GEOCARBSULF: A combined model for Phanerozoic atmospheric O₂ and CO₂     

Robert A. Berner 《Geochimica et cosmochimica acta》2006,70(23):5653-5664

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.  相似文献   

Carbon isotope evidence implying high O₂/CO₂ ratios in the Permo-Carboniferous atmosphere     

D.J. Beerling  J.A. LakeR.A. Berner  L.J. HickeyD.W. Taylor  D.L. Royer 《Geochimica et cosmochimica acta》2002,66(21):3757-3767

Theoretical models predict a marked increase in atmospheric O₂ to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO₂ level. An upper O₂ value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O₂ to 35% increases isotopic fractionation (Δ¹³C) during growth relative to control plants grown at 21% O₂. Despite some effect of the background atmospheric CO₂ level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O₂ could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ¹³C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ¹³C excursion is consistent with the effects of a high O₂ atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ¹³C record against experimental data yields a predicted O₂/CO₂ mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O₂ in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O₂ levels.  相似文献   

BRYOCARB: A process-based model of thallose liverwort carbon isotope fractionation in response to CO₂, O₂, light and temperature     

Benjamin J. Fletcher 《Geochimica et cosmochimica acta》2006,70(23):5676-5691

Evidence from laboratory experiments indicates that fractionation against the heavy stable isotope of carbon (Δ¹³C) by bryophytes (liverworts and mosses) is strongly dependent on atmospheric CO₂. This physiological response may therefore provide the basis for developing a new terrestrial CO₂ proxy [Fletcher, B.J., Beerling, D.J., Brentnall, S.J., Royer, D.L., 2005. Fossil bