δ13C-DIC is then used to quantify the metabolic DIC flux associated with changes in the carbon isotopic signature. Correlations are also found between δ13C-DIC and naturally-occurring Radium isotopes (224Ra and 228Ra), which have well-identified sources from the seafloor and coastal boundaries. The relationship between δ13C-DIC and the longer-lived 228Ra isotope (half-life = 5.8 years) is used to derive a metabolic DIC flux from the European continental coastline. 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (TA) compared to the more conventional use of salinity as a tracer. Coastal alkalinity inputs are calculated using relationships with 228Ra, and ratios of DIC and TA suggest denitrification as the main metabolic pathway for the formation of these coastal inputs. Finally, coastal TA inputs are translated into inputs of protons to quantify their impact on the buffering capacity of the Southern North Sea.

  9. Effects of nitrogen deposition on carbon sequestration in Chinese fir forest ecosystems.

    PubMed

    Wei, Xiaohua; Blanco, Juan A; Jiang, Hong; Kimmins, J P Hamish

    2012-02-01

    Nitrogen deposition and its ecological effects on forest ecosystems have received global attention. We used the ecosystem model FORECAST to assess the effects of nitrogen deposition on carbon sequestration in Chinese fir planted forests in SE China. This topic is important as China is intensifying its reforestation efforts to increase forest carbon sequestration for combating climate change impacts, using Chinese fir as the most important plantation species. A series of scenarios including seven N deposition levels (1, 5, 10, 20, 30, 40 and 50kg ha(-1)y(-1)), three management regime (rotation lengths of 15, 30 and 50 years) and two site qualities (nutrient poor and fertile sites) were defined for the simulations. Our results showed that N deposition increased carbon sequestration in Chinese fir forests, but the efficiency of the increasing effect is reduced as N deposition levels increase. When N deposition levels exceeded 20-30kg ha(-1)y(-1), the incremental effects of N deposition on forest C pools were marginal. This suggests that N deposition levels above 20-30kg ha(-1)y(-1) could lead to N saturation in Chinese fir forest soils. Any additional amounts of N input from deposition would likely be leached out. Total above-ground C was more sensitive to N deposition than to rotation length and site quality. It was also estimated that the contributions of N deposition to C sequestration in all Chinese fir forests in South-East China are 7.4×10(6)MgCy(-1) under the current N deposition levels (5 to 10kg ha(-1)y(-1)) and could reach up to 16×10(6)MgCy(-1) if N deposition continues increasing and reaches levels of 7.5 to 15kg N ha(-1)y(-1).

  10. Assessing the paleoenvironmental potential of Pliocene to Holocene tufa deposits along the Ghaap Plateau escarpment (South Africa) using stable isotopes

    NASA Astrophysics Data System (ADS)

    Doran, Taylor Louise; Herries, Andy I. R.; Hopley, Philip J.; Sombroek, Hank; Hellstrom, John; Hodge, Ed; Kuhn, Brian F.

    2015-07-01

    The tufa deposits of the Ghaap Plateau escarpment provide a rich, yet minimally explored, geological archive of climate and environmental history coincident with hominin evolution in South Africa. This study examines the sedimentary and geochemical records of ancient and modern tufas from Buxton-Norlim Limeworks, Groot Kloof, and Gorrokop, to assess the potential of these sediments for providing reliable chronologies of high-resolution, paleoenvironmental information. Chronometric dating demonstrates that tufa formation has occurred from at least the terminal Pliocene through to the modern day. The stable isotope records show a trend toward higher, more variable δ18O and δ13C values with decreasing age from the end of the Pliocene onwards. The long-term increase in δ18O values corresponds to increasingly arid conditions, while increasing δ13C values reflect the changing proportion of C3/C4 vegetation in the local environment. Analysis of the Thabaseek Tufa, in particular, provides valuable evidence for reconstructing the depositional and chronological context of the enigmatic Taung Child (Australopithecus africanus). Collectively, the results of the present study demonstrate the potential of these deposits for developing high-precision records of climate change and, ultimately, for understanding the causal processes relating climate and hominin evolution.

  11. HF treatment effect for carbon deposition on silicon (111) by DC sputtering technique

    SciTech Connect

    Aji, A. S. Darma, Y.

    2014-03-24

    Surface modifications of Si (111) substrate by HF solution for thin film carbon deposition have been systematically studied. Thin film carbon on Si (111) has been deposited using DC Unbalanced Magnetron Sputtering with carbon pellet doped by 5% Fe as the target. EDAX characterization confirmed that the carbon fraction on Si substrate much higher by dipping a clean Si substrate by HF solution before sputtering process in comparison with carbon fraction on Si substrate just after conventional RCA. Moreover, SEM and AFM images show the uniform thin film carbon on Si with HF treatment, in contrast to the Si without HF solution treatment. These experimental results suggest that HF treatment of Si surface provide Si-H bonds on top Si surface that useful to enhance the carbon deposition during sputtering process. Furthermore, we investigate the thermal stability of thin film carbon on Si by thermal annealing process up to 900 °C. Atomic arrangements during annealing process were characterized by Raman spectroscopy. Raman spectra indicate that thin film carbon on Si is remaining unchanged until 600 °C and carbon atoms start to diffuse toward Si substrate after annealing at 900 °C.

  12. Plasma-deposited amorphous hydrogenated carbon films and their tribological properties

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; Pouch, John J.; Alterovitz, Samuel A.

    1989-01-01

    Recent work on the properties of diamondlike carbon films and their dependence on preparation conditions are reviewed. The results of the study indicate that plasma deposition enables one to deposit a variety of amorphous hydrogenated carbon (a-C:H ) films exhibiting more diamondlike behavior to more graphitic behavior. The plasma-deposited a-C:H can be effectively used as hard, wear-resistant, and protective lubricating films on ceramic materials such as Si(sub 3)N(sub 4) under a variety of environmental conditions such as moist air, dry nitrogrn, and vacuum.

  13. Chemical vapor-deposited carbon nanofibers on carbon fabric for supercapacitor electrode applications

    PubMed Central

    2012-01-01

    Entangled carbon nanofibers (CNFs) were synthesized on a flexible carbon fabric (CF) via water-assisted chemical vapor deposition at 800°C at atmospheric pressure utilizing iron (Fe) nanoparticles as catalysts, ethylene (C2H4) as the precursor gas, and argon (Ar) and hydrogen (H2) as the carrier gases. Scanning electron microscopy, transmission electron microscopy, and electron dispersive spectroscopy were employed to characterize the morphology and structure of the CNFs. It has been found that the catalyst (Fe) thickness affected the morphology of the CNFs on the CF, resulting in different capacitive behaviors of the CNF/CF electrodes. Two different Fe thicknesses (5 and 10 nm) were studied. The capacitance behaviors of the CNF/CF electrodes were evaluated by cyclic voltammetry measurements. The highest specific capacitance, approximately 140 F g−1, has been obtained in the electrode grown with the 5-nm thickness of Fe. Samples with both Fe thicknesses showed good cycling performance over 2,000 cycles. PMID:23181897

  14. STABLE CARBON ISOTOPE EVIDENCE FOR COUPLING BETWEEN SEDIMENTARY BACTERIA AND SEAGRASSES IN A SUB-TROPICAL LAGOON

    EPA Science Inventory

    We measured stable carbon isotope ratios (d13C) in phospholipid fatty acids (PLFAs) to identify the primary carbon source utilized by sedimentary bacteria in Lower Laguna Madre, Texas, which is a seagrass dominated lagoon. Comparisons were made between three differing habitat ty...

  15. Stable carbon isotopic evidence for methane oxidation in plumes above Hydrate Ridge, Cascadia Oregon Margin

    NASA Astrophysics Data System (ADS)

    Grant, Nicholas J.; Whiticar, Michael J.

    2002-12-01

    The transport and consumption of methane in the water column in the vicinity of the cold seeps of Hydrate Ridge on the Cascadia Oregon Margin were characterized using measurements of the stable carbon isotope composition of methane. The δ13C-CH4 values measured in the water column ranged from approximately -65 to -16‰, PDB. The combination of measured methane concentration data and the stable carbon isotope values from the same depths support the hypothesis of biogenically produced methane which enters the water column from dissolving bubbles released from cold seepages, likely as a consequence of destabilized methane hydrate (δ13C-CH4 = -65‰, PDB). Kinetic fractionation factors, α, associated with aerobic bacterial methane oxidation in the water column were calculated using a Rayleigh distillation equation applied to a subset of the data. Fractionation factors ranged from 1.002 to 1.013 (mean = 1.008) and were in the lower end of the range of those reported in the literature, a result likely due to the influence of temperature and mixing in plume waters. The fraction of methane remaining after oxidation calculated using the same Rayleigh model approach suggests that the aerobic oxidation of methane in the water column over Hydrate Ridge is nearly quantitative.

  16. Trophic discrimination factors of stable carbon and nitrogen isotopes in hair of corn fed wild boar.

    PubMed

    Holá, Michaela; Ježek, Miloš; Kušta, Tomáš; Košatová, Michaela

    2015-01-01

    Stable isotope measurements are increasingly being used to gain insights into the nutritional ecology of many wildlife species and their role in ecosystem structure and function. Such studies require estimations of trophic discrimination factors (i.e. differences in the isotopic ratio between the consumer and its diet). Although trophic discrimination factors are tissue- and species-specific, researchers often rely on generalized, and fixed trophic discrimination factors that have not been experimentally derived. In this experimental study, captive wild boar (Sus scrofa) were fed a controlled diet of corn (Zea mays), a popular and increasingly dominant food source for wild boar in the Czech Republic and elsewhere in Europe, and trophic discrimination factors for stable carbon (Δ13C) and nitrogen (Δ15N) isotopes were determined from hair samples. The mean Δ13C and Δ15N in wild boar hair were -2.3‰ and +3.5‰, respectively. Also, in order to facilitate future derivations of isotopic measurements along wild boar hair, we calculated the average hair growth rate to be 1.1 mm d(-1). Our results serve as a baseline for interpreting isotopic patterns of free-ranging wild boar in current European agricultural landscapes. However, future research is needed in order to provide a broader understanding of the processes underlying the variation in trophic discrimination factors of carbon and nitrogen across of variety of diet types.

  17. Trophic Discrimination Factors of Stable Carbon and Nitrogen Isotopes in Hair of Corn Fed Wild Boar

    PubMed Central

    Holá, Michaela; Ježek, Miloš; Kušta, Tomáš; Košatová, Michaela

    2015-01-01

    Stable isotope measurements are increasingly being used to gain insights into the nutritional ecology of many wildlife species and their role in ecosystem structure and function. Such studies require estimations of trophic discrimination factors (i.e. differences in the isotopic ratio between the consumer and its diet). Although trophic discrimination factors are tissue- and species- specific, researchers often rely on generalized, and fixed trophic discrimination factors that have not been experimentally derived. In this experimental study, captive wild boar (Sus scrofa) were fed a controlled diet of corn (Zea mays), a popular and increasingly dominant food source for wild boar in the Czech Republic and elsewhere in Europe, and trophic discrimination factors for stable carbon (Δ13C) and nitrogen (Δ15N) isotopes were determined from hair samples. The mean Δ13C and Δ15N in wild boar hair were –2.3 ‰ and +3.5 ‰, respectively. Also, in order to facilitate future derivations of isotopic measurements along wild boar hair, we calculated the average hair growth rate to be 1.1 mm d-1. Our results serve as a baseline for interpreting isotopic patterns of free-ranging wild boar in current European agricultural landscapes. However, future research is needed in order to provide a broader understanding of the processes underlying the variation in trophic discrimination factors of carbon and nitrogen across of variety of diet types. PMID:25915400

  18. Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

    NASA Astrophysics Data System (ADS)

    Wintel, J.; Hösen, E.; Koppmann, R.; Krebsbach, M.

    2013-04-01

    Measurements of stable carbon isotope ratios in VOC are a powerful tool to identify sources or to track both dynamical and chemical processes. During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer and the lower free troposphere over south-west Germany. These samples were analysed with respect to VOC mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer. In this study we present the results for toluene, one of the major anthropogenic pollutants. In the boundary layer we observed rather fresh emissions mixing into the background and derived a toluene source isotope ratio of δ13C = -28.2 ± 0.5 ‰. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We estimated the photochemical age of toluene in the atmosphere in two different ways (using isotope ratios and mixing ratios, respectively). The results differ strongly in the planetary boundary layer, probably due to mixing processes, but are compatible with each other in the free troposphere.

  19. Solution Deposition Methods for Carbon Nanotube Field-Effect Transistors

    DTIC Science & Technology

    2009-06-01

    solution prior to spin - coating . A comparison of the results for each deposition method will help to determine which conditions are useful for producing CNT devices for chemical sensing and electronic applications.

  20. Method of depositing multi-layer carbon-based coatings for field emission

    DOEpatents

    Sullivan, John P.; Friedmann, Thomas A.

    1999-01-01

    A novel field emitter device for cold cathode field emission applications, comprising a multi-layer resistive carbon film. The multi-layered film of the present invention is comprised of at least two layers of a resistive carbon material, preferably amorphous-tetrahedrally coordinated carbon, such that the resistivities of adjacent layers differ. For electron emission from the surface, the preferred structure comprises a top layer having a lower resistivity than the bottom layer. For edge emitting structures, the preferred structure of the film comprises a plurality of carbon layers, wherein adjacent layers have different resistivities. Through selection of deposition conditions, including the energy of the depositing carbon species, the presence or absence of certain elements such as H, N, inert gases or boron, carbon layers having desired resistivities can be produced. Field emitters made according the present invention display improved electron emission characteristics in comparison to conventional field emitter materials.

  1. Method of depositing multi-layer carbon-based coatings for field emission

    DOEpatents

    Sullivan, J.P.; Friedmann, T.A.

    1999-08-10

    A novel field emitter device is disclosed for cold cathode field emission applications, comprising a multi-layer resistive carbon film. The multi-layered film of the present invention is comprised of at least two layers of a resistive carbon material, preferably amorphous-tetrahedrally coordinated carbon, such that the resistivities of adjacent layers differ. For electron emission from the surface, the preferred structure comprises a top layer having a lower resistivity than the bottom layer. For edge emitting structures, the preferred structure of the film comprises a plurality of carbon layers, wherein adjacent layers have different resistivities. Through selection of deposition conditions, including the energy of the depositing carbon species, the presence or absence of certain elements such as H, N, inert gases or boron, carbon layers having desired resistivities can be produced. Field emitters made according the present invention display improved electron emission characteristics in comparison to conventional field emitter materials. 8 figs.

  2. More stable hybrid organic solar cells deposited on amorphous Si electron transfer layer

    SciTech Connect

    Samiee, Mehran; Modtland, Brian; Dalal, Vikram L.; Aidarkhanov, Damir

    2014-05-26

    We report on defect densities, performance, and stability of organic/inorganic hybrid solar cells produced using n-doped inorganic amorphous silicon-carbide layers as the electron transport layer (ETL). The organic material was poly-3-hexyl-thiophene (P3HT) and heterojunction was formed using phenyl-C{sub 71}-Butyric-Acid-Methyl Ester (PCBM). For comparison, inverted solar cells fabricated using Cs{sub 2}CO{sub 3} as ETL were fabricated. Defect densities and subgap quantum efficiency curves were found to be nearly identical for both types of cells. The cells were subjected to 2xsun illumination and it was found that the cells produced using doped a-Si as ETL were much more stable than the cells produced using Cs{sub 2}CO{sub 3}.

  3. More stable hybrid organic solar cells deposited on amorphous Si electron transfer layer

    NASA Astrophysics Data System (ADS)

    Samiee, Mehran; Modtland, Brian; Aidarkhanov, Damir; Dalal, Vikram L.

    2014-05-01

    We report on defect densities, performance, and stability of organic/inorganic hybrid solar cells produced using n-doped inorganic amorphous silicon-carbide layers as the electron transport layer (ETL). The organic material was poly-3-hexyl-thiophene (P3HT) and heterojunction was formed using phenyl-C71-Butyric-Acid-Methyl Ester (PCBM). For comparison, inverted solar cells fabricated using Cs2CO3 as ETL were fabricated. Defect densities and subgap quantum efficiency curves were found to be nearly identical for both types of cells. The cells were subjected to 2xsun illumination and it was found that the cells produced using doped a-Si as ETL were much more stable than the cells produced using Cs2CO3.

  4. Thermally induced transformations of amorphous carbon nanostructures fabricated by electron beam induced deposition.

    PubMed

    Kulkarni, Dhaval D; Rykaczewski, Konrad; Singamaneni, Srikanth; Kim, Songkil; Fedorov, Andrei G; Tsukruk, Vladimir V

    2011-03-01

    We studied the thermally induced phase transformations of electron-beam-induced deposited (EBID) amorphous carbon nanostructures by correlating the changes in its morphology with internal microstructure by using combined atomic force microscopy (AFM) and high resolution confocal Raman microscopy. These carbon deposits can be used to create heterogeneous junctions in electronic devices commonly known as carbon-metal interconnects. We compared two basic shapes of EBID deposits: dots/pillars with widths from 50 to 600 nm and heights from 50 to 500 nm and lines with variable heights from 10 to 150 nm but having a constant length of 6 μm. We observed that during thermal annealing, the nanoscale amorphous deposits go through multistage transformation including dehydration and stress-relaxation around 150 °C, dehydrogenation within 150-300 °C, followed by graphitization (>350 °C) and formation of nanocrystalline, highly densified graphitic deposits around 450 °C. The later stage of transformation occurs well below commonly observed graphitization for bulk carbon (600-800 °C). It was observed that the shape of the deposits contribute significantly to the phase transformations. We suggested that this difference is controlled by different contributions from interfacial footprints area. Moreover, the rate of graphitization was different for deposits of different shapes with the lines showing a much stronger dependence of its structure on the density than the dots.

  5. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2015-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  6. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Hangx, S.; Pijnenburg, R. P.; Niemeijer, A. R.; Bakker, E.; Samuelson, J. E.; Spiers, C. J.

    2014-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  7. N-type thermoelectric recycled carbon fibre sheet with electrochemically deposited Bi2Te3

    NASA Astrophysics Data System (ADS)

    Pang, E. J. X.; Pickering, S. J.; Chan, A.; Wong, K. H.

    2012-06-01

    An N-type thermoelectric recycled carbon fibre sheet with bismuth telluride coating has been successfully synthesised through an electrodeposition technique. The Seebeck coefficient and electrical properties of the combined recycled carbon fibre sheet and bismuth telluride films are reported. Classification of the crystal structure, surface morphology and the elemental composition of the resulting deposits are methodically characterised by XRD, SEM and EDX correspondingly. Cyclic voltammetry is also carried out in nitric acid solutions to investigate the right range of deposition potential. An N-type thermoelectric sheet was successfully synthesised with the highest attainable Seebeck coefficient of -54 μV/k with an electrical resistivity of 8.9 × 10-5 ohm m. The results shows slight differences in morphologies and thermoelectric properties for the films deposited at varying deposition potential. The increase in thermoelectrical properties of the recycled carbon fibre is in line with the development of using coated recycled fibre for thermoelectrical applications.

  8. A modelling approach to find stable and reliable soil organic carbon values for further regionalization.

    NASA Astrophysics Data System (ADS)

    Bönecke, Eric; Franko, Uwe

    2015-04-01

    Soil organic matter (SOM) and carbon (SOC) might be the most important components to describe soil fertility of agricultural used soils. It is sensitive to temporal and spatial changes due to varying weather conditions, uneven crops and soil management practices and still struggles with providing reliable delineation of spatial variability. Soil organic carbon, furthermore, is an essential initial parameter for dynamic modelling, understanding e.g. carbon and nitrogen processes. Alas it requires cost and time intensive field and laboratory work to attain and using this information. The objective of this study is to assess an approach that reduces efforts of laboratory and field analyses by using method to find stable initial soil organic carbon values for further soil process modelling and regionalization on field scale. The demand of strategies, technics and tools to improve reliable soil organic carbon high resolution maps and additionally reducing cost constraints is hence still facing an increasing attention of scientific research. Although, it is nowadays a widely used practice, combining effective sampling schemes with geophysical sensing techniques, to describe within-field variability of soil organic carbon, it is still challenging large uncertainties, even at field scale in both, science and agriculture. Therefore, an analytical and modelling approach might facilitate and improve this strategy on small and large field scale. This study will show a method, how to find reliable steady state values of soil organic carbon at particular points, using the approved soil process model CANDY (Franko et al. 1995). It is focusing on an iterative algorithm of adjusting the key driving components: soil physical properties, meteorological data and management information, for which we quantified the input and the losses of soil carbon (manure, crop residues, other organic inputs, decomposition, leaching). Furthermore, this approach can be combined with geophysical

  9. Synthesis of thin films in boron-carbon-nitrogen ternary system by microwave plasma enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Kukreja, Ratandeep Singh

    The Boron Carbon Nitorgen (B-C-N) ternary system includes materials with exceptional properties such as wide band gap, excellent thermal conductivity, high bulk modulus, extreme hardness and transparency in the optical and UV range that find application in most fields ranging from micro-electronics, bio-sensors, and cutting tools to materials for space age technology. Interesting materials that belong to the B-C-N ternary system include Carbon nano-tubes, Boron Carbide, Boron Carbon Nitride (B-CN), hexagonal Boron Nitride ( h-BN), cubic Boron Nitride (c-BN), Diamond and beta Carbon Nitride (beta-C3N4). Synthesis of these materials requires precisely controlled and energetically favorable conditions. Chemical vapor deposition is widely used technique for deposition of thin films of ceramics, metals and metal-organic compounds. Microwave plasma enhanced chemical vapor deposition (MPECVD) is especially interesting because of its ability to deposit materials that are meta-stable under the deposition conditions, for e.g. diamond. In the present study, attempt has been made to synthesize beta-carbon nitride (beta-C3N4) and cubic-Boron Nitride (c-BN) thin films by MPECVD. Also included is the investigation of dependence of residual stress and thermal conductivity of the diamond thin films, deposited by MPECVD, on substrate pre-treatment and deposition temperature. Si incorporated CNx thin films are synthesized and characterized while attempting to deposit beta-C3N4 thin films on Si substrates using Methane (CH4), Nitrogen (N2), and Hydrogen (H2). It is shown that the composition and morphology of Si incorporated CNx thin film can be tailored by controlling the sequence of introduction of the precursor gases in the plasma chamber. Greater than 100mum size hexagonal crystals of N-Si-C are deposited when Nitrogen precursor is introduced first while agglomerates of nano-meter range graphitic needles of C-Si-N are deposited when Carbon precursor is introduced first in the

  10. Whole watershed quantification of net carbon fluxes by erosion and deposition within the Christina River Basin Critical Zone Observatory

    NASA Astrophysics Data System (ADS)

    Aufdenkampe, A. K.; Karwan, D. L.; Aalto, R. E.; Marquard, J.; Yoo, K.; Wenell, B.; Chen, C.

    2012-12-01

    to organic carbon and nitrogen content with stable isotope (13C, 15N) and radiocarbon (14C) abundance to quantify OC/SA and organic carbon sources and mean age. We then use multivariate mixing model analysis to quantify the fractional contribution of each source end-member to each sample of suspended or deposited sediments. Last, we calculate a predicted OC/SA based on source end-member mixing and compare to the measured OC/SA to quantify net change in mineral complexed carbon.

  11. Whole Watershed Quantification of Net Carbon Fluxes by Erosion and Deposition within the Christina River Basin Critical Zone Observatory

    NASA Astrophysics Data System (ADS)

    Aufdenkampe, A. K.; Karwan, D. L.; Aalto, R. E.; Marquard, J.; Yoo, K.; Wenell, B.; Chen, C.

    2013-12-01

    to organic carbon and nitrogen content with stable isotope (13C, 15N) and radiocarbon (14C) abundance to quantify OC/SA and organic carbon sources and mean age. We then use multivariate mixing model analysis to quantify the fractional contribution of each source end-member to each sample of suspended or deposited sediments. Last, we calculate a predicted OC/SA based on source end-member mixing and compare to the measured OC/SA to quantify net change in mineral complexed carbon. Aufdenkampe, A.K. et al. Riverine coupling of biogeochemical cycles between land, oceans, and atmosphere. Frontiers Ecol. Environ. 9, 53-60 (2011). Walling, D. E. Tracing suspended sediment sources in catchments and river systems. Sci. Total Environ. 34, 159-184 (2005).

  12. Influence of carbon nanotubes coatings onto carbon fiber by oxidative treatments combined with electrophoretic deposition on interfacial properties of carbon fiber composite

    NASA Astrophysics Data System (ADS)

    Deng, Chao; Jiang, Jianjun; Liu, Fa; Fang, Liangchao; Wang, Junbiao; Li, Dejia; Wu, Jianjun

    2015-12-01

    To improve the interfacial performance of carbon fiber (CF) and epoxy resin, carbon nanotubes (CNTs) coatings were utilized to achieve this purpose through coating onto CF by the treatment with hydrogen peroxide and concentrated nitric acid combined with electrophoretic deposition (EPD) process. The influence of electrophoretically deposited CNTs coatings on the surface properties of CFs were investigated by Fourier transform infrared spectrometer, atomic force microscopy, scanning electron microscopy and dynamic contact angle analysis. The results indicated that the deposition of carbon nanotubes introduced some polar groups to carbon fiber surfaces, enhanced surface roughness and changed surface morphologies of carbon fibers. Surface wettability of carbon fibers may be significantly improved by increasing surface free energy of the fibers due to the deposition of CNTs. The thickness and density of the coatings increases with the introduction of pretreatment of the CF during the EPD process. Short beam shear test was performed to examine the effect of carbon fiber functionalization on mechanical properties of the carbon fiber/epoxy resin composites. The interfacial adhesion of CNTs/CF reinforced epoxy composites showed obvious enhancement of interlaminar shear strength by 60.2% and scanning electron microscope photographs showed that the failure mode of composites was changed after the carbon fibers were coated with CNTs.

  13. Metrology and Optical Characterization of Plasma Enhanced Chemical Vapor Deposition, (PECVD), low temperature deposited Amorphous Carbon films

    NASA Astrophysics Data System (ADS)

    Ferrieu, F.; Chaton, C.; Neira, D.; Beitia, C.; Mota, L. Proenca; Papon, A. M.; Tarnowka, A.

    2007-09-01

    Amorphous Carbon films deposited by PECVD (RF) have recently been introduced as a new material for semiconductor processing, e.g. in 193 nm ARC lithography [1] and in the DRAM production [2]. A large amount of literature has already been published on with regard to the applications of this class of material [3]. Hence, it has been reported that Amorphous Carbon films undergo a hydrogen chemical desorption when deposited above 500 °C, together with an amorphous to graphite phase transition. Unfortunately, the intrinsic nature of the amorphous carbons depends strongly upon deposition techniques. Film morphology can be completely different from one case to another since there are so many deposition techniques. Optical characterization of these films has also undergone development for several decades. In Spectroscopic Ellipsometry (SE), several models have been proposed from simple Lorentz oscillators' absorption, toward the Tauc Lorentz or Forhoui Bloomer equations. Nevertheless, none of these models sufficiently quantitatively explain the experimental data. In some cases, a simple `Effective Medium Approximation', (EMA), is able to determine the sp2/sp3 bounds present in the film. However, the validity limitation of this approach remains questionable when considering films in a wide range of film thicknesses. In line, metrology for semiconductor requires robust models, which account for parameters such as temperature deposition, stress and film resistivity as well. Different solutions are investigated from our optical measurements, including a biaxial anisotropy hypothesis, which has been proposed by J. Leng et al. [3] from BPR (Beam Reflectometry Profile) and with SE measurements [4]. Our results are considered, together with other surface analysis techniques (XRD, IR and Raman) and confronted to TEM observations.

  14. Induced carbon deposition by local hydrocarbon injection into detached divertor plasmas in JET

    NASA Astrophysics Data System (ADS)

    Jet Efda Contributors Airila, M. I.; Coad, J. P.; Brezinsek, S.; Belo, P.; Groth, M.; Kirschner, A.; Makkonen, T.; Stamp, M. F.; Strachan, J. D.; Widdowson, A. M.; Wiesen, S.

    2011-08-01

    During detachment experiments of JET in 2007 (Brezinsek et al., 2009 [1]), 1 × 1022 molecules of 12CD4 were injected at a rate of about 5 × 1020 s-1 into L-mode plasma. The injection was done at the outer strike point in the centre of the horizontal target, just before opening the machine. The deposited layers were analyzed for deuterium post mortem after the removal of tiles. The heaviest local D deposition density is found immediately upstream of the gas inlet, but downstream the deposition is found over a larger area. In total, 3.7 × 1020 deuterium atoms were found locally deposited; if the mean D/C in the deposits is 0.4, then about 10% of the injected carbon was locally deposited. Transport and local deposition of the injected carbon was modeled with the 3D Monte Carlo impurity transport code ERO (Kirschner et al., 2000 [2]). The plasma background was generated with the onion-skin solver of the DIVIMP code (Stangeby and Elder, 1992 [3]). Locally deposited fraction is reproduced with ERO but the distribution not satisfactorily. In particular the poloidal transport of carbon is several times weaker than measured.

  15. Surface and corrosion characteristics of carbon plasma implanted and deposited nickel-titanium alloy

    SciTech Connect

    Poon, R.W.Y.; Liu, X.Y.; Chung, C.Y.; Chu, P.K.; Yeung, K.W.K.; Lu, W.W.; Cheung, K.M.C.

    2005-05-01

    Nickel-titanium shape memory alloys (NiTi) are potentially useful in orthopedic implants on account of their super-elastic and shape memory properties. However, the materials are prone to surface corrosion and the most common problem is out-diffusion of harmful Ni ions from the substrate into body tissues and fluids. In order to improve the corrosion resistance and related surface properties, we used the technique of plasma immersion ion implantation and deposition to deposit an amorphous hydrogenated carbon coating onto NiTi and implant carbon into NiTi. Both the deposited amorphous carbon film and carbon plasma implanted samples exhibit much improved corrosion resistances and surface mechanical properties and possible mechanisms are suggested.

  16. Solar-induced chemical vapor deposition of diamond-type carbon films

    DOEpatents

    Pitts, J. Roland; Tracy, C. Edwin; King, David E.; Stanley, James T.

    1994-01-01

    An improved chemical vapor deposition method for depositing transparent continuous coatings of sp.sup.3 -bonded diamond-type carbon films, comprising: a) providing a volatile hydrocarbon gas/H.sub.2 reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and b) directing a concentrated solar flux of from about 40 to about 60 watts/cm.sup.2 through said reactant mixture to produce substrate temperatures of about 750.degree. C. to about 950.degree. C. to activate deposition of the film on said substrate.

  17. Solar-induced chemical vapor deposition of diamond-type carbon films

    DOEpatents

    Pitts, J.R.; Tracy, C.E.; King, D.E.; Stanley, J.T.

    1994-09-13

    An improved chemical vapor deposition method for depositing transparent continuous coatings of sp[sup 3]-bonded diamond-type carbon films, comprises: (a) providing a volatile hydrocarbon gas/H[sub 2] reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and (b) directing a concentrated solar flux of from about 40 to about 60 watts/cm[sup 2] through said reactant mixture to produce substrate temperatures of about 750 C to about 950 C to activate deposition of the film on said substrate. 11 figs.

  18. High-Temperature Carbon Deposition on Oxide Surfaces by CO Disproportionation

    PubMed Central

    2016-01-01

    Carbon deposition due to the inverse Boudouard reaction (2CO → CO2 + C) has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 in comparison to CH4 by a variety of different chemical, structural, and spectroscopic characterization techniques, including electrochemical impedance spectroscopy (EIS), Fourier-transform infrared (FT-IR) spectroscopy and imaging, Raman spectroscopy, and electron microscopy. Consentaneously, all experimental methods prove the formation of a more or less conducting carbon layer (depending on the used oxide) of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in flowing CO at temperatures above ∼1023 K. All measurements show that during carbon deposition, a more or less substantial surface reduction of the oxides takes place. These results, therefore, reveal that the studied pure oxides can act as efficient nonmetallic substrates for CO-induced growth of highly distorted graphitic carbon with possible important technological implications especially with respect to treatment in pure CO or CO-rich syngas mixtures. Compared to CH4, more carbon is generally deposited in CO under otherwise similar experimental conditions. Although Raman and electron microscopy measurements do not show substantial differences in the structure of the deposited carbon layers, in particular, electrochemical impedance measurements reveal major differences in the dynamic growth process of the carbon layer, eventually leading to less percolated islands and suppressed metallic conductivity in comparison to CH4-induced graphite. PMID:26877828

  19. Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin, Colombia

    NASA Astrophysics Data System (ADS)

    Cortes, Jorge E.; Rincon, Jose M.; Jaramillo, Jose M.; Philp, R. Paul; Allen, Jon

    2010-03-01

    Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography-isotopic ratio-mass spectrometry (GC-IRMS). GC-IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ13C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC-IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.

  20. Effect of carbon deposition by carbon monoxide disproportionation on electrochemical characteristics at low temperature operation for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Sumi, Hirofumi; Lee, Yi-Hsuan; Muroyama, Hiroki; Matsui, Toshiaki; Kamijo, Motohisa; Mimuro, Shin; Yamanaka, Mitsugu; Nakajima, Yasushi; Eguchi, Koichi

    2011-05-01

    The deterioration by carbon deposition was evaluated for electrolyte- and anode-supported solid oxide fuel cells (SOFCs) in comparison with carbon monoxide disproportionation and methane cracking. The polarization resistance of the nickel-yttria stabilized zirconia (Ni-YSZ) anode increased with a rise in CO concentration in H2-CO-CO2 mixture for the electrolyte-supported cells at 923 K. The resistance, however, did not change against CO concentration for the anode-supported cells. In a methane fuel with a steam/carbon (S/C) ratio of 0.1, the cell performance decreased for both of the cells at 1073 K. A large amount of agglomerated amorphous carbon was deposited from the anode surface to the interface between the anode and the electrolyte after power generation at S/C = 0.1 in methane fuel. On the other hand, the crystalline graphite was deposited only at the anode surface for the anode-supported cell after power generation in CO-CO2 mixture. These results suggest that the reaction rate of CO disproportionation is faster than that of methane cracking. The deposited carbon near the anode/electrolyte interface caused the increase in the polarization resistance.

  1. Methane carbon stable isotope signatures in waters and sediments of the Laptev Sea Shelf

    NASA Astrophysics Data System (ADS)

    Samarkin, V.; Semiletov, I. P.; Finke, N.; Shakhova, N. E.; Joye, S. B.

    2012-12-01

    There are a number of areas characterized high water column methane concentrations and active seafloor methane seepage zones along the shelf of the Laptev Sea. Degrading subsea permafrost, which is rich in organic carbon and possibly containing metastable methane gas hydrates, is considered a potent source of methane in this area. To better understand possible methane sources generating high methane areas of the Laptev Sea, carbon stable isotope signatures of water column methane and in surface and deep drill core sediment samples were obtained during summer 2011 and spring 2012 field campaigns. The δ13C values of methane dissolved in seawater at the drill site varied from -37.8 to -75.7 ‰. The range of δ13C values of methane in the surface sediments was from -51.3 to -58.2 ‰ and in drill core samples (up to 26.5 m depth) values ranged from -77.8 to -100 ‰. Methane carbon isotope signatures in seawater reflect various sources of methane and the influence of active aerobic methane oxidation in seawater and surface sediments. Significant depletion of methane from drill core with δ13C (to -100‰) is characteristic of hydrogenotrophic methanogenesis at cold near 0°C in situ temperatures, which was confirmed with δ14C-radiotracer rate incubations.

  2. Assimilation of benzene carbon through multiple trophic levels traced by different stable isotope probing methodologies.

    PubMed

    Bastida, Felipe; Jechalke, Sven; Bombach, Petra; Franchini, Alessandro G; Seifert, Jana; von Bergen, Martin; Vogt, Carsten; Richnow, Hans H

    2011-08-01

    The flow of benzene carbon along a food chain consisting of bacteria and eukaryotes, including larvae (Diptera: Chironomidae), was evaluated by total lipid fatty acids (TLFAs)-, amino acid- and protein-stable isotope probing (SIP). A coconut-fibre textile, colonized by a benzene-degrading biofilm, was sampled in a system established for the remediation of benzene, toluene, ethylbenzene and xylenes (BTEX)-polluted groundwater and incubated with (12)C- and [(13)C(6)]-benzene (>99 at.%) in a batch-scale experiment for 2-8 days. After 8 days, Chironomus sp. larvae were added to study carbon flow to higher trophic levels. Gas chromatography-combustion-isotope ratio monitoring mass spectrometry of TLFA showed increased isotope ratios in the (13)C-benzene-incubated biofilm. A higher (13)C-enrichment was observed in TLFAs, indicative of Gram-negative bacteria than for Gram-positive. Fatty acid indicators of eukaryotes showed significant (13)C-incorporation, but to a lower extent than bacterial indicators. Fatty acids extracted from larvae feeding on (13)C-biofilm reached an isotopic ratio of 1.55 at.%, illustrating that the larvae feed, to some extent, on labelled biomass. No (13)C-incorporation was detectable in larval proteins after their separation by sodium-dodecyl sulphate-polyacrylamide gel electrophoresis and analysis by nano-liquid-chromatography-mass spectrometry. The flow of benzene-derived carbon could be traced in a food web consisting of bacteria and eukaryotes.

  3. Stable carbon isotope ratio in atmospheric CO2 collected by new diffusive devices.

    PubMed

    Proto, Antonio; Cucciniello, Raffaele; Rossi, Federico; Motta, Oriana

    2014-02-01

    In this paper, stable carbon isotope ratios (δ (13)C) were determined in the atmosphere by using a Ca-based sorbent, CaO/Ca12Al14O33 75:25 w/w, for passively collecting atmospheric CO2, in both field and laboratory experiments. Field measurements were conducted in three environments characterized by different carbon dioxide sources. In particular, the environments under consideration were a rather heavily trafficked road, where the source of CO2 is mostly vehicle exhaust, a rural unpolluted area, and a private kitchen where the major source of CO2 was gas combustion. Samplers were exposed to the free atmosphere for 3 days in order to allow collection of sufficient CO2 for δ(13)C analysis, then the collected CO2 was desorbed from the adsorbent with acid treatment, and directly analyzed by nondispersive infrared (NDIR) instrument. δ (13)C results confirmed that the samplers collected representative CO2 samples and no fractionation occurred during passive trapping, as also confirmed by an appositely designed experiment conducted in the laboratory. Passive sampling using CaO/Ca12Al14O33 75:25 w/w proved to be an easy and reliable method to collect atmospheric carbon dioxide for δ (13)C analysis in both indoor and outdoor places.

  4. Tracing Carbon Sources through Aquatic and Terrestrial Food Webs Using Amino Acid Stable Isotope Fingerprinting

    PubMed Central

    Larsen, Thomas; Ventura, Marc; Andersen, Nils; O’Brien, Diane M.; Piatkowski, Uwe; McCarthy, Matthew D.

    2013-01-01

    Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ13C patterns among amino acids (δ13CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ13CAA patterns in contrast to bulk δ13C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ13CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ13C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ13C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs. PMID:24069196

  5. Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

    PubMed

    Larsen, Thomas; Ventura, Marc; Andersen, Nils; O'Brien, Diane M; Piatkowski, Uwe; McCarthy, Matthew D

    2013-01-01

    Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13)C patterns among amino acids (δ(13)CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13)CAA patterns in contrast to bulk δ(13)C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13)CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13)C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13)C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

  6. Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Stern, Jennifer C.; Summers, David P.; Kubo, Mike; Yassar, Saima

    2006-01-01

    Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

  7. Thermally stable yttrium-scandium oxide high-k dielectrics deposited by a solution process

    NASA Astrophysics Data System (ADS)

    Hu, Wenbing; Frost, Bradley; Peterson, Rebecca L.

    2016-03-01

    We investigated the thermal stability of electrical properties in ternary alloy (Y x Sc1-x )2O3 high-k oxides as a function of yttrium fraction, x. The yttrium-scandium oxide dielectric films are deposited using a facile ink-based process. The oxides have a stoichiometry-dependent relative dielectric constant of 26.0 to 7.7 at 100 kHz, low leakage current density of 10-8 A·cm-2, high breakdown field of 4 MVṡcm-1, and interface trap density of 1012 cm-2·eV-1 with silicon. Compared with binary oxides, ternary alloys exhibit less frequency dispersion of the dielectric constant and a higher crystallization temperature. After crystallization is induced through a 900 °C anneal, ternary (Y0.6Sc0.4)2O3 films maintain their low leakage current and high breakdown field. In contrast, the electrical performance of the binary oxides significantly degrades following the same treatment. The solution-processed ternary oxide dielectrics demonstrated here may be used as high-k gate insulators in complementary metal-oxide semiconductor (CMOS) technologies, in novel electronic material systems and devices, and in printed, flexible thin film electronics, and as passivation layers for high power devices. These oxides may also be used as insulators in fabrication process flows that require a high thermal budget.

  8. Crosslinked redox polymer enzyme electrodes containing carbon nanotubes for high and stable glucose oxidation current.

    PubMed

    MacAodha, Domhnall; Ferrer, Maria Luisa; Conghaile, Peter Ó; Kavanagh, Paul; Leech, Dónal

    2012-11-14

    Co-immobilisation approaches for preparation of glucose-oxidising films of [Os(2,2'-bipyridine)(2)(poly-vinylimidazole)(10)Cl] and glucose oxidase on glassy carbon electrodes are compared. Electrodes prepared by crosslinking using glutaraldehyde vapour, without and with a NaBH(4) reduction, provide higher glucose oxidation current than those prepared using a well-established diepoxide method. Addition of multi walled carbon nanotubes to the film deposition solutions produces an enhanced glucose oxidation current density of 5 mA cm(-2) at 0.35 V vs. Ag/AgCl, whilst improving the operational stability of the current signal. Carbon nanotube, glutaraldehyde vapour crosslinked, films on electrodes, reduced by NaBH(4), retain 77% of initial catalytic current over 24 hours of continuous amperometric testing in a 37 °C, 50 mM phosphate buffer solution containing 150 mM NaCl and 100 mM glucose. Potential application of this approach to implantable enzymatic biofuel cells is demonstrated by production of glucose oxidation currents, under pseudo-physiological conditions, using mediating films with lower redox potentials.

  9. Production of carbon monoxide by charged particle deposition.

    NASA Technical Reports Server (NTRS)

    Green, A. E. S.; Sawada, T.; Edgar, B. C.; Uman, M. A.

    1973-01-01

    Recent studies of electron energy deposition in CO2 and CO based upon a large set of electron impact cross sections are utilized to estimate the telluric CO directly produced by various charged-particle deposition mechanisms. The mechanisms considered are (1) lightning, (2) cloud coronal discharges, (3) background radioactivity, (4) natural electrostatic discharges, (5) photoelectrons in the ionosphere, (6) auroral electrons, (7) auroral protons, (8) cosmic rays, and (9) solar wind. 'Ball park' estimates of the global CO production by each of these mechanisms are given. Apart from mechanisms 1, 2, and 5, all CO production mechanisms are estimated to be small compared to artificial sources. If, as appears to be the case, the hot oxygen atoms and ions and other atomic species immediately produced by these three charged-particle deposition mechanisms react rapidly with CO2 to produce CO, these mechanisms can readily lead to CO production levels in the multimegaton-per-year range.

  10. Quantification of Gaseous Elemental Mercury Dry Deposition to Environmental Surfaces using Mercury Stable Isotopes in a Controlled Environment

    NASA Astrophysics Data System (ADS)

    Rutter, A. P.; Schauer, J. J.; Shafer, M. M.; Olson, M.; Robinson, M.; Vanderveer, P.; Creswell, J. E.; Parman, A.; Mallek, J.; Gorski, P.

    2009-12-01

    atmospheric turbulence and wind speed. GEM enriched in stable isotope 198 (GEM-198) was released into the room from source at elevated but environmentally relevant concentrations of GEM-198 for several days. Uptake of GEM-198 from deciduous and conifer trees, grass turf, 3 types of soil, sand, concrete, asphalt, and adsorbent coated deposition coupons were quantified over several days. Exposures were conducted between 10oC and 30oC, in dark and light conditions. Mercury was recovered from the samples using acidic digestions and surface leaches, and then analyzed for the content of GEM-198 by high resolution ICPMS. Experimental results demonstrated that uptake by White Ash, White Spruce, and Kentucky bluegrass were significantly higher than uptakes measured for two Wisconsin soils, peat, sand, concrete and asphalt at all of the conditions studied. Deposition resistances for surface transfer processes for were calculated for each of the substrates across the conditions studied for use in atmospheric model simulations.

  11. Structure and phase composition of deposited tantalum-carbon films

    NASA Astrophysics Data System (ADS)

    Tuleushev, Yu. Zh.; Volodin, V. N.; Zhakanbaev, E. A.; Alimzhan, B.

    2016-08-01

    Ion plasma sputtering and the subsequent codeposition of ultrafine tantalum and carbon particles were used to prepare coatings with 4.6-71.5 at % C. Structural studies of the coatings showed the existence of carbon solid solutions in β Ta at carbon contents to 4.6 at %, carbon solid solutions in α Ta at carbon contents of 4.6-10.3 at %, and direct synthesis of TaC at carbon contents of 44.7-71.5 at %. During heat treatments to 700°C, the substantial concentration widening of regions of the existence of Ta2C and TaC was found. The lattice parameters of hexagonal Ta2C and fcc TaC carbides were determined for composition ranges of the existence of phases during heating to 700°C. Upon heating above 600°C, the progressive transition of quasiamorphous Ta2C carbide into the crystalline Ta2C carbide was found to take place. The possibility of applying the direct synthesis of TaC carbide in engineering was noted.

  12. Stable Carbon Isotopic Fractionation in Smoke and Char Produced During Biomass Burning

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Hsieh, Y.

    2006-12-01

    Stable isotopic ratio of carbon has been used extensively as a tracer of carbon sources in the environment. It has been documented that burning of C4 grasses resulted in significant depletion of C13 in the charcoal while burning of wood and C3 grass did not. This study was initiated to investigate the stable carbon isotopic fractionation of the smoke and char produced during biomass burnings. Samples of Juncus romerianus (C3 salt marsh grass) and Spartina alterniflora (C4 salt marsh grass), Eremochloa ophiuroides (centipede, a C4 lawn grass) and woody debris of a pine forest were colleted and burned in open air fire place. The particulate matter with diameters less than 2.5 micron (PM2.5) emitted from the burning was collected using a PM sampler. The original biomass, PM2.5, black C in PM2.5 and char (ash) were analyzed for their C, N and S thermograms using a multi-elemental scanning thermal analyzer and their stable C isotopic ratios were measured using an EA-IRMS. The results indicate that burning of wood and C3 grass did not produce significant C isotopic fractionation in PM2.5, black C in PM2.5 and char with respect to the original material. However, there was a significant C13-depletion in PM2.5 (-6.2 per mil), black C in PM2.5 (-4.6 per mil) and chars (-4.6 per mil) produced by burning of the C4 centipede grass; whereas the C4 Spartina salt marsh grass produced a C13-depletion in PM2.5 (-2.3 per mil) and black C in PM2.5 (-3.6 per mil), and a slight C13-enrichment in char (0.5 per mil). The isotope fractionation associated with burning of C4 vegetation is probably dependent on species and burning conditions and warrant further study.

  13. Post-depositional fractionation of nitrate stable isotopes in Antarctic snow: towards constraining past UV radiation and reactive nitrogen cycling

    NASA Astrophysics Data System (ADS)

    Frey, M. M.; Morin, S.; Savarino, J. P.; Erbland, J.

    2009-12-01

    Recent studies on atmospheric particulate nitrate (NO3-) demonstrated that the nitrogen and triple oxygen stable isotopic composition of NO3- allows constraining not only atmospheric sources and sinks but also oxidation pathways of reactive nitrogen. However, extending this tool to past atmospheres using ice cores can be complicated by post-depositional mass loss and fractionation via UV-photolysis and evaporation. A new 60-yr firn record of 15N/14N and 18O/16O isotopic ratios in NO3- from Dome C, Antarctica (75° S, 123° E) shows strong fractionation compared to the atmospheric signal and a significant anti-correlation (r=-0.75, p<0.01). We propose that at low accumulation sites the nitrate stable isotope record preserves the imprint of processes driving post-depositional fractionation and therefore can be used to infer past levels of UV-radiation and NO3- loss from snow. The former is supported by a strong correlation between δ15N(NO3-) and modeled annual UV radiation at Dome C (r = 0.7, p<0.001). Furthermore, first quantum-chemical model calculations of the photolytic fractionation constant of the nitrogen isotope are consistent with field and lab observations and show a strong sensitivity to the spectrum of actinic flux. We discuss the proposed model framework as a first step towards an isotopic atmosphere-snow transfer function and implications not only for ice core interpretation but also for our understanding of reactive nitrogen cycling above snow surfaces.

  14. Barrier properties to surrogates of hydrogenated carbon nano-films deposited on PET by plasma-enhanced chemical vapour deposition.

    PubMed

    Oliveira, Éder C; Echegoyen, Yolanda; Nerin, Cristina; Cruz, Sandra A

    2014-01-01

    Poly(ethylene terephthalate) resin was contaminated with a series of surrogates using a US Food and Drug Administration protocol. The contaminated samples were coated with two different kinds of hydrogenated amorphous carbon thin films (a-C:H): one with diamond-like hydrogenated amorphous carbon and another with polymer-like hydrogenated carbon (PLCH) phases. To evaluate the barrier properties of the a-C:H films, migration assays were performed using food simulants. After the tests, analysis by gas chromatography with different detectors was carried out. The appearance of the films before and after the migration experiments was studied by field emission scanning electron microscopy. The results showed that a-C:H films have good barrier properties for most of the evaluated compounds, mainly when they are deposited as PLCH phase.

  15. Physical vapor deposition synthesis of tungsten monocarbide (WC) thin films on different carbon substrates

    SciTech Connect

    Weigert, E. C.; Humbert, M. P.; Mellinger, Z. J.; Ren, Q.; Beebe, T. P. Jr.; Bao, L.; Chen, J. G.

    2008-01-15

    The synthesis of tungsten monocarbide (WC) thin films has been performed by physical vapor deposition on various substrates including glassy carbon, carbon fiber sheet, carbon foam, and carbon cloth. The WC and W{sub 2}C phase contents of these films have been evaluated with bulk and surface analysis techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy. These characterization techniques were also used to determine the effects of synthesis by nonreactive and reactive sputtering. The synthesis of WC particles supported on the carbon fiber substrate has also been accomplished using the temperature programmed reaction method. Overall, the results demonstrate that the phase purity of tungsten carbides can be controlled by the deposition environment and annealing temperatures.

  16. Formation of catalyst nanoparticles and nucleation of carbon nanotubes in chemical vapor deposition.

    PubMed

    Verissimo, C; Aguiar, M R; Moshkalev, S A

    2009-07-01

    Multi-walled carbon nanotubes and other carbon nanostructures have been grown using catalytic thermal chemical vapor deposition method in a horizontal tubular quartz furnace at atmospheric pressure. The mechanisms of nanotubes/nanofibers nucleation and growth are analyzed. A new model explaining the nanotube nucleation as a specific instability occurring on the catalyst particle surface supersaturated with carbon is presented. It is also shown that an axially symmetric instability, giving rise to the nanotube nucleation, is developed when certain critical conditions such as temperature, supersaturation and catalyst volume are achieved. For smaller temperatures, another mechanism of carbon segregation from supersaturated catalyst particles has been observed. In this case, flat rather than tubular graphitic layers are formed. These findings are important for better understanding and control of the synthesis of different carbon nanoforms using chemical vapor deposition.

  17. Continuous growth of single-wall carbon nanotubes using chemical vapor deposition

    DOEpatents

    Grigorian, Leonid; Hornyak, Louis; Dillon, Anne C; Heben, Michael J

    2008-10-07

    The invention relates to a chemical vapor deposition process for the continuous growth of a carbon single-wall nanotube where a carbon-containing gas composition is contacted with a porous membrane and decomposed in the presence of a catalyst to grow single-wall carbon nanotube material. A pressure differential exists across the porous membrane such that the pressure on one side of the membrane is less than that on the other side of the membrane. The single-wall carbon nanotube growth may occur predominately on the low-pressure side of the membrane or, in a different embodiment of the invention, may occur predominately in between the catalyst and the membrane. The invention also relates to an apparatus used with the carbon vapor deposition process.

  18. Continuous growth of single-wall carbon nanotubes using chemical vapor deposition

    DOEpatents

    Grigorian, Leonid; Hornyak, Louis; Dillon, Anne C; Heben, Michael J

    2014-09-23

    The invention relates to a chemical vapor deposition process for the continuous growth of a carbon single-wall nanotube where a carbon-containing gas composition is contacted with a porous membrane and decomposed in the presence of a catalyst to grow single-wall carbon nanotube material. A pressure differential exists across the porous membrane such that the pressure on one side of the membrane is less than that on the other side of the membrane. The single-wall carbon nanotube growth may occur predominately on the low-pressure side of the membrane or, in a different embodiment of the invention, may occur predominately in between the catalyst and the membrane. The invention also relates to an apparatus used with the carbon vapor deposition process.

  19. Investigating landfill-impacted groundwater seepage into headwater streams using stable carbon isotopes

    NASA Astrophysics Data System (ADS)

    Atekwana, E. A.; Krishnamurthy, R. V.

    2004-07-01

    The impact of landfill contaminated groundwater along a reach of a small stream adjacent to a municipal landfill was investigated using stable carbon isotopes as a tracer. Groundwater below the stream channel, groundwater seeping into the stream, groundwater from the stream banks and stream water were sampled and analysed for dissolved inorganic carbon (DIC) and the isotope ratio of DIC (13CDIC). Representative samples of groundwater seeping into the stream were collected using a device (a seepage well) specifically designed for collecting samples of groundwater seeping into shallow streams with soft sediments. The DIC and 13CDIC of water samples ranged from 52 to 205 mg C/L and -16.9 to +5.7 relative to VPDB standard, respectively. Groundwater from the stream bank adjacent to the landfill and some samples of groundwater below the stream channel and seepage into the stream showed evidence of 13C enriched DIC (δ13CDIC = -2.3 to +5.7), which we attribute to landfill impact. Stream water and groundwater from the stream bank opposite the landfill did not show evidence of landfill carbon (δ13CDIC = -10.0 to -16.9). A simple mixing model using DIC and δ13CDIC showed that groundwater below the stream and groundwater seeping into the stream could be described as a mixture of groundwater with a landfill carbon signature and uncontaminated groundwater. This study suggests that the hyporheic zone at the stream-groundwater interface probably was impacted by landfill contaminated groundwater and may have significant ecological implications for this ecotone.

  20. Delivery of albuterol and ipratropium bromide from two nebulizer systems in chronic stable asthma. Efficacy and pulmonary deposition

    SciTech Connect

    Johnson, M.A.; Newman, S.P.; Bloom, R.; Talaee, N.; Clarke, S.W.

    1989-07-01

    Bronchodilator responses to both nebulized albuterol (salbutamol) and ipratropium bromide and aerosol delivery to the tracheobronchial tree have been assessed in eight patients with chronic stable asthma (mean baseline FEV1, 50 percent; reversibility greater than 20 percent). Two commercially available nebulizer systems were used, namely, a Turret nebulizer operated at a compressed gas flow rate of 12 L/min (droplet MMD, 3.3 mu) and an Inspiron nebulizer driven at 6 L/min (MMD, 7.7 mu). Albuterol was given as doses of 250 micrograms, 250 micrograms, 500 micrograms, and 1,000 micrograms (cumulative dose, 2 mg) and ipratropium bromide as doses of 50 micrograms, 50 micrograms, 100 micrograms, and 200 micrograms (cumulative dose, 400 micrograms) at intervals of 35 minutes. For albuterol, bronchodilatation was significantly (p less than 0.05) greater at all dosage levels with the Turret. For ipratropium, bronchodilatation was similar for both nebulizers. Measurements of aerosol deposition using /sup 99m/Tc-labelled pentetic acid (diethylenetriamine pentaacetic acid; DTPA) showed that 9.1 +/- 1.1 percent and 2.7 +/- 0.2 percent of the dose reached the lungs during nebulization to dryness for Turret and Inspiron, respectively (p less than 0.01); distribution within the lungs was similar for the two aerosols. Selection of nebulizer apparatus can influence delivery of aerosol and subsequent bronchodilator response to albuterol in patients with chronic stable asthma but is less important for aerosol delivery of ipratropium bromide in these patients.

  1. Enhanced N Deposition and Peatland Carbon Stocks in Boreal Alberta

    NASA Astrophysics Data System (ADS)

    Turetsky, M. R.; Halsey, L. A.; Vitt, D. H.; Wieder, R. K.

    2003-12-01

    Increased deposition of reactive nitrogen due to anthropogenic activities may stimulate plant growth and soil C turnover in N-limited ecosystems. Many peatland ecosystems are particularly sensitive to nitrogen deposition due their ombrotrophic nature. Here, we capitalize on a regional gradient of N deposition associated with several decades of oil sands mining. At six peatlands varying in atmospheric N loading (modeled from 1.45-3.26 kg N ha-1 yr-1), we measured Sphagnum fuscum net primary productivity (NPP). NPP rates were higher at Steepbank Bog (mean of 600 g m-2 yr-1) than at the five sites with lower N deposition (pooled mean of 182 g m-2 yr-1). At the site with the highest (Steepbank Bog) and lowest (Bleak Lake Bog) N loading, we quantified rates of C storage by 210Pb dating. Over the past 30 years of mining activity, rates of vertical peat accumulation were higher at Steepbank Bog (19.4 +/-0.4 cm) than at Bleak Lake Bog (13.9 +/-2.0 cm). However, there were no differences between sites in cumulative C storage over this 30-yr period (Steepbank: 5.0 +/-0.2 kg C m-2, Bleak Lake: 5.0 +/-0.4 kg C m-2). Together, these data suggest that increased N availability stimulates plant growth rates, leading to greater vertical accumulation of peat. However, enhanced N deposition does not appear to influence C storage in these sites, possibly due to lower peat bulk density and/or greater microbial activity.

  2. Does more intense burning in warmer, drier boreal forest create more stable black carbon in soils?

    NASA Astrophysics Data System (ADS)

    Kane, E.; Hockaday, W.

    2012-04-01

    Over the past four decades, arctic and boreal regions of the Northern Hemisphere have undergone a higher degree of warming than any other region on earth, and as one result, the frequency of fire in the North American boreal forest region has more than doubled within this timeframe. Many boreal forests contain deep organic layers that are a significant reservoir of terrestrial carbon and their burning in wildfires not only releases trace gasses to the atmosphere but also regulates long-term carbon storage. On the other hand, the formation of pyrogenic C (charcoal and black carbon (BC)) during wildfires may act as a long-term SOC sink. However, recent publications have shown that pyrogenic C in soils may not be as stable as conventionally thought, and in fact, the size of the C sink generated by pyrogenic C in boreal forest soils continues to be an issue of debate. We suggest that burning conditions largely determine the susceptibility of char to microbial attack in the decades to centuries following fire. Our previous work has shown that warmer, south facing sites accumulated more BC in surface mineral soil horizons than did colder sites with greater permafrost extent. We have used quantitative nuclear magnetic resonance to measure the degree of aromatic ring condensation in charcoal structure and have shown that the number of condensed aromatic carbons increases exponentially with fire temperature. We hypothesize that the stability of BC in the soil system is largely controlled by the interactivity of changes in burn condition and landscape position. We expect there to be more stable BC (higher degree of aromatic ring condensation) generated in very hot fires occurring on warmer, drier, south-facing aspects, which typically lack permafrost. In our initial analysis of macroscopic charcoal found in surface mineral soils (A horizons) across climate gradients in interior Alaska, radiocarbon ages are highly variable within and across landscape positions. In fact, we

  3. Improving stable carbon and oxygen isotope geochemical measurements in dolomite: reference material and acid fractionation factor

    NASA Astrophysics Data System (ADS)

    Vandeginste, V.; John, C. M.; Jourdan, A.; Davis, S.

    2010-12-01

    The analysis of stable carbon and oxygen isotope composition is one of the most commonly used techniques in stratigraphic and diagenetic research of carbonate rocks. The wide-spread use and easy access of this long-established method has the side effect that little attention is paid to fundamental calibrations. Dolomite is often measured against a calcite standard (NBS19), and the acid fractionation factor used to calibrate is based on the one for calcite. To date, no reference material exists for dolomite. In this study, which is part of dolomite research in the Qatar Carbonates and Carbon Storage Research Centre project, we focus on two main goals. First, we characterize a current standard of dolomite used for major and minor elemental geochemistry, and assess its suitability as a new dolomite standard for δ18O and δ13C. Second, we attempt to better constrain the acid fractionation factor for dolomite and assess the influence of different dolomite types on this fractionation factor. As only two third of the total oxygen in the carbonate is released in the form of CO2 during acid reaction, a fractionation between the reacting carbonate and the resulting gas will occur. A recent study by Kim et al. (2007) improved on the acid fractionation factors for calcite and aragonite. Often, the acid fractionation factor for dolomite is used to calculate δ18O and δ13C from the values obtained by calibration with the calcite standard. Only two studies (from the 1980’s) have attempted to constrain the acid fractionation factor for dolomite, of which only Rosenbaum and Sheppard (1986) did experiments not only at 25°C, but also at 50 and 100°C. The dataset of the latter authors is, however, very limited and contains only two dolomite samples. We aim at improving the constraints on the acid fractionation factor of dolomite by reacting a wide range of different types of dolomite at a wide range of acid temperature, and compare this to the absolute isotopic composition of

  4. Long-term Carbon and Nitrogen Dynamics at SPRUCE Revealed through Stable Isotopes in Peat Profiles

    NASA Astrophysics Data System (ADS)

    Hobbie, E. A.

    2015-12-01

    Carbon and nitrogen turnover in peatlands is of considerable interest because peat is a large reservoir of stored carbon that could emit greenhouse gases in response to climate change. Because peat cores preserve a long-term record of system carbon and nitrogen dynamics, it is possible to use stable isotopes as markers of changes in carbon (C) and nitrogen (N) dynamics over time. Here, we used δ15N and δ13C patterns throughout the depth profile of peat cores to understand controls over C-N cycling in the Marcell S1 forested bog in northern Minnesota. In multiple regression analyses, δ15N and δ13C correlated strongly with depth, plot location, %C, %N, and each other. Negative correlation of δ15N with %N presumably reflected removal of 15N-depleted N via denitrification, diffusion, or plant N transfer via mycorrhizal fungi. A step increase in the depth coefficient for δ15N of ~3‰ from -25 cm to -35 cm suggested that the N removal process primarily operates at a discrete depth corresponding to the juncture between aerobic and anaerobic layers defined by the water table. Higher δ15N and lower δ13C in plots closer to uplands may reflect distinct hydrology and accompanying shifts in C and N dynamics in the lagg area fringing the bog. The Suess effect (declining δ13CO2 since the Industrial Revoluation) and aerobic decomposition lowered δ13C in recent surficial samples. Small increases in δ13C at -112 cm (4300 calibrated years BP) and -85 cm (3800 calibrated years BP) may reflect C dynamics during a suspected transitional fen stage (based on paleoecology at a nearby bog), when reduced methanotrophy retained less 13C-depleted carbon derived from methane than in later periods. The C/N decreased until about -85 cm and thereafter remained steady, suggesting that the active zone of aerobic processing during drought may extend to this depth. The inflection point in calculated carbon accumulation rates at this depth supports this conclusion.

  5. Stable and controlled amphoteric doping by encapsulation of organic molecules inside carbon nanotubes.

    PubMed

    Takenobu, Taishi; Takano, Takumi; Shiraishi, Masashi; Murakami, Yousuke; Ata, Masafumi; Kataura, Hiromichi; Achiba, Yohji; Iwasa, Yoshihiro

    2003-10-01

    Single-walled carbon nanotubes (SWNTs) have strong potential for molecular electronics, owing to their unique structural and electronic properties. However, various outstanding issues still need to be resolved before SWNT-based devices can be made. In particular, large-scale, air-stable and controlled doping is highly desirable. Here we present a method for integrating organic molecules into SWNTs that promises to push the performance limit of these materials for molecular electronics. Reaction of SWNTs with molecules having large electron affinity and small ionization energy achieved p- and n-type doping, respectively. Optical characterization revealed that charge transfer between SWNTs and molecules starts at certain critical energies. X-ray diffraction experiments revealed that molecules are predominantly encapsulated inside SWNTs, resulting in an improved stability in air. The simplicity of the synthetic process offers a viable route for the large-scale production of SWNTs with controlled doping states.

  6. Facile synthesis of stable superhydrophobic nanocomposite based on multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Mokarian, Zahra; Rasuli, Reza; Abedini, Yousefali

    2016-04-01

    A facile approach to fabricate a stable superhydrophobic composite comprising multi-walled carbon nanotubes and silicone rubber has been reported. Contact angle of de-ionized water droplets on the prepared surface was measured with the value of near 159°; while water droplets easily rolled off and bounced on it. Surface free energy of the superhydrophobic coating was examined by three methods about 26 mJ/m2. The prepared film shows good stability under high stress conditions such as ultraviolet exposure, heating, pencil hardness test, attacking with different pH value and ionic-strength solutions. In addition, remarkable stability of the coating was observed after soaking in condensed hydrochloric acid, 5 wt.% NaCl aqueous solution, boiling water and tape test.

  7. The effects of early diagenesis on the chemical and stable carbon isotopic composition of wood

    USGS Publications Warehouse

    Spiker, E. C.; Hatcher, P.G.

    1987-01-01

    Studies of modern and ancient buried wood show that there is a linear correlation between carbohydrate content and the stable carbon isotope composition as carbohydrates are preferentially degraded during early diagenesis. As the carbohydrate content decreases, the ??13C value of the degraded wood decreases 1 to 2 per mil, approaching the value of the residual lignin. These results indicate that carbohydrate degradation products are lost and not incorporated into the aromatic structure as lignin is selectively preserved during early diagenesis of wood. These results also indicate that attempts to quantify terrestrial inputs to modern sedimentary organic matter based on ??13C values should consider the possibility of a 1 to 2 per mil decrease in the ??13C value of degraded wood. ?? 1987.

  8. Carbon : nickel nanocomposite templates - predefined stable catalysts for diameter-controlled growth of single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Melkhanova, Svetlana; Haluska, Miro; Hübner, René; Kunze, Tim; Keller, Adrian; Abrasonis, Gintautas; Gemming, Sibylle; Krause, Matthias

    2016-08-01

    Carbon : nickel (C : Ni) nanocomposite templates (NCTs) were used as catalyst precursors for diameter-controlled growth of single-walled carbon nanotubes (SWCNTs) by chemical vapor deposition (CVD). Two NCT types of 2 nm thickness were prepared by ion beam co-sputtering without (type I) or with assisting Ar+ ion irradiation (type II). NCT type I comprised Ni-rich nanoparticles (NPs) with defined diameter in an amorphous carbon matrix, while NCT type II was a homogenous C : Ni film. Based on the Raman spectra of more than 600 individual SWCNTs, the diameter distribution obtained from both types of NCT was determined. SWCNTs with a selective, monomodal diameter distribution are obtained from NCT type I. About 50% of the SWCNTs have a diameter of (1.36 +/- 0.10) nm. In contrast to NCT type I, SWCNTs with a non-selective, relatively homogeneous diameter distribution from 0.80 to 1.40 nm covering 88% of all SWCNTs are obtained from NCT type II. From both catalyst templates predominantly separated as-grown SWCNTs are obtained. They are free of solvents or surfactants, exhibit a low degree of bundling and contain negligible amounts of MWCNTs. The study demonstrates the advantage of predefined catalysts for diameter-controlled SWCNT synthesis in comparison to in situ formed catalysts.Carbon : nickel (C : Ni) nanocomposite templates (NCTs) were used as catalyst precursors for diameter-controlled growth of single-walled carbon nanotubes (SWCNTs) by chemical vapor deposition (CVD). Two NCT types of 2 nm thickness were prepared by ion beam co-sputtering without (type I) or with assisting Ar+ ion irradiation (type II). NCT type I comprised Ni-rich nanoparticles (NPs) with defined diameter in an amorphous carbon matrix, while NCT type II was a homogenous C : Ni film. Based on the Raman spectra of more than 600 individual SWCNTs, the diameter distribution obtained from both types of NCT was determined. SWCNTs with a selective, monomodal diameter distribution are obtained from NCT

  9. Strong and stable doping of carbon nanotubes and graphene by MoOx for transparent electrodes.

    PubMed

    Hellstrom, Sondra L; Vosgueritchian, Michael; Stoltenberg, Randall M; Irfan, Irfan; Hammock, Mallory; Wang, Yinchao Bril; Jia, Chuancheng; Guo, Xuefeng; Gao, Yongli; Bao, Zhenan

    2012-07-11

    MoO(x) has been used for organic semiconductor doping, but it had been considered an inefficient and/or unstable dopant. We report that MoO(x) can strongly and stably dope carbon nanotubes and graphene. Thermally annealed MoO(x)-CNT composites can form durable thin film electrodes with sheet resistances of 100 Ω/sq at 85% transmittance plain and 85 Ω/sq at 83% transmittance with a PEDOT:PSS adlayer. Sheet resistances change less than 10% over 20 days in ambient and less than 2% with overnight heating to 300 °C in air. The MoO(x) can be easily deposited either by thermal evaporation or from solution-based precursors. Excellent stability coupled with high conductivity makes MoO(x)-CNT composites extremely attractive candidates for practical transparent electrodes.

  10. Carbon nanofiber growth in plasma-enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Denysenko, I.; Ostrikov, K.; Cvelbar, U.; Mozetic, M.; Azarenkov, N. A.

    2008-10-01

    A theoretical model to describe the plasma-assisted growth of carbon nanofibers (CNFs) is proposed. Using the model, the plasma-related effects on the nanofiber growth parameters, such as the growth rate due to surface and bulk diffusion, the effective carbon flux to the catalyst surface, the characteristic residence time and diffusion length of carbon atoms on the catalyst surface, and the surface coverages, have been studied. The dependence of these parameters on the catalyst surface temperature and ion and etching gas fluxes to the catalyst surface is quantified. The optimum conditions under which a low-temperature plasma environment can benefit the CNF growth are formulated. These results are in good agreement with the available experimental data on CNF growth and can be used for optimizing synthesis of related nanoassemblies in low-temperature plasma-assisted nanofabrication.

  11. A comprehensive theory for the coupling between terrestrial carbon and water cycles, supported by stable carbon isotope measurements from leaves

    NASA Astrophysics Data System (ADS)

    Wang, H.; Cornwell, W.; Wright, I. J.; Prentice, I. C.

    2014-12-01

    Stomata actively regulate the CO2 concentration inside plant leaves, which co-determines the biochemical rate of photosynthesis. Stomatal behaviour thus controls leaf-level water-use efficiency and the 'exchange rate' between the terrestrial carbon and hydrological cycles. Least-cost theory (based on the hypothesis that plants minimize the combined unit costs of maintaining the capacities for water transport and carbon uptake) predicts that (a) long-term mean values of the ci/ca ratio, i.e. the ratio of leaf-internal to ambient CO2 concentration, should be independent of both photon flux density and ca; and (b) these values should vary systematically with growing-season vapour pressure deficit, growth temperature, and atmospheric pressure. Stable carbon isotope (δ13C) measurements provide an integrated measure of the ci/ca in C3 plants. A number of previous studies have focused on the aridity dependence of δ13C. The temperature dependence seems to have been overlooked, but the elevation dependence has been known for a long time: plants at high elevations have systematically lowered ci/ca, and correspondingly increased photosynthetic capacity (Vcmax). Why this should be is a long-standing puzzle: there are various speculative explanations in the literature, and a certain amount of controversy. By contrast, least-cost theory provides quantitative predictions of all three environmental effects. We have analysed a large (3652) set of δ13C measurements from C3 plants, spanning all latitudes and biomes, and shown that these predictions are quantitatively consistent with environmental dependences that can be shown in the measurements using a generalized linear model. This analysis implies the ability to predict ci/ca ratios for large-scale terrestrial ecosystem modelling. Combined with the long-standing 'co-ordination hypothesis' for the control of photosynthetic capacity, least-cost theory provides a basis for a remarkably simple global model for gross primary

  12. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions.

  13. Carbon Nitride Thin Films Deposited by Cathodic Electrodeposition

    NASA Astrophysics Data System (ADS)

    Cao, Chuanbao; Fu, Jiyu; Zhu, Hesun

    Carbon nitride thin films were prepared by cathodic electrodeposition. The dicyandiamide compound dissovled in acetone was selected as the organic precursor. Single crystal silicon wafers and conductive glass (ITO) wafers were used as substrates. XPS measurements indicated that the films composed of carbon and nitrogen elements. The nitrogen content reached 41%. The polycrystalline β-C3N4 should exit in the prepared film from TED measurements. The nano hardness of the films on ITO substrates were as high as 13 GPa. The structure and properties were studies.

  14. Bulk and Stable Isotopic Compositions of Carbonate Minerals in Martian Meteorite Allan Hills 84001: No Proof of High Formation Temperature

    NASA Technical Reports Server (NTRS)

    Treiman, Allan H.; Romanek, Christopher S.

    1998-01-01

    Understanding the origin of carbonate minerals in the Martian meteorite Allan Hills (ALH) 84001 is crucial to evaluating the hypothesis that they contain traces of ancient Martian life. Using arguments based on chemical equilibria among carbonates and fluids, an origin at greater than 650 C (inimical to life) has been proposed. However, the bulk and stable isotopic compositions of the carbonate minerals are open to multiple interpretations and so lend no particular support to a high-temperature origin. Other methods (possibly less direct) will have to be used to determine the formation temperature of the carbonates in ALH 84001.

  15. A Model-Based Analysis of Nitrogen Deposition: Effects on Forest Carbon Sequestration

    NASA Astrophysics Data System (ADS)

    Dezi, S.; Medlyn, B. E.; Tonon, G.; Magnani, F.

    2009-04-01

    Over the last 150 years nitrogen deposition has increased, especially in the northern hemisphere, mainly due to the use of fossil fuels, deforestation and agricultural practices. Although the impact of this increase on the terrestrial carbon cycle is still uncertain, it is likely that this large perturbation of the global nitrogen cycle will have important effects on carbon cycling, particularly via impacts on forest carbon storage. In the present work we investigated qualitatively the overall response of forest carbon sequestration to nitrogen deposition, and the relative importance of different mechanisms that bring about this response. For this purpose we used the G'DAY forest carbon-nitrogen cycling model (Comins and McMurtrie 1993), introducing some new assumptions which focus on the effect of nitrogen deposition. Specifically the new assumptions are: (i) foliar litterfall and specific leaf area (SLA) are functions of leaf nitrogen concentration; (ii) belowground C allocation is a function of net primary production (NPP); (iii) forest canopies can directly take up nitrogen; (iv) management of forests occurs; (v) leaching occurs only for nitrate nitrogen. We investigated the effect of each assumption on net ecosystem production (NEP), with a step increase in nitrogen deposition from a steady state of 0.4 gN m-2 yr-1 to 2 gN m-2 yr-1, and then running the old and new model versions for different nitrogen deposition levels. Our analysis showed that nitrogen deposition can have a large effect on forest carbon storage at ecosystem level. In particular the effect of the assumptions (ii), (iii) and (iv) seem to be of greater importance, giving rise to a markedly higher level of forest carbon sequestration than in their absence. On the contrary assumptions (i) and (v) seem not to have any particular effect on the NEP simulated. Finally, running the models for different levels of nitrogen deposition showed that estimating forest carbon exchange without taking into

  16. Electrophoretic Deposition of Carbon Nanotubes on 3-Amino-Propyl-Triethoxysilane (APTES) Surface Functionalized Silicon Substrates

    PubMed Central

    Sarkar, Anirban; Daniels-Race, Theda

    2013-01-01

    Fabrication of uniform thin coatings of multi-walled carbon nanotubes (MWCNTs) by electrophoretic deposition (EPD) on semiconductor (silicon) substrates with 3-aminopropyl-triethoxysilane (APTES) surface functionalization has been studied extensively in this report. The gradual deposition and eventual film formation of the carbon nanotubes (CNTs) is greatly assisted by the Coulombic force of attraction existing between the positively charged –NH2 surface groups of APTES and the acid treated, negatively charged nanotubes migrating towards the deposition surfaces. The remarkable deposition characteristics of the CNT coatings by EPD in comparison to the dip coating method and the influence of isopropyl (IPA)-based CNT suspension in the fabricated film quality has also been revealed in this study. The effect of varying APTES concentration (5%–100%) on the Raman spectroscopy and thickness of the deposited CNT film has been discussed in details, as well. The deposition approach has eliminated the need of metal deposition in the electrophoretic deposition approach and, therefore, establishes a cost-effective, fast and entirely room temperature-based fabrication strategy of CNT thin films for a wide range of next generation electronic applications.

  17. Characterization of high temperature deposited Ti-containing hydrogenated carbon thin films

    NASA Astrophysics Data System (ADS)

    Shi, B.; Meng, W. J.; Evans, R. D.

    2004-12-01

    A detailed structural and mechanical characterization was performed on Ti-containing hydrogenated amorphous carbon (Ti-C:H) thin films deposited at ˜600°C by plasma assisted hybrid chemical/physical vapor deposition. The structural and mechanical characteristics of these specimens were compared to those deposited at the lower temperature of ˜250°C. The results indicated that Ti-C :H consisted of a nanocrystalline TiC phase and a hydrogenated amorphous carbon (a-C:H) phase, and that Ti atoms were incorporated into Ti-C :H predominantly as B1-TiC. Deposition at ˜600°C promoted TiC precipitation, resulting in little Ti dissolution within the a-C :H matrix. High temperature deposited Ti-C :H specimens were found to possess lower modulus and hardness values as compared to low temperature deposited specimens, especially at low Ti compositions. This is rationalized by electron microscopy evidence of increased short and medium range graphitic order within the a-C :H matrix of high temperature deposited Ti-C :H, and supported by additional Raman spectroscopic observations. Heat treatments at 600 °C combined with Raman scattering measurements showed that the a-C :H matrix in high temperature deposited Ti-C :H specimens appears to be less structurally sensitive to additional annealing.

  18. Carbonate sediment deposits on the reef front around Oahu, Hawaii

    USGS Publications Warehouse

    Hampton, M.A.; Blay, C.T.; Murray, C.J.

    2004-01-01

    Large sediment deposits on the reff front around Oahu are a possible resource for replenishing eroded beaches. High-resolution subbottom profiles clearly depict the deposits in three study areas: Kailua Bay off the windward coast, Makua to Kahe Point off the leeward coast, and Camp Erdman to Waimea off the north coast. Most of the sediment is in water depths between 20 and 100 m, resting on submerged shelves created during lowstands of sea level. The mapped deposits have a volume of about 4 ?? 108 m3 in water depths less than 100 m, being thickest off the mouth of channels carved into the modern insular shelf, from which most of the sediment issues. Vibracore samples contain various amounts of sediment of similar size to the sand on Oahu beaches, with the most compatible prospects located off Makaha, Haleiwa, and Camp Erdman, and the least compatible ones located in Kailua Bay. Laboratory tests show a positive correlation of abrasion with Halimeda content: samples from Kailua Bay suffered high amounts of attrition, but others were comparable to tested beach samples. The common gray color of the offshore sediment, aesthetically undesirable for sand on popular tourist beaches, was diminished in the laboratory by soaking in heated hydrogen peroxide. ?? Taylor and Francis Inc.

  19. Carbonate Sediment Deposits on the Reef Front Around Oahu, Hawaii

    SciTech Connect

    Hampton, M A.; Blay, Charles T.; Murray, Christopher J.

    2004-06-01

    Large sediment deposits on the reef front around Oahu are a possible resource for replenishing eroded beaches. High-resolution subbottom profiles clearly depict the deposits in three study areas: Kailua Bay off the windward coast, Makua to Kahe Point off the leeward coast, and Camp Erdman to Waimea off the north coast. Most of the sediment is in water depths between 20 and 100 m, resting on submerged shelves created during lowstands of sea level. The mapped deposits have a volume of about 400 million cubic meters in water depths less than 100 m, being thickest off the mouth of channels carved into the modern insular shelf, from which most of the sediment issues. Vibracore samples contain various amounts of sediment of similar size to the sand on Oahu beaches, with the most compatible prospects located off Makaha, Haleiwa, and Camp Erdman and the least compatible ones located in Kailua Bay. Laboratory tests show a positive correlation of abrasion with Halimeda content; samples from Kailua Bay suffered high amounts of attrition but others were comparable to tested beach samples.

  20. Depositing nanometer-sized particles of metals onto carbon allotropes

    NASA Technical Reports Server (NTRS)

    Watson, Kent A. (Inventor); Fallbach, Michael J. (Inventor); Ghose, Sayata (Inventor); Smith, Joseph G. (Inventor); Delozier, Donavon M. (Inventor); Connell, John W. (Inventor)

    2010-01-01

    A process for depositing nanometer-sized metal particles onto a substrate in the absence of aqueous solvents, organic solvents, and reducing agents, and without any required pre-treatment of the substrate, includes preparing an admixture of a metal compound and a substrate by dry mixing a chosen amount of the metal compound with a chosen amount of the substrate; and supplying energy to the admixture in an amount sufficient to deposit zero valance metal particles onto the substrate. This process gives rise to a number of deposited metallic particle sizes which may be controlled. The compositions prepared by this process are used to produce polymer composites by combining them with readily available commodity and engineering plastics. The polymer composites are used as coatings, or they are used to fabricate articles, such as free-standing films, fibers, fabrics, foams, molded and laminated articles, tubes, adhesives, and fiber reinforced articles. These articles are well-suited for many applications requiring thermal conductivity, electrical conductivity, antibacterial activity, catalytic activity, and combinations thereof.

  1. Stable carbon isotopes in dissolved inorganic carbon: extraction and implications for quantifying the contributions from silicate and carbonate weathering in the Krishna River system during peak discharge.

    PubMed

    Laskar, Amzad H; Gandhi, Naveen; Thirumalai, Kaustubh; Yadava, Madhusudan G; Ramesh, Rengaswamy; Mahajan, Ramakant R; Kumar, Dharmendra

    2014-06-01

    We present a comparative study of two offline methods, a newly developed method and an existing one, for the measurement of the stable carbon isotopic composition (δ(13)C) of dissolved inorganic carbon (DIC; δ(13)CDIC) in natural waters. The measured δ(13)CDIC values of different water samples, prepared from laboratory Na2CO3, ground and oceanic waters, and a laboratory carbonate isotope standard, are found to be accurate and reproducible to within 0.5 ‰\\ (1σ). The extraction of CO2 from water samples by these methods does not require pre-treatment or sample poisoning and can be applied to a variety of natural waters to address carbon cycling in the hydrosphere. In addition, we present a simple method (based on a two-end-member mixing model) to estimate the silicate-weathering contribution to DIC in a river system by using the concentration of DIC and its δ(13)C. This approach is tested with data from the Krishna River system as a case study, thereby quantifying the contribution of silicate and carbonate weathering to DIC, particularly during peak discharge.

  2. Carbonate-shelf depositional environments of the Ordovician Viola formation in South-Central Kansas

    USGS Publications Warehouse

    Newell, K.D.

    2000-01-01

    The Upper Ordovician Viola Formation, an important petroleum reservoir in the Midcontinent, is a carbonate unit present over much of the subsurface in Kansas. The Viola is composed of two fining-upward sedimentary packages that are separated from each other by a minor karstic surface representing a brief period of exposure. Each package represents a third-order sedimentary cycle and consists of an echinoderm-rich packstone overlain by a thicker lime mudstone. The echinoderm-rich packstone was deposited nearshore in agitated waters, but subsequently was bioturbated. The overlying lime mudstone was deposited in deeper, quiet waters, and locally contains storm-deposited carbonate sands. Subtle growth of the Central Kansas Arch and Pratt Anticline (structures transecting the depositional shelf) is indicated by packstones and grainstones being thicker over these arches, whereas finer grained lithologies dominate in basinal areas on the arch flanks. Structureless lime mudstones, probably intensely bioturbated, grade into laminated lime mudstones farther basinward.

  3. Fractionation of stable Sr isotopes during carbonate precipitation and surface sorption process

    NASA Astrophysics Data System (ADS)

    Liu, H.; You, C.; Huang, K.; Tu, Y.; Chung, C.

    2010-12-01

    Stable strontium (Sr) isotope has been used as a new tool for constraining the Sr budget in seawater. To further understand the controlling factors of Sr marine mass balance, we study Sr isotope fractionation of new δ87/86Sr* (measured 87Sr/86Sr without normalization) and δ88/86Sr in carbonate precipitation and Sr sorption experiments. For such purpose, a high-precision analytical technique was developed using MC-ICP-MS (Neptune, Thermo Scientific). NIST SRM 3169 Zr standard was doped into samples for mass bias correction, with implementation of combined the standard-sample bracketing method and the Zr internal normalization. In this manner, the 92Zr/90Zr in SRM 3169 was certified by 88Sr/86Sr in SRM 987, calculated off-line via exponential law. The long term external reproducibility for δ87/86Sr* and δ88/86Sr analyses is better than ±0.040‰ and ±0.018‰ (2σ), respectively. Carbonates obtained from the inorganic precipitation experiments display a small, but significant temperature dependent isotopic fractionation trend at 5-40 degrees C in both calcites and aragonites. Sr sorption experiments were performed to evaluate the associated Sr isotope fractionation mechanism.

  4. Stable support based on highly graphitic carbon xerogel for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Jin, Hong; Zhang, Huamin; Ma, Yuanwei; Xu, Ting; Zhong, Hexiang; Wang, Meiri

    Highly graphitic carbon xerogel (GCX) is prepared by the modified sol-gel polymerization process using cobalt nitrate as the catalyst, followed by high temperature treatment at 1800 °C. The as-prepared GCX is explored as a stable support for Pt in proton exchange membrane fuel cells. The results of N 2 sorption measurement and X-ray diffraction analysis (XRD) reveal that GCX has a better mesoporous structure and a preferably higher degree of graphitization, compared with the commercial XC-72 carbon black. The transmission electron microscopy (TEM) image indicates that Pt nanoparticles are well dispersed on GCX and exhibit relatively narrow size distribution. Accelerated aging test (AAT) based on potential cycling is used to investigate the durability of the as-prepared Pt/GCX in comparison with the commercial Pt/C. Electrochemical analysis demonstrates that the catalyst with GCX as a support exhibits an alleviated degradation rate of electrochemical active surface area (39% for Pt/GCX and 53% for Pt/C). The results of single cell durability tests indicate that the voltage loss of Pt/GCX at 100 mA cm -2 is about 50% lower than that of Pt/C. GCX is expected to be a corrosion resistant electrocatalyst support.

  5. Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric CO2 by the Phoenix Lander

    NASA Technical Reports Server (NTRS)

    Niles, Paul B.; Boynton, W. V.; Hoffman, J. H.; Ming, D. W.; Hamara, D.

    2010-01-01

    Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars [1]. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated Delta(sup 13)C values measured in carbonates in martian meteorites [2-4] it has been proposed that the martian atmosphere was enriched in 13C [8]. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated Delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in C-13 relative to CO2 in the terrestrial atmosphere[ 7, 9-11]. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander [12] included a magnetic-sector mass spectrometer (EGA) [13] which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils.

  6. Atomic-layer-deposition-assisted formation of carbon nanoflakes on metal oxides and energy storage application.

    PubMed

    Guan, Cao; Zeng, Zhiyuan; Li, Xianglin; Cao, Xiehong; Fan, Yu; Xia, Xinhui; Pan, Guoxiang; Zhang, Hua; Fan, Hong Jin

    2014-01-29

    Nanostructured carbon is widely used in energy storage devices (e.g., Li-ion and Li-air batteries and supercapacitors). A new method is developed for the generation of carbon nanoflakes on various metal oxide nanostructures by combining atomic layer deposition (ALD) and glucose carbonization. Various metal oxide@nanoflake carbon (MO@f-C) core-branch nanostructures are obtained. For the mechanism, it is proposed that the ALD Al2 O3 and glucose form a composite layer. Upon thermal annealing, the composite layer becomes fragmented and moves outward, accompanied by carbon deposition on the alumina skeleton. When tested as electrochemical supercapacitor electrode, the hierarchical MO@f-C nanostructures exhibit better properties compared with the pristine metal oxides or the carbon coating without ALD. The enhancement can be ascribed to increased specific surface areas and electric conductivity due to the carbon flake coating. This peculiar carbon coating method with the unique hierarchical nanostructure may provide a new insight into the preparation of 'oxides + carbon' hybrid electrode materials for energy storage applications.

  7. Stable isotopic compositions of carbonates from the Mesoproterozoic Bangemall Group, northwestern Australia

    NASA Technical Reports Server (NTRS)

    Buick, R.; Des Marais, D. J.; Knoll, A. H.

    1995-01-01

    Marine carbonate rocks from the Mesoproterozoic Bangemall Group of northwestern Australia show little deviation (+/-1.3%) in whole-rock delta 13C(carb)-values about a mean of -0.5%. This narrow range persists despite close sampling (every 10-20 m) through long sections (up to 2500 m) that are geographically widespread (up to 250 km apart), over many depositional environments (supralittoral to outer shelf), sediment sources (stromatolitic bioherms to detrital calcilutites) and rock types (pure limestones to dolomitic shales). The only major excursions from the norm seem related to unusual environmental or post-depositional processes, as they are correlated with large enrichments (to -3%) or depletions (to -16%) in 18O. Relatively heavy delta 13C-values, up to +2.5%, occur in a single bed of brecciated ferruginous dolostone at a single locality; these abnormal values may result from local evaporitic conditions. Limey and shaley nodular dolostones have delta 13C-values as low as -4.3%, probably caused by remineralization of organic matter during late and patchy dolomitization. Most notably, sharp negative excursions in delta 13C, up to -8.4%, occur in bleached kerogen-free rocks with mineral assemblages of dolomite + quartz + calcite +/- tremolite + talc, reflecting isotopic re-equilibration in thick metamorphic aureoles around dolerite intrusions. General environmental variations are minor, with delta 13C-values of peritidal facies tending to be slightly positive whereas those of subtidal facies are slightly negative. There are no strong secular trends, but subtle fluctuations within the range -2 to +l% can be correlated along the northwestern margin of the basin. This resembles the pattern seen in other Mesoproterozoic successions, but is markedly unlike the heavy background (> +5%) and extreme variations (up to l0%) in delta 13C evident in Neoproterozoic successions of similar thickness and environmental setting. Hence, in contrast to the Neoproterozoic, the global

  8. Stable isotopic compositions of carbonates from the Mesoproterozoic Bangemall Group, northwestern Australia.

    PubMed

    Buick, R; Des Marais, D J; Knoll, A H

    1995-06-20

    Marine carbonate rocks from the Mesoproterozoic Bangemall Group of northwestern Australia show little deviation (+/-1.3%) in whole-rock delta 13C(carb)-values about a mean of -0.5%. This narrow range persists despite close sampling (every 10-20 m) through long sections (up to 2500 m) that are geographically widespread (up to 250 km apart), over many depositional environments (supralittoral to outer shelf), sediment sources (stromatolitic bioherms to detrital calcilutites) and rock types (pure limestones to dolomitic shales). The only major excursions from the norm seem related to unusual environmental or post-depositional processes, as they are correlated with large enrichments (to -3%) or depletions (to -16%) in 18O. Relatively heavy delta 13C-values, up to +2.5%, occur in a single bed of brecciated ferruginous dolostone at a single locality; these abnormal values may result from local evaporitic conditions. Limey and shaley nodular dolostones have delta 13C-values as low as -4.3%, probably caused by remineralization of organic matter during late and patchy dolomitization. Most notably, sharp negative excursions in delta 13C, up to -8.4%, occur in bleached kerogen-free rocks with mineral assemblages of dolomite + quartz + calcite +/- tremolite + talc, reflecting isotopic re-equilibration in thick metamorphic aureoles around dolerite intrusions. General environmental variations are minor, with delta 13C-values of peritidal facies tending to be slightly positive whereas those of subtidal facies are slightly negative. There are no strong secular trends, but subtle fluctuations within the range -2 to +l% can be correlated along the northwestern margin of the basin. This resembles the pattern seen in other Mesoproterozoic successions, but is markedly unlike the heavy background (> +5%) and extreme variations (up to l0%) in delta 13C evident in Neoproterozoic successions of similar thickness and environmental setting. Hence, in contrast to the Neoproterozoic, the global

  9. Pyrolytic deposition of nanostructured titanium carbide coatings on the surface of multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Kremlev, K. V.; Ob"edkov, A. M.; Ketkov, S. Yu.; Kaverin, B. S.; Semenov, N. M.; Gusev, S. A.; Tatarskii, D. A.; Yunin, P. A.

    2016-05-01

    Nanostructured titanium carbide coatings have been deposited on the surface of multiwalled carbon nanotubes (MWCNTs) by the MOCVD method with bis(cyclopentadienyl)titanium dichloride precursor. The obtained TiC/MWCNT hybrid materials were characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. It is established that a TiC coating deposits onto the MWCNT surface with the formation of a core-shell (MWSNT-TiC) type structure.

  10. Stable Carbon Isotope Ratios and Biodegradation Rates of BTEX Compounds at the Tranguch Gasoline Site, Hazelton, Pennsylvania

    DTIC Science & Technology

    2005-03-03

    Absence of Stable Carbon Isotope Fractionation of Satu- rated and Polycyclic Aromatic Hydrocarbons During Aerobic Bacterial Biodegradation ,” Org... biodegradation ; measure the overall metabolic activity and state of the on-site bacterial consortia; and determine fuel hydrocarbon stable isotope ratios...Hazleton, Pennsylvania. The goal of this study was to determine the rates and efficacy of on-site bacterial fuel hydrocarbon biodegradation ; measure

  11. Annealing-Based Electrical Tuning of Cobalt-Carbon Deposits Grown by Focused-Electron-Beam-Induced Deposition.

    PubMed

    Puydinger Dos Santos, Marcos V; Velo, Murilo F; Domingos, Renan D; Zhang, Yucheng; Maeder, Xavier; Guerra-Nuñez, Carlos; Best, James P; Béron, Fanny; Pirota, Kleber R; Moshkalev, Stanislav; Diniz, José A; Utke, Ivo

    2016-11-30

    An effective postgrowth electrical tuning, via an oxygen releasing method, to enhance the content of non-noble metals in deposits directly written with gas-assisted focused-electron-beam-induced deposition (FEBID) is presented. It represents a novel and reproducible method for improving the electrical transport properties of Co-C deposits. The metal content and electrical properties of Co-C-O nanodeposits obtained by electron-induced dissociation of volatile Co2(CO)8 precursor adsorbate molecules were reproducibly tuned by applying postgrowth annealing processes at 100 °C, 200 °C, and 300 °C under high-vacuum for 10 min. Advanced thin film EDX analysis showed that during the annealing process predominantly oxygen is released from the Co-C-O deposits, yielding an atomic ratio of Co:C:O = 100:16:1 (85:14:1) with respect to the atomic composition of as-written Co:C:O = 100:21:28 (67:14:19). In-depth Raman analysis suggests that the amorphous carbon contained in the as-written deposit turns into graphite nanocrystals with size of about 22.4 nm with annealing temperature. Remarkably, these microstructural changes allow for tuning of the electrical resistivity of the deposits over 3 orders of magnitude from 26 mΩ cm down to 26 μΩ cm, achieving a residual resistivity of ρ2K/ρ300 K = 0.56, close to the value of 0.53 for pure Co films with similar dimensions, making it especially interesting and advantageous over the numerous works already published for applications such as advanced scanning-probe systems, magnetic memory, storage, and ferroelectric tunnel junction memristors, as the graphitic matrix protects the cobalt from being oxidized under an ambient atmosphere.

  12. Amorphous Ultrathin SnO2 Films by Atomic Layer Deposition on Graphene Network as Highly Stable Anodes for Lithium-Ion Batteries.

    PubMed

    Xie, Ming; Sun, Xiang; George, Steven M; Zhou, Changgong; Lian, Jie; Zhou, Yun

    2015-12-23

    Amorphous SnO2 (a-SnO2) thin films were conformally coated onto the surface of reduced graphene oxide (G) using atomic layer deposition (ALD). The electrochemical characteristics of the a-SnO2/G nanocomposites were then determined using cyclic voltammetry and galvanostatic charge/discharge curves. Because the SnO2 ALD films were ultrathin and amorphous, the impact of the large volume expansion of SnO2 upon cycling was greatly reduced. With as few as five formation cycles best reported in the literature, a-SnO2/G nanocomposites reached stable capacities of 800 mAh g(-1) at 100 mA g(-1) and 450 mAh g(-1) at 1000 mA g(-1). The capacity from a-SnO2 is higher than the bulk theoretical values. The extra capacity is attributed to additional interfacial charge storage resulting from the high surface area of the a-SnO2/G nanocomposites. These results demonstrate that metal oxide ALD on high surface area conducting carbon substrates can be used to fabricate high power and high capacity electrode materials for lithium-ion batteries.

  13. The Stable Carbon Isotope Ratio Analysis of Atmospheric Non-Methane Hydrocarbons in Los Angeles, California

    NASA Astrophysics Data System (ADS)

    Gotoh, A. A.; Tyler, S. C.; Meinardi, S.; Gervais, K.; Blake, D. R.

    2003-12-01

    Los Angeles type photochemical air pollution is caused by non-methane hydrocarbons (NMHCs) reacting with hydroxyl radicals and nitrous oxides in the presence of light. To create more effective control strategies in reducing such air pollution, it is essential to have both a better understanding of the complex photochemical processes of NMHCs and the sources of these compounds. From the past successful studies of other atmospheric trace gases such as methane and carbon monoxide, we expect that the stable carbon ratio (13C/12C, reported as a δ 13C value) of each of these hydrocarbons will also reflect the δ 13C value of the source material and/or provide formation on chemical loss processes that fractionate C isotopes. We have developed a NMHC preconcentrator system which enables us to measure δ 13C values using a continuous-flow gas chromatography combustion isotope ratio mass spectrometer (cf-GC/C/IRMS). Our system is similar to the successful design pioneered in Rudolph et al. (1997), but is custom designed by our laboratory. Stable carbon isotope measurements of any of the C2-C5 NMHCs in field and/or lab studies are scarce to date. Our system allows us to report on δ 13C measurements of ethane, ethene, ethyne, propane, propene, n-butane, i-butane, 1-butene, n-pentane, i-pentane, and methyl chloride. To see if we can learn the specific sources contributing to the emissions of a given NMHC within a region by comparing isotopic signatures of its potential sources to δ 13C measurements of it within the local air mass, urban air samples were collected in 3 different cities of Los Angeles County, California, USA, during the summer of 2003 and analyzed for the concentrations and δ 13C values of NMHCs. To our knowledge, this is the first δ 13C analysis of ambient NMHCs conducted in the United States. We report the results of the δ 13C analyses and concentration measurements for selected NMHC species from the urban air samples, and their implications for the local

  14. Stable carbon isotopic compositions of organic acids in total suspended particles and dusts from Guangzhou, China

    NASA Astrophysics Data System (ADS)

    Ma, Shexia; Peng, Ping'an; Song, Jianzhong; Zhao, Jinping; He, Lulu; Sheng, Guoying; Fu, Jiamo

    2010-10-01

    Stable carbon isotopic compositions of individual organic acids were determined in total suspended particles and dusts from Guangzhou. The δ 13C values of high molecular weight n-alkanoic acids (C 20-C 28) varied from -34.1‰ to -32.4‰ and tended to be heavier in summer and lighter in winter. These δ 13C values indicate that high molecular weight n-alkanoic acids were derived mainly from emission by C 3 plants. Reduced biological synthesis of high molecular weight n-alkanoic acids in winter may be the reason for the light carbon isotopic composition. The δ 13C values of low molecular weight n-alkanoic acids (C 10-C 18) changed from -31.7‰ to -30.3‰ and exhibited a reverse seasonal trend, i.e., heavier in winter and lighter in summer. Slightly heavier δ 13C values of low molecular weight n-alkanoic acids than those of high molecular weight n-alkanoic acids suggested that they may be emitted from blended sources, e.g., anthropogenic sources and vegetation waxes. Lighter δ 13C values in summer may be attributed to relatively low anthropogenic sources and high botanic sources in summer. Dicarboxylic acids and aromatic acids have been proposed as secondary products from photochemical degradation. The average δ 13C values of dicarboxylic acids and aromatic acids were heavier, and ranged from -25.2‰ to -22.9‰ and from -30.0‰ to -27.6‰, respectively. Both dicarboxylic acids and aromatic acids displayed the same temporal variations in the δ 13C values, i.e., negative δ 13C in the summer samples and positive in the winter samples, which may be controlled by photochemical reactions; they are generally severe in winter in Guangzhou under the monsoon weather system. The heaviest δ 13C values were observed in dicarboxylic acids, indicating that dicarboxylic acids were formed by fast and more complete oxidation reactions. These results indicate that the stable carbon isotopic composition of organic acids may provide important information about sources and

  15. Characteristic Study of Boron Doped Carbon Nanowalls Films Deposited by Microwave Plasma Enhanced Chemical Vapor Deposition.

    PubMed

    Lu, Chunyuan; Dong, Qi; Tulugan, Kelimu; Park, Yeong Min; More, Mahendra A; Kim, Jaeho; Kim, Tae Gyu

    2016-02-01

    In this research, catalyst-free vertically aligned boron doped carbon nanowalls films were fabricated on silicon (100) substrates by MPECVD using feeding gases CH4, H2 and B2H6 (diluted with H2 to 5% vol) as precursors. The substrates were pre-seeded with nanodiamond colloid. The fabricated CNWs films were characterized by Scanning Electron Microscopy (SEM) and Raman Spectroscopy. The data obtained from SEM confirms that the CNWs films have different density and wall thickness. From Raman spectrum, a G peak around 1588 cm(-1) and a D band peak at 1362 cm(-1) were observed, which indicates a successful fabrication of CNWs films. The EDX spectrum of boron doped CNWs film shows the existence of boron and carbon. Furthermore, field emission properties of boron doped carbon nanowalls films were measured and field enhancement factor was calculated using Fowler-Nordheim plot. The result indicates that boron doped CNWs films could be potential electron emitting materials.

  16. Facile synthesis of carbon/MoO3 nanocomposites as stable battery anodes

    NASA Astrophysics Data System (ADS)

    Ding, Jiang; Abbas, Syed Ali; Hanmandlu, Chintam; Lin, Lin; Lai, Chao-Sung; Wang, Pen-Cheng; Li, Lain-Jong; Chu, Chih-Wei; Chang, Chien-Cheng

    2017-04-01

    Pristine MoO3 is a potential anode material for lithium-ion batteries (LIBs), due to its high specific capacity (1117 mA h g-1); it suffers, however, from poor cyclability, resulting from a low conductivity and large volume changes during lithiation/delithiation process. Here we adopt a facile two-step method in which pristine bulk MoO3 is first converted into MoO3 nanorods (MoO3 NR) through mechanical grinding, to buffer the continuous volume changes, and then coated with amorphous carbon through simple stirring and heating, to provide high electronic and ionic conductivities. Electrochemical tests reveal that the carbon-coated MoO3 nanorods (C-MoO3 NRs) exhibit outstanding specific capacity (856 mA h g-1 after 110 cycles at a current density of 0.1 C); remarkable cycle life, among the best reported for carbon-based MoO3 nanostructures (485 mA h g-1 after 300 cycles at 0.5 C and 373 mA h g-1 after 400 cycles at 0.75 C); and greatly improved capacity retention (up to 90.4% after various C-rates) compared to bulk MoO3. We confirm the versatility of the C-MoO3 NR anodes by preparing flexible batteries that display stable performance, even in bent state. This simple approach toward C-MoO3 NR anodes proceeds without rigorous chemical synthesis or extremely high temperatures, making it a scalable solution to prepare high-capacity anodes for next-generation LIBs.

  17. Preliminary identification of ground-water nitrate sources using nitrogen and carbon stable isotopes, Kansas

    USGS Publications Warehouse

    Townsend, M.A.; Macko, S.A.

    2007-01-01

    Increasing nitrate-N in ground water is a problem in areas with limited ground-water supplies, such as central Kansas. Nitrate-N concentrations in ground water in the study area in Ellis County range from 0.9 to 26 mg/L. Calculated mean values observed in soil cores are 1.2-15 mg/kg. The ??15N signatures of the ground waters are more enriched (+16.8 to +28.7???) than those of the soils (+8.4 to +1 3.7???), strongly suggesting that nitrate-N sources are not from mineralized and labile nitrogen present in the unsaturated zone. Soil cores were collected near municipal wells to determine if soil nitrogen was a contributing source to the ground water. Increased ??15N of total nitrogen with depth suggests that microbial mineralization processes and possible denitrification or volatilization isotope enrichments have affected the observed ?? 15N signatures in the soil. However, the observed soil-nitrogen values are not of sufficient magnitude to explain the nitrate-N concentrations or associated ??15N values observed in the ground water. Stable carbon isotopes provide some supporting evidence that soils are not a major contributor to the observed nitrate-N concentration in the ground water. ?? 13C values of the dissolved organic carbon (DOC) in soils generally become more enriched with depth while corresponding ground-water ??13C (DOC) values are more depleted than in the overlying soils. Carbon isotope values of the soils are indicative of a C4 plant source that is enriched by microbial processes. The ??13C (DOC) of ground water indicates C3 values that may reflect impacts from animal-waste sources.

  18. Annual and seasonal distribution of intertidal foraminifera and stable carbon isotope geochemistry, Bandon Marsh, Oregon, USA

    USGS Publications Warehouse

    Milker, Yvonne; Horton, Benjamin; Vane, Christopher; Engelhart, Simon; Nelson, Alan R.; Witter, Robert C.; Khan, Nicole S.; Bridgeland, William

    2014-01-01

    We investigated the influence of inter-annual and seasonal differences on the distribution of live and dead foraminifera, and the inter-annual variability of stable carbon isotopes (d13C), total organic carbon (TOC) values and carbon to nitrogen (C/N) ratios in bulk sediments from intertidal environments of Bandon Marsh (Oregon, USA). Living and dead foraminiferal species from 10 stations were analyzed over two successive years in the summer (dry) and fall (wet) seasons. There were insignificant inter-annual and seasonal variations in the distribution of live and dead species. But there was a noticeable decrease in calcareous assemblages (Haynesina sp.) between live populations and dead assemblages, indicating that most of the calcareous tests were dissolved after burial; the agglutinated assemblages were comparable between constituents. The live populations and dead assemblages were dominated by Miliammina fusca in the tidal flat and low marsh, Jadammina macrescens, Trochammina inflata and M. fusca in the high marsh, and Trochamminita irregularis and Balticammina pseudomacrescens in the highest marsh to upland. Geochemical analyses (d13C, TOC and C/N of bulk sedimentary organic matter) show no significant influence of inter-annual variations but a significant correlation of d13C values (R = 20.820, p , 0.001), TOC values (R = 0.849, p , 0.001) and C/N ratios (R = 0.885, p , 0.001) to elevation with respect to the tidal frame. Our results suggest that foraminiferal assemblages and d13C and TOC values, as well as C/N ratios, in Bandon Marsh are useful in reconstructing paleosea-levels on the North American Pacific coast.

  19. Evaluating the Contributions of Atmospheric Deposition of Carbon and Other Nutrients to Nitrification in Alpine Environments

    NASA Astrophysics Data System (ADS)

    Oldani, K. M.; Mladenov, N.; Williams, M. W.

    2013-12-01

    The Colorado Front Range of the Rocky Mountains contains undeveloped, barren soils, yet in this environment there is strong evidence for a microbial role in increased nitrogen (N) export. Barren soils in alpine environments are severely carbon-limited, which is the main energy source for microbial activity and sustenance of life. It has been shown that atmospheric deposition can contain high amounts of organic carbon (C). Atmospheric pollutants, dust events, and biological aerosols, such as bacteria, may be important contributors to the atmospheric organic C load. In this stage of the research we evaluated seasonal trends in the chemical composition and optical spectroscopic (fluorescence and UV-vis absorbance) signatures of snow, wet deposition, and dry deposition in an alpine environment at Niwot Ridge in the Rocky Mountains of Colorado to obtain a better understanding of the sources and chemical character of atmospheric deposition. Our results reveal a positive trend between dissolved organic carbon concentrations and calcium, nitrate and sulfate concentrations in wet and dry deposition, which may be derived from such sources as dust and urban air pollution. We also observed the presence of seasonally-variable fluorescent components that may be attributed to fluorescent pigments in bacteria. These results are relevant because atmospheric inputs of carbon and other nutrients may influence nitrification in barren, alpine soils and, ultimately, the export of nitrate to alpine watersheds.

  20. Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

    NASA Technical Reports Server (NTRS)

    Sunkara, M. K.; Ueno, M.; Lian, G.; Dickey, E. C.

    2001-01-01

    We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

  1. Ironstone deposits hosted in Eocene carbonates from Bahariya (Egypt)-New perspective on cherty ironstone occurrences

    NASA Astrophysics Data System (ADS)

    Afify, A. M.; Sanz-Montero, M. E.; Calvo, J. P.

    2015-11-01

    This paper gives new insight into the genesis of cherty ironstone deposits. The research was centered on well-exposed, unique cherty ironstone mineralization associated with Eocene carbonates from the northern part of the Bahariya Depression (Egypt). The economically important ironstones occur in the Naqb Formation (Early Eocene), which is mainly formed of shallow marine carbonate deposits. Periods of lowstand sea-level caused extensive early dissolution (karstification) of the depositional carbonates and dolomitization associated with mixing zones of fresh and marine pore-water. In faulted areas, the Eocene carbonate deposits were transformed into cherty ironstone with preservation of the precursor carbonate sedimentary features, i.e. skeletal and non-skeletal grain types, thickness, bedding, lateral and vertical sequential arrangement, and karst profiles. The ore deposits are composed of iron oxyhydroxides, mainly hematite and goethite, chert in the form of micro- to macro-quartz and chalcedony, various manganese minerals, barite, and a number of subordinate sulfate and clay minerals. Detailed petrographic analysis shows that quartz and iron oxides were coetaneous and selectively replaced carbonates, the coarse dolomite crystals having been preferentially transformed into quartz whereas the micro-crystalline carbonates were replaced by the iron oxyhydroxides. A number of petrographic, sedimentological and structural features including the presence of hydrothermal-mediated minerals (e.g., jacobsite), the geochemistry of the ore minerals as well as the structure-controlled location of the mineralization suggest a hydrothermal source for the ore-bearing fluids circulating through major faults and reflect their proximity to centers of magmatism. The proposed formation model can contribute to better understanding of the genetic mechanisms of formation of banded iron formations (BIFs) that were abundant during the Precambrian.

  2. Stable carbon isotopes of dissolved inorganic carbon for a zonal transect across the subpolar North Atlantic Ocean in summer 2014

    NASA Astrophysics Data System (ADS)

    Humphreys, Matthew P.; Greatrix, Florence M.; Tynan, Eithne; Achterberg, Eric P.; Griffiths, Alex M.; Fry, Claudia H.; Garley, Rebecca; McDonald, Alison; Boyce, Adrian J.

    2016-06-01

    The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in samples collected during June-July 2014 in the subpolar North Atlantic. Sample collection was carried out on the RRS James Clark Ross cruise JR302, part of the "Radiatively Active Gases from the North Atlantic Region and Climate Change" (RAGNARoCC) research programme. The observed δ13CDIC values for cruise JR302 fall in a range from -0.07 to +1.95 ‰, relative to the Vienna Pee Dee Belemnite standard. From duplicate samples collected during the cruise, the 1σ precision for the 341 results is 0.08 ‰, which is similar to our previous work and other studies of this kind. We also performed a cross-over analysis using nearby historical δ13CDIC data, which indicated that there were no significant systematic offsets between our measurements and previously published results. We also included seawater reference material (RM) produced by A. G. Dickson (Scripps Institution of Oceanography, USA) in every batch of analysis, enabling us to improve upon the calibration and quality-control procedures from a previous study. The δ13CDIC is consistent within each RM batch, although its value is not certified. We report δ13CDIC values of 1.15 ± 0.03 ‰ and 1.27 ± 0.05 ‰ for batches 141 and 144 respectively. Our JR302 δ13CDIC data can be used - along with measurements of other biogeochemical variables - to constrain the processes that control DIC in the interior ocean, in particular the oceanic uptake of anthropogenic carbon dioxide and the biological carbon pump. Our δ13CDIC results are available from the British Oceanographic Data Centre - doi:10.5285/22235f1a-b7f3-687f-e053-6c86abc0c8a6.

  3. Growth mechanism of carbon nanotubes grown by microwave plasma-assisted chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Muneyoshi, T.; Okai, M.; Yaguchi, T.; Sasaki, S.

    2001-10-01

    To investigate the most suitable deposition conditions and growth mechanism, we grew carbon nanotubes (CNTs) by microwave plasma-assisted chemical vapor deposition under various conditions. The experimental parameters we varied were (a) the mixture ratio of methane in hydrogen, (b) the total gas pressure, and (c) the bias electric current. We found that the bias electric current was the most influential parameter in determining the shape of CNTs. We believe that the growth process of CNTs can be explained by using the solid solubility curves of metal-carbon phase diagrams. Selective growth and low-temperature growth of CNTs can also be understood from these phase diagrams.

  4. Thin germanium carbon layers deposited directly on silicon for metal oxide semiconductor devices

    NASA Astrophysics Data System (ADS)

    Kelly, D. Q.; Wiedmann, I.; García-Gutierrez, D. I.; José-Yacamán, M.; Banerjee, S. K.

    2007-01-01

    We report the growth process and materials characterization of germanium-carbon alloys (Ge1-xCx) deposited directly on Si (1 0 0) substrates by ultra-high-vacuum chemical vapour deposition. The Ge1-xCx films are characterized by transmission electron microscopy, etch-pit density, x-ray diffraction, secondary ion mass spectrometry and electron energy loss spectroscopy. The results show that the films exhibit low threading dislocation densities despite significant strain relaxation. We also present evidence for carbon segregation in the Ge1-xCx and interpret these results as a strain relaxation mechanism.

  5. Paired carbon stable-isotope records for the Cenomanian Stage (100.5 -93.9 Ma): correlation tool and Late Cretaceous pCO2 record?

    NASA Astrophysics Data System (ADS)

    Jarvis, Ian; Gröcke, Darren; Laurin, Jiří; Selby, David; Roest-Ellis, Sascha; Miles, Andrew; Lignum, John; Gale, Andrew; Kennedy, Jim

    2016-04-01

    Carbon stable-isotope stratigraphy of marine carbonates (δ13Ccarb) provides remarkable insights into past variation in the global carbon cycle, and has become firmly established as a powerful global correlation tool. Continuous δ13Ccarb time series are becoming increasingly available for much of the geological record, including the Upper Cretaceous. However, our knowledge of stratigraphic variation in the carbon isotopic composition of sedimentary organic matter (δ13Corg) is much poorer, and is generally restricted to organic-rich sedimentary successions and/or key boundary intervals. Close coupling exists between the global isotopic composition of the reduced and oxidised carbon reservoirs on geological time scales, but the stratigraphic resolution of most long-term δ13Corg Mesozoic records is inadequate to identify leads and lags in the responses of the two reservoirs to carbon cycle perturbations. Cenomanian times (100.5-93.9 Ma) represent perhaps the best documented episode of eustatic rise in sea level in Earth history and the beginning of the Late Mesozoic thermal maximum, driving global expansion of epicontinental seas and the onset of widespread pelagic and hemipelagic carbonate deposition. Significant changes occurred in global stable-isotope records, including two prominent perturbations of the carbon cycle - the Mid-Cenomanian Event I (MCEI; ~96.5-96.2 Ma) and Oceanic Anoxic Event 2 (OAE2; ~94.5-93.8 Ma). OAE2, one of two truly global Cretaceous OAEs, was marked by the widespread deposition of black shales, and a global positive carbon stable-isotope excursion of 2.0 - 2.5‰ δ13Ccarb, and up to 7‰ in the sulphur-bound phytane biomarker. MCEI, by contrast, shows a <1‰ δ13Ccarb excursion and no associated black shales in most areas. Here, we present detailed paired δ13Ccarb and δ13Corg stable-isotope records for the entire Cenomanian Stage, based on an Upper Albian - Lower Turonian composite reference section from the Vocontian Basin of SE

  6. Gastric mucosal status susceptible to lanthanum deposition in patients treated with dialysis and lanthanum carbonate.

    PubMed

    Ban, Shinichi; Suzuki, Syunji; Kubota, Kenji; Ohshima, Susumu; Satoh, Hideaki; Imada, Hiroki; Ueda, Yoshihiko

    2017-02-01

    Lanthanum carbonate is a popular chemical which is administered for patients with end-stage kidney disease to reduce the absorption of phosphate, and lanthanum deposition in the gastroduodenal mucosa has recently been reported. The aim of this study was to assess whether any histologic changes of the gastric mucosa are related to the deposition of lanthanum. Twenty-four patients who revealed the histology of lanthanum deposition on gastroduodenal biopsy between 2011 and 2014 were included in the study, and their clinical records and gastroduodenal biopsies obtained from 2011 to 2015 were reviewed, adding the review of gastroduodenal biopsies before 2011 if possible. Analysis of the deposited materials by scanning electron microscopy-energy dispersive x-ray spectroscopy was performed for a representative gastric biopsy. All patients were diagnosed as having renal insufficiency due to chronic kidney disease and treated with dialysis for more than 5 years, with confirmation of lanthanum carbonate use for 22 patients. Of 121 gastric biopsies and 10 duodenal ones between 2011 and 2015, 86 gastric biopsies (71.1%) and 3 duodenal biopsies (30%), respectively, revealed histology consistent with lanthanum deposition, which was confirmed by scanning electron microscopy-energy dispersive x-ray spectroscopy analysis for a representative case. The deposition tended to occur in the gastric mucosa with regenerative change, intestinal metaplasia, or foveolar hyperplasia (P<.05). Such mucosal changes were observed in about half of the gastric biopsy samples obtained prior to 2010, in which no lanthanum deposition was identified irrespective of the gastric mucosal status. Although direct association between lanthanum deposition and clinical symptoms is not clear, the evaluation of the gastric mucosal status (prior to administration) seems to be important to predict lanthanum deposition when lanthanum carbonate is administered for patients with chronic kidney disease treated with

  7. Spray-gun deposition of catalyst for large area and versatile synthesis of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Gohier, A.; Kim, K.-H.; Norman, E. D.; Gorintin, L.; Bondavalli, P.; Cojocaru, C. S.

    2012-06-01

    Spray gun deposition technique was investigated for large area deposition of nano-catalysts. In particular, we studied iron chloride salts solutions as catalyst precursor for the synthesis of carbon nanotubes (CNTs). Iron chloride salts are shown to decompose upon thermal annealing into Fe(III) oxide based species that make it suitable for further growth of various carbon nanotube structures. Depending on the spraying process, versatile synthesis of 2-D single-walled carbon nanotube network as well as vertically aligned carbon nanotubes arrays on functional substrates can be achieved. Such simple process for the preparation of CNT-based architecture opens new perspectives in the field of thin-film transistor and nanostructured electrodes.

  8. Carbon deposition during oxygen production using high temperature electrolysis and mitigation methods

    NASA Astrophysics Data System (ADS)

    Bernadowski, Timothy Adam, Jr.

    Carbon dioxide in the Martian atmosphere can be converted to oxygen during high temperature electrolysis for use in life-support and fuel systems on manned missions to the red planet. During electrolysis of carbon dioxide to produce oxygen, carbon can deposit on the electrolysis cell resulting in lower efficiency and possibly cell damage. This would be detrimental, especially when the oxygen product is used as the key element of a space life support system. In this thesis, a theoretical model was developed to predict hazardous carbon deposition conditions under various operating conditions within the Martian atmosphere. The model can be used as a guide to determine the ideal operating conditions of the high-temperature oxygen production system. A parallel experimental investigation is underway to evaluate the accuracy of the theoretical model. The experimental design, cell fabrication, and some preliminary results as well as future work recommendations are also presented in this thesis.

  9. Characterization of carbon deposits from jet fuel on Inconel 600 and Inconel X surfaces

    SciTech Connect

    Altin, O.; Eser, S.

    2000-03-01

    Flow reactor experiments were conducted to study carbon deposit formation from decomposition of a jet fuel (JP-8) at 500 C and 500 psig for 5 h on the surface of two superalloys, Inconel 600 and Inconel X. The deposits collected on superalloy surfaces were characterized by temperature-programmed oxidation, size exclusion microscopy, and energy-dispersive X-ray spectroscopy. Significantly lower deposition on Inconel X compared to that on Inconel 600 was attributed to the presence of minor elemental compounds, such as Al, T, Nb, and Ta in the Inconel X alloy.

  10. Chemical Vapor Deposition Growth of Linked Carbon Monolayers with Acetylenic Scaffoldings on Silver Foil.

    PubMed

    Liu, Rong; Gao, Xin; Zhou, Jingyuan; Xu, Hua; Li, Zhenzhu; Zhang, Shuqing; Xie, Ziqian; Zhang, Jin; Liu, Zhongfan

    2017-03-02

    Graphdiyne analogs, linked carbon monolayers with acetylenic scaffoldings, are fabricated by adopting low-temperature chemical vapor deposition which provides a route for the synthesis of two-dimensional carbon materials via molecular building blocks. The electrical conductivity of the as-grown films can reach up to 6.72 S cm(-1) . Moreover, the films show potential as promising substrates for fluorescence suppressing and Raman advancement.

  11. Intermediate-temperature solid oxide fuel cell employing reformed effective biogas: Power generation and inhibition of carbon deposition

    NASA Astrophysics Data System (ADS)

    Miyake, Michihiro; Iwami, Makoto; Goto, Kenta; Iwamoto, Kazuhito; Morimoto, Koki; Shiraishi, Makoto; Takatori, Kenji; Takeuchi, Mizue; Nishimoto, Shunsuke; Kameshima, Yoshikazu

    2017-02-01

    A power generation system consisting of an intermediate-temperature solid oxide fuel cell (IT-SOFC) and an external reformer for biogas is developed, and its performance is investigated for advanced use of effective biogas. The IT-SOFC is fueled with syngas produced via biogas reforming, and is successfully operated at 600 and 700 °C using Ni0.8Cu0.2 alloy/gadolinia-doped ceria electrolyte (Ni0.8Cu0.2/GDC) cermet anodes and a LaAlO3 supported-Ni (Ni/LaAlO3) catalyst. The Ni/LaAlO3 catalyst stably exhibits high reforming performance for effective biogas at 800 °C for 27 h, and carbon deposition on the catalyst is prevented. The electrochemical performance of the Ni0.8Cu0.2/GDC cermet anode using syngas fuel possessing a H2:CO ratio of approximately 3:1 is comparable to the performance achieved with H2 fuel; the anode remains stable after 24 h of operation at 700 °C without interruption and is unaffected by carbon deposition.

  12. Nickel-based anode with water storage capability to mitigate carbon deposition for direct ethanol solid oxide fuel cells.

    PubMed

    Wang, Wei; Su, Chao; Ran, Ran; Zhao, Bote; Shao, Zongping; Tade, Moses O; Liu, Shaomin

    2014-06-01

    The potential to use ethanol as a fuel places solid oxide fuel cells (SOFCs) as a sustainable technology for clean energy delivery because of the renewable features of ethanol versus hydrogen. In this work, we developed a new class of anode catalyst exemplified by Ni+BaZr0.4Ce0.4Y0.2O3 (Ni+BZCY) with a water storage capability to overcome the persistent problem of carbon deposition. Ni+BZCY performed very well in catalytic efficiency, water storage capability and coking resistance tests. A stable and high power output was well maintained with a peak power density of 750 mW cm(-2) at 750 °C. The SOFC with the new robust anode performed for seven days without any sign of performance decay, whereas SOFCs with conventional anodes failed in less than 2 h because of significant carbon deposition. Our findings indicate the potential applications of these water storage cermets as catalysts in hydrocarbon reforming and as anodes for SOFCs that operate directly on hydrocarbons.

  13. Investigating Environmental Influences on the Morphology and Stable Isotope Changes in a Holocene Peat Deposit from Congaree National Park

    NASA Astrophysics Data System (ADS)

    Wesselschmidt, N.; Werts, S. P.

    2011-12-01

    Congaree National Park, near Columbia, South Carolina, is a floodplain forest that contains the United States' largest contiguous track of old-growth bottomland forest as well as one of the highest natural canopies that remains on Earth. A portion of the park contains a groundwater fed muckswamp and is in the footprint of several ancient meanders of the Congaree River. Within one ancient meander lies an extensive peat deposit assembled over thousands of years from the formation of an oxbow lake. The aim of this study is to investigate the environmental influences affecting the development of this peat deposit and implications on paleoclimate investigation of the southeastern US since the last ice age. From this deposit, a 3.5 meter long core was extracted with a basal date of 21,000 years before present (kyr). We have sampled this core for δ13C and δ15N values in both the bulk peat and in monocot macrofossils which were present through most sections of the entire core. The bulk peat was sampled at key changes in morphology and the monocot samples were taken at 8 cm intervals. This data reveals a sawtooth pattern of variation of about 1% throughout the lower two meters (-28.5 to -29.5%) before a much more negative excursion down to -30% in the last half a meter. We have also obtained several radiocarbon dates indicating that the initial oxbow lake filled within approximately 1000 years followed by a depositional hiatus or erosional surface occurring between 10,000 and 20,000 kyr. This was followed by a period of slow peat accumulation through 3500 kyr. In more recent years (<160 yrs), an inorganic lens has developed within the upper 10 cm of the core. Further investigation into this section of the core suggest the possibility of vertical leaching and subsequent removal of organic material from this section. Results from this study have implications in further investigations into carbon cycling and storage within Congaree National Park.

  14. Patterned growth of carbon nanotubes obtained by high density plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Mousinho, A. P.; Mansano, R. D.

    2015-03-01

    Patterned growth of carbon nanotubes by chemical vapor deposition represents an assembly approach to place and orient nanotubes at a stage as early as when they are synthesized. In this work, the carbon nanotubes were obtained at room temperature by High Density Plasmas Chemical Vapor Deposition (HDPCVD) system. This CVD system uses a new concept of plasma generation, where a planar coil coupled to an RF system for plasma generation was used with an electrostatic shield for plasma densification. In this mode, high density plasmas are obtained. We also report the patterned growth of carbon nanotubes on full 4-in Si wafers, using pure methane plasmas and iron as precursor material (seed). Photolithography processes were used to pattern the regions on the silicon wafers. The carbon nanotubes were characterized by micro-Raman spectroscopy, the spectra showed very single-walled carbon nanotubes axial vibration modes around 1590 cm-1 and radial breathing modes (RBM) around 120-400 cm-1, confirming that high quality of the carbon nanotubes obtained in this work. The carbon nanotubes were analyzed by atomic force microscopy and scanning electron microscopy too. The results showed that is possible obtain high-aligned carbon nanotubes with patterned growth on a silicon wafer with high reproducibility and control.

  15. Woody plant encroachment into grasslands leads to accelerated erosion of previously stable organic carbon from dryland soils

    NASA Astrophysics Data System (ADS)

    Puttock, Alan; Dungait, Jennifer A. J.; Macleod, Christopher J. A.; Bol, Roland; Brazier, Richard E.

    2014-12-01

    Drylands worldwide are experiencing rapid and extensive environmental change, concomitant with the encroachment of woody vegetation into grasslands. Woody encroachment leads to changes in both the structure and function of dryland ecosystems and has been shown to result in accelerated soil erosion and loss of soil nutrients. Covering 40% of the terrestrial land surface, dryland environments are of global importance, both as a habitat and a soil carbon store. Relationships between environmental change, soil erosion, and the carbon cycle are uncertain. There is a clear need to further our understanding of dryland vegetation change and impacts on carbon dynamics. Here two grass-to-woody ecotones that occur across large areas of the southwestern United States are investigated. This study takes a multidisciplinary approach, combining ecohydrological monitoring of structure and function and a dual-proxy biogeochemical tracing approach using the unique natural biochemical signatures of the vegetation. Results show that following woody encroachment, not only do these drylands lose significantly more soil and organic carbon via erosion but that this includes significant amounts of legacy organic carbon which would previously have been stable under grass cover. Results suggest that these dryland soils may not act as a stable organic carbon pool, following encroachment and that accelerated erosion of carbon, driven by vegetation change, has important implications for carbon dynamics.

  16. Effects of early seafloor processes on skeletal carbonate deposits, Ross Sea, Antarctica

    NASA Astrophysics Data System (ADS)

    Frank, T. D.; Färber, C.; James, N. P.

    2015-12-01

    Although relatively rare in space and time, skeletal carbonates deposited in glacially influenced settings hold great potential for improving understanding of the oceanography of the high latitudes. Accumulation in an environment where ocean water is close to carbonate undersaturation has major implications for component preservation and thus potential translation into the geological record. To understand the effects of early seafloor processes, we investigate Quaternary deposits of carbonates recovered in piston cores from the Ross Sea, Antarctica. In this setting, unconsolidated skeletal gravels and sands mantle areas of the outer shelf swept by bottom currents and beneath a zone of high primary productivity. Deposits are dominated locally by either stylasterine hydrocorals, barnacles, or bryozoans, comprising assemblages that differ from those living today. Radiocarbon ages indicate that carbonate factories were most prolific during the leadup to the Last Glacial Maximum, when sediment input was minimized, and have been mostly dormant since. Although there is little evidence for dissolution, skeletal debris is highly fragmented, abraded, and intensely bioeroded. The degree of destruction by these processes is highly selective amongst taxa, with skeletal structure influencing resistance to physical and biological breakdown. Overlapping generations of endolithic borings reflect moderate to high nutrient availability and repeated exposure of grains to infestation. Preserved grains are entirely calcitic and lack evidence of inorganic precipitation, implying potential taphonomic loss of aragonitic components. Observations indicate that seafloor processes in this setting combine to destroy a significant amount of carbonate as well as alter original depositional textures of deposits. Interpretations of ancient glaciomarine carbonates must consider the potential for significant biases created by destructive early seafloor processes.

  17. Stable carbon isotopes as indicators for micro-geomorphic changes in palsa peats

    NASA Astrophysics Data System (ADS)

    Alewell, Christine; Giessler, Reiner; Klaminder, Jonathan; Rollog, Mark

    2010-05-01

    Global climate change is significantly threatening stability and functioning of permafrost soils in extended areas of the northern latitudes and / or at high altitudes. A thawing of permafrost soils will most likely result in a positive feedback mechanism due to accelerated degradation of soil organic matter. The latter will not only induce release of substantial amounts of carbon into the atmosphere but also thermokast erosion and thus degradation of these unique systems. As such, biodiversity and functioning of these ecosystems are under immediate threat. One very unique northern ecosystem type are palsa peats, also called palsa mires. Palsa mires are a type of peat land typified by characteristic high mounds (called hummocks), each with a permanently frozen core. The freezing of the underlying horizons uplift these hummocks out of the groundwater saturated zone. Between the hummocks are wet depressions called hollows, which develop where the ground surface is frozen only for part of the year. Palsa mires are common in the former USSR, Canada and parts of Scandinavia and characterized by a unique geochemistry and biodiversity. If these sensitive ecosystems are exposed to environmental change, not only hydrology and vegetation composition but also degradation and mineralisation patterns of soil organic matter will change. The latter should be reflected in stable carbon isotope depth profiles. We investigated the depth distribution of stable carbon isotopes in Palsa mires of northern Sweden (Stordalen and Storflaket near Abisco, Lapland). Our data indicate that stable isotope depth profiles are influenced by environmental change and/ or soil forming processes in space and time. We find a consistent difference between depth profiles of hummocks and hollows. Hollows which are influenced by thermokarst erosion and are thus affected by thawing, breaking and submerging of peat chunks into the hollows, differ in their isotope depth profile from undisturbed hollows. The

  18. Stable oxygen and carbon isotope characteristics in speleothems from Southern Africa - how good are they?

    NASA Astrophysics Data System (ADS)

    Holmgren, K.

    2009-04-01

    Much remains to be understood about the interaction between the African climate system, its surrounding ocean-atmosphere climate variability and the global climate system. A better understanding of the regional climate evolution is crucial for understanding global climate dynamics and issues surrounding environmental change throughout Africa and a prerequisite for increasing climate forecasting capabilities for the region. As part of developing this understanding, a longer term perspective that reaches beyond the information available from instrumental records is required. Speleothems are frequently abundant in southern Africa. Quite a few records are now available, reporting significant changes in climate and environmental conditions over longer and shorter time scales. Conclusions are mainly based on the stable isotopic composition of the speleothems. The interpretation of the stable isotope data is, however, not always straight-forward, since many processes contribute to the observed signal in the speleothem and these processes may influence the signal differently at different spatial and temporal scales. For example was the Makapansgat speleothem oxygen isotope record, originally interpreted as being generally determined by shifts in atmospheric circulation pattern (Lee-Thorp et al. 2001, Holmgren et al. 2003), recently challenged and re-interpreted by Partin et al. (2008) to reflect annual rainfall amounts. Historically, less attention has been paid to the stable carbon isotope composition in speleothems. Today, an increasing number of studies demonstrate the potential of stable carbon variations as providing additional information on climate and environment. Measured variations can be a function of the amount of C3 versus C4 vegetation, vegetation cover and soil biological activity, bedrock proportion, rainfall amount and the drip rate. Clearly the multitudes of plausible processes behind the isotopic composition of speleothems in southern Africa (as well as

  19. Kinetics of laser chemical vapor deposition of carbon and refractory metals

    NASA Astrophysics Data System (ADS)

    Gao, Feng

    2000-10-01

    Three-dimensional laser chemical vapor deposition (3D-LCVD) has been used to grow rods of carbon, tungsten, titanium, and hafnium from a variety of hydrocarbons and metal halide-based precursors. A novel computerized 3D-LCVD system was designed and successfully used in the experiments. A focused Nd:Yag laser beam (lambda = 1.06 mum) was utilized to locally heat up a substrate to deposition temperature. The rods, which grew along the axis of the laser beam, had a typical diameter of 30--80 mum and a length of about 1 mm. The precursors for carbon deposition were the alkynes: propyne, butyne, pentyne, hexyne, and octyne. Propyne gave the highest deposition rate, in excess 3 mm/s at high laser powers (0.45 W) and high partial pressures (3000 mbar). the temperature dependence and pressure dependence were both non-linear functions of the growth rate. the temperature dependence could be separated into two regions---the kinetically limited region, which obeys the Arrhenius relationship, and the transport limited region, which is explained by diffusion of the precursors to the reaction zone. The pressure dependence showed that the reaction order for the different precursors varied from 2.5 for propyne to 1.3 for octyne. The precursors used deposit the refractory metals were tungsten hexafloride, titanium tetraiodide and hafnium chloride. The only successful precursor was tungsten hexafluoride, which readily produced tungsten rods when mixed with hydrogen. Rod diameters typically ranged from 50 mum to 400 mum and the average length of the rods were about 1 mm. Much lower deposition rates, less than 4.5 mum/s were obtained in this case as compared to carbon deposition. By an optimization of the LCVD process, it was possible to deposit high-quality single crystal tungsten rods. They were all oriented in the <100> direction.

  20. Stable isotope natural abundance of nitrous oxide emitted from Antarctic tundra soils: effects of sea animal excrement depositions.

    PubMed

    Zhu, Renbin; Liu, Yashu; Li, Xianglan; Sun, Jianjun; Xu, Hua; Sun, Liguang

    2008-11-01

    Nitrous oxide (N2O), a greenhouse gas, is mainly emitted from soils during the nitrification and denitrification processes. N2O stable isotope investigations can help to characterize the N2O sources and N2O production mechanisms. N2O isotope measurements have been conducted for different types of global terrestrial ecosystems. However, no isotopic data of N2O emitted from Antarctic tundra ecosystems have been reported although the coastal ice-free tundra around Antarctic continent is the largest sea animal colony on the global scale. Here, we report for the first time stable isotope composition of N2O emitted from Antarctic sea animal colonies (including penguin, seal and skua colonies) and normal tundra soils using in situ field observations and laboratory incubations, and we have analyzed the effects of sea animal excrement depositions on stable isotope natural abundance of N2O. For all the field sites, the soil-emitted N2O was 15N- and 18O-depleted compared with N2O in local ambient air. The mean delta values of the soil-emitted N2O were delta15N = -13.5 +/- 3.2 per thousand and delta18O = 26.2 +/- 1.4 per thousand for the penguin colony, delta15N = -11.5 +/- 5.1 per thousand and delta18O = 26.4 +/- 3.5 per thousand for the skua colony and delta15N = -18.9 +/- 0.7 per thousand and delta18O = 28.8 +/- 1.3 per thousand for the seal colony. In the soil incubations, the isotopic composition of N2O was measured under N2 and under ambient air conditions. The soils incubated under the ambient air emitted very little N2O (2.93 microg N2O--N kg(-1)). Under N2 conditions, much more N2O was formed (9.74 microg N2O--N kg(-1)), and the mean delta15N and delta18O values of N2O were -19.1 +/- 8.0 per thousand and 21.3 +/- 4.3 per thousand, respectively, from penguin colony soils, and -17.0 +/- 4.2 per thousand and 20.6 +/- 3.5 per thousand, respectively, from seal colony soils. The data from in situ field observations and laboratory experiments point to denitrification as the

  1. Tracing the Sources of Atmospheric Phosphorus Deposition to a Tropical Rain Forest in Panama Using Stable Oxygen Isotopes.

    PubMed

    Gross, A; Turner, B L; Goren, T; Berry, A; Angert, A

    2016-02-02

    Atmospheric dust deposition can be a significant source of phosphorus (P) in some tropical forests, so information on the origins and solubility of atmospheric P is needed to understand and predict patterns of forest productivity under future climate scenarios. We characterized atmospheric dust P across a seasonal cycle in a tropical lowland rain forest on Barro Colorado Nature Monument (BCNM), Republic of Panama. We traced P sources by combining remote sensing imagery with the first measurements of stable oxygen isotopes in soluble inorganic phosphate (δ(18)OP) in dust. In addition, we measured soluble inorganic and organic P concentrations in fine (<1 μm) and coarse (>1 μm) aerosol fractions and used this data to estimate the contribution of P inputs from dust deposition to the forest P budget. Aerosol dry mass was greater in the dry season (December to April, 5.6-15.7 μg m(-3)) than the wet season (May to November, 3.1-7.1 μg m(-3)). In contrast, soluble P concentrations in the aerosols were lower in the dry season (980-1880 μg P g(-1)) than the wet season (1170-3380 μg P g(-1)). The δ(18)OP of dry-season aerosols resembled that of nearby forest soils (∼19.5‰), suggesting a local origin. In the wet season, when the Trans-Atlantic Saharan dust belt moves north close to Panama, the δ(18)OP of aerosols was considerably lower (∼15.5‰), suggesting a significant contribution of long-distance dust P transport. Using satellite retrieved aerosol optical depth (AOD) and the P concentrations in aerosols we sampled in periods when Saharan dust was evident we estimate that the monthly P input from long distance dust transport during the period with highest Saharan dust deposition is 88 ± 31 g P ha(-1) month(-1), equivalent to between 10 and 29% of the P in monthly litter fall in nearby forests. These findings have important implications for our understanding of modern nutrient budgets and the productivity of tropical forests in the region under future

  2. Dominant formation of the microsized carbon coils by a short time SF6 flow incorporation during the initial deposition stage.

    PubMed

    Jeon, Young-Chul; Yi, Soung Soo; Kim, Sung-Hoon

    2013-08-01

    By SF6 gas incorporation for relatively short time during the initial deposition stage, carbon coils could be formed on nickel catalyst layer-deposited silicon oxide substrate using C2H2 and H2 as source gases under thermal chemical vapor deposition system. The characteristics (formation density and morphology) of as-grown carbon coils were investigated as a function of SF6 flow injection time. 5-min SF6 flow injection time is appropriate to produce the dominant microsized geometry for carbon coils without the appearance of the nanosized carbon coils. The geometry for the microsized carbon coils follows a typical double-helix structure and the shape of the rings constituting the coils is a flat-type. Fluorine's intrinsic etching characteristics for the nanosized carbon coils during the initial deposition stage seems to be the cause for the dominant formation of the microsized carbon coils in the case of 5-min SF6 flow injection time.

  3. Tilting of carbon encapsulated metallic nanocolumns in carbon-nickel nanocomposite films by ion beam assisted deposition

    SciTech Connect

    Krause, Matthias; Muecklich, Arndt; Zschornak, Matthias; Wintz, Sebastian; Gemming, Sibylle; Abrasonis, Gintautas; Oates, Thomas W. H.; Luis Endrino, Jose

    2012-07-30

    The influence of assisting low-energy ({approx}50-100 eV) ion irradiation effects on the morphology of C:Ni ({approx}15 at. %) nanocomposite films during ion beam assisted deposition (IBAD) is investigated. It is shown that IBAD promotes the columnar growth of carbon encapsulated metallic nanoparticles. The momentum transfer from assisting ions results in tilting of the columns in relation to the growing film surface. Complex secondary structures are obtained, in which a significant part of the columns grows under local epitaxy via the junction of sequentially deposited thin film fractions. The influence of such anisotropic film morphology on the optical properties is highlighted.

  4. Source and evolution of ore-forming hydrothermal fluids in the northern Iberian Pyrite Belt massive sulphide deposits (SW Spain): evidence from fluid inclusions and stable isotopes

    NASA Astrophysics Data System (ADS)

    Sánchez-España, Javier; Velasco, Francisco; Boyce, Adrian J.; Fallick, Anthony E.

    2003-08-01

    A fluid inclusion and stable isotopic study has been undertaken on some massive sulphide deposits (Aguas Teñidas Este, Concepción, San Miguel, San Telmo and Cueva de la Mora) located in the northern Iberian Pyrite Belt. The isotopic analyses were mainly performed on quartz, chlorite, carbonate and whole rock samples from the stockworks and altered footwall zones of the deposits, and also on some fluid inclusion waters. Homogenization temperatures of fluid inclusions in quartz mostly range from 120 to 280 °C. Salinity of most fluid inclusions ranges from 2 to 14 wt% NaCl equiv. A few cases with Th=80-110 °C and salinity of 16-24 wt% NaCl equiv., have been also recognized. In addition, fluid inclusions from the Soloviejo Mn-Fe-jaspers (160-190 °C and ≈6 wt% NaCl equiv.) and some Late to Post-Hercynian quartz veins (130-270 °C and ≈4 wt% NaCl equiv.) were also studied. Isotopic results indicate that fluids in equilibrium with measured quartz (δ18Ofluid ≈-2 to 4‰), chlorites (δ18Ofluid ≈8-14‰, δDfluid ≈-45 to -27‰), whole rocks (δ18Ofluid ≈4-7‰, δDfluid ≈-15 to -10‰), and carbonates (δ18Oankerite ≈14.5-16‰, δ13Cfluid =-11 to -5‰) evolved isotopically during the lifetime of the hydrothermal systems, following a waxing/waning cycle at different temperatures and water/rock ratios. The results (fluid inclusions, δ18O, δD and δ13C values) point to a highly evolved seawater, along with a variable (but significant) contribution of other fluid reservoirs such as magmatic and/or deep metamorphic waters, as the most probable sources for the ore-forming fluids. These fluids interacted with the underlying volcanic and sedimentary rocks during convective circulation through the upper crust.

  5. Amorphous hollow carbon spheres synthesized using radio frequency plasma-enhanced chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Yang, G. M.; Xu, Q.; Tian, H. W.; Wang, X.; Zheng, W. T.

    2008-10-01

    We report a method to synthesize amorphous hollow carbon spheres, with diameters ranging from 100 to 800 nm, which are dispersed among bent graphitized carbon nanotubes using radio frequency plasma-enhanced chemical vapour deposition in mixed CH4/H2 gases. The products are characterized by techniques including scanning electron microscopy, energy-dispersive x-ray spectroscopy, Raman spectroscopy and transmission electron microscopy. It is found that MgO and Ni nanoparticles together with hydrogen play important roles in the formation of the spheres. A possible formation mechanism for the carbon composites has been proposed.

  6. Magnetism of pure, disordered carbon films prepared by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Höhne, R.; Han, K.-H.; Esquinazi, P.; Setzer, A.; Semmelhack, H.; Spemann, D.; Butz, T.

    2004-05-01

    We have studied the magnetization of disordered, pure carbon films in order to search for signs of para-, ferro-or antiferromagnetism. Carbon films on silicon substrates were produced by pulsed laser deposition in high vacuum and at room temperature using pressed ultra-clean graphite powder as target. The magnetization shows a Curie-Weiss behaviour added to a temperature-independent term. Annealing the films at 1000°C and in high-vacuum eliminates completely the Curie-Weiss contribution. We compare our results with those recently obtained in activated carbon fibers.

  7. Simulation of catalyst behavior during chemical vapor deposition processing of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Nishi, Kazuki; Inoue, Shuhei; Matsumura, Yukihiko

    2014-06-01

    Nucleation of carbon nanotubes is considered to start with the supersaturation of carbon atoms dissolved in a catalyst. In chemical vapor deposition synthesis, it is believed that condensation of the source gas terminates the growth. However, some experimental studies have suggested that termination is primarily affected by catalyst behavior. We modified the potential functions and observed the behavior of carbon-iron mixed nanoparticles by a molecular dynamics method and found that the iron fraction melted at the equivalent temperature of growth termination. Thus, we concluded that the catalyst fusion prevented nucleation that would normally occur as a consequence of solution supersaturation.

  8. Increased calcium absorption from synthetic stable amorphous calcium carbonate: Double-blind randomized crossover clinical trial in post-menopausal women

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Calcium supplementation is a widely recognized strategy for achieving adequate calcium intake. We designed this blinded, randomized, crossover interventional trial to compare the bioavailability of a new stable synthetic amorphous calcium carbonate (ACC) with that of crystalline calcium carbonate (C...

  9. Comparative depositional geometries and facies within windward rimmed platform and carbonate ramp sequences

    SciTech Connect

    Boss, S.K.; Rasmussen, K.A.; Neumann, A.C. )

    1992-01-01

    Northern Great Bahama Bank (NGBB) combines geomorphic aspects of rimmed platforms and carbonate ramps in a windward (high-energy) environment. Analysis of Holocene sediment cores, seismic reflection mapping of the Holocene-Pleistocene unconformity and transgressive Holocene deposits and petrographic study of excavated Holocene submarine-cemented horizons provides an integrated view of evolving depositional geometries within both rimmed platform and ramp settings. Cores display gross textural and compositional homogeneity; all sediments are medium to coarse sands comprised of composite peloids, Halimeda sp., benthic foraminifera and molluscs. Three-dimensional seismic mapping reveals that this basal unconformity exhibits variation in topographic relief related to both constructional and erosional processes; rimmed portions of the platform are associated with topographic plateaus'' with fringing eolianite ridges or (rarely) reefs. These plateaus'' are separated by a somewhat deeper (ca. 5m deep) trough'' exhibiting little relief, but sloping seaward to form a ramp. Multiple intrasequence cemented horizons are a common feature of the thinner deposits of the NGBB ramp where tidal exchange is vigorous and sediment deposition is episodic or in dynamic balance with sediment export. Thus, rimmed carbonate platform facies are thick marine sands with relatively little submarine cementation while open, unsheltered ramp facies are characterized by thin sediment sequences containing numerous, discontinuous submarine-cemented horizons. In the absence of other obvious facies or geomorphic indicators (e.g. preserved reefal rims), the preservation of similar depositional features in ancient limestones may serve as a useful discriminant of rimmed platform versus carbonate ramp settings.

  10. Si–Cu alloy nanowires grown by oblique angle deposition as a stable negative electrode for Li-ion batteries

    SciTech Connect

    Polat, B. D.; Keles, O.; Chen, Z. H.; Amine, K.

    2016-03-29

    Thin films having nanocolumnar arrays made of various Si–Cu atomic ratios (90–10, 80–20, 70–30 %) are fabricated by an ion-assisted oblique angle co-deposition technique to produce stable negative electrodes for lithium-ion batteries. Cu is added into the electrode because of its ductility and electron conductivity. Cu plays a crucial role in holding the electrode together, minimizing overall capacity loss and enabling faster electron transfer. Plus, Cu is inactive versus Li?; therefore, Si–Cu variation is expected to affect the electrochemical performances of the electrodes. In this work, the effect of Si–Cu atomic ratios on the morphologies and the structures of the electrodes are studied. Plus, the uses of these nanocolumns with different Cu contents are evaluated as anodes by electrochemical tests. The morphological analyses demonstrate that an increase in Si–Cu atomic ratio affects the width of the nanocolumns and the homogeneity of the thin film morphology. The increase in Cu content dramatically improves the capacity retention of Si–Cu anodes, whereas it decreases the initial discharge capacity.

  11. Recyclable and stable silver deposited magnetic nanoparticles with poly (vinyl pyrrolidone)-catechol coated iron oxide for antimicrobial activity.

    PubMed

    Mosaiab, Tamim; Jeong, Chan Jin; Shin, Gyo Jic; Choi, Kyung Ho; Lee, Sang Kug; Lee, Iksoo; In, Insik; Park, Sung Young

    2013-10-01

    This paper introduces a facile method to make highly stable and recyclable antimicrobial magnetic nanoparticles (NPs). Initially, magnetic iron oxide nanoparticles (IONPs) were coated with poly (vinyl pyrrolidone) conjugated catechol (PVP-CCDP). Afterward, silver nanoparticles (Ag(0)) were deposited onto PVP-CCDP coated IONPs using remain catechol. The prepared nanoparticles showed long term (~4 weeks) colloidal stability and redispersibility, respectively, against external magnetic field and over a broad range of pH (4-12). The NPs were characterized by UV-vis, SEM, XPS, and XRD measurements. TEM and DLS analyses showed that the mean particle size of PVP-CCDP coated IONPs/Ag(0) were about 72 nm. The recyclable magnetic NPs possessed a high antibacterial effect against the model microbes Staphylococcus aureus and Escherichia coli and could be separated easily using magnet following antibacterial test for repeated uses and maintained 100% antibacterial efficiency during three cycles. In MTT assay, the magnetic nanoparticles possessed no measureable cytotoxicity to live cells.

  12. Energetic deposition of carbon in a cathodic vacuum arc with a biased mesh

    NASA Astrophysics Data System (ADS)

    Moafi, A.; Lau, D. W. M.; Sadek, A. Z.; Partridge, J. G.; McKenzie, D. R.; McCulloch, D. G.

    2011-04-01

    Carbon films were deposited in a filtered cathodic vacuum arc with a bias potential applied to a conducting mesh mounted in the plasma stream between the source and the substrate. We determined the stress and microstructural properties of the resulting carbon films and compared the results with those obtained using direct substrate bias with no mesh. Since the relationship between deposition energy and the stress, sp2 fraction and density of carbon are well known, measuring these film properties enabled us to investigate the effect of the mesh on the energy and composition of the depositing flux. When a mesh was used, the film stress showed a monotonic decrease for negative mesh bias voltages greater than 400V, even though the floating potential of the substrate did not vary. We explain this result by the neutralization of some ions when they are near to or passing through the negatively biased mesh. The microstructure of the films showed a change from amorphous to glassy carbonlike with increasing bias. Potential applications for this method include the deposition of carbon films with controlled stress on low conductivity substrates to form rectifying or ohmic contacts.

  13. Industrial Scale Synthesis of Carbon Nanotubes Via Fluidized Bed Chemical Vapor Deposition: A Senior Design Project

    ERIC Educational Resources Information Center

    Smith, York R.; Fuchs, Alan; Meyyappan, M.

    2010-01-01

    Senior year chemical engineering students designed a process to produce 10 000 tonnes per annum of single wall carbon nanotubes (SWNT) and also conducted bench-top experiments to synthesize SWNTs via fluidized bed chemical vapor deposition techniques. This was an excellent pedagogical experience because it related to the type of real world design…

  14. Field emission characteristics of nano-structured carbon films deposited on differently pretreated Mo films

    NASA Astrophysics Data System (ADS)

    Wang, Longyang; Wang, Xiaoping; Wang, Lijun; Zhang, Lei

    2008-12-01

    Nano-structured carbon films (NCFs) were grown on Mo layers by microwave plasma chemical vapor deposition (MPCVD) system. The Mo layers were deposited on ceramic substrates by electron beam deposition method and were pretreated by different techniques, which include ultrasonically scratching and laser-grooving technology (10 line/mm). NCFs were characterized by a field emission type scanning electron microscope (FE-SEM), Raman spectra and field emission (FE) I- V measurements. Effects of process parameters on morphologies, structures and FE properties of NCFs were examined. The experimental results show that two kinds of NCFs deposited at the same parameters employed for the MPCVD process were respectively composed of carbon nano-balls and reticular carbon nano-tubes inlayed by carbon nano-balls with dissimilar disorder structures, both NCFs showed each merits and exhibited good field emission properties, especially shown in the uniformity of FE, the uniform field emission images with areas of 4 cm 2 were obtained. Growth mechanism influenced by different pretreated method was discussed and the possible FE mechanisms of the NCFs were also investigated. Finally, the process characteristics of laser-grooving technology were analyzed, and its potential applications were predicted.

  15. Atmospheric pCO2 control on speleothem stable carbon isotope compositions

    NASA Astrophysics Data System (ADS)

    Breecker, Daniel O.

    2017-01-01

    The stable carbon isotope compositions of C3 plants are controlled by the carbon isotope composition of atmospheric CO2 (δ13Ca) and by the stomatal response to water stress. These relationships permit the reconstruction of ancient environments and assessment of the water use efficiency of forests. It is currently debated whether the δ13C values of C3 plants are also controlled by atmospheric pCO2. Here I show that globally-averaged speleothem δ13C values closely track atmospheric pCO2 over the past 90 kyr. After accounting for other possible effects, this coupling is best explained by a C3 plant δ13C sensitivity of - 1.6 ± 0.3 ‰ / 100 ppmV CO2 during the Quaternary. This is consistent with 20th century European forest tree ring δ13C records, providing confidence in the result and suggesting that the modest pCO2-driven increase in water use efficiency determined for those ecosystems and simulated by land surface models accurately approximates the global average response. The δ13C signal from C3 plants is transferred to speleothems relatively rapidly. Thus, the effect of atmospheric pCO2 should be subtracted from new and existing speleothem δ13C records so that residual δ13C shifts can be interpreted in light of the other factors known to control spleleothem δ13C values. Furthermore, global average speleothem δ13C shifts may be used to develop a continuous radiometric chronology for Pleistocene atmospheric pCO2 fluctuations and, by correlation, ice core climate records.

  16. Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

    NASA Astrophysics Data System (ADS)

    Alperin, M. J.; Blair, N. E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

    1992-09-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from "noncompetitive" substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94‰. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in 13C, reaching a maximum δ13C value of -42‰. Third, the acetate pool experienced a precipitous decline from >5 mM to <20 μM and methane production was again dominated by CO2 reduction. The δ13C of methane produced during this final phase ranged from -46 to -58‰. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8% of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

  17. Stable isotopes of helium, nitrogen and carbon in a coastal submarine hydrothermal system

    NASA Astrophysics Data System (ADS)

    Vidal, Francisco V.; Welhan, John; Vidal, Victor M. V.

    1982-03-01

    Geothermal gases from submarine and subaerial hot springs in Ensenada, Baja California Norte, Mexico, were sampled for determination of gas chemistry and helium, nitrogen and stable carbon isotope composition. The submarine hot spring gas is primarily nitrogen (56.1% by volume) and methane (43.5% by volume), whereas nearby subaerial hot spring gases are predominantly nitrogen (95-99% by volume). The N 2/Ar ratios and σ 15N values of the subaerial hot spring gas indicate that it is atmospheric air, depleted in oxygen and enriched in helium. The submarine hot spring gas is most probably derived from marine sediments of Cretaceous age rich in organic matter. CH 4 is a major component of the gas mixture ( σ 13C = -44.05% 0), with only minor amounts of CO 2 ( σ13C= -10.46% 0). The σ 15N of N 2 is + 0.2% 0 with a very high N 2/Ar ratio of 160. The calculated isotopic equilibra tion temperature for CH 4CO 2 carbon exchange at depth in the Punta Banda submarine geothermal field is approximately 200°C in agreement with other geothermometry estimates. The 3He/ 4He ratios of the hot spring gases range from 0.3 to 0.6 times the atmospheric ratio, indicating that helium is predominantly derived from the radioactive decay of U and Th within the continental crust. Thus,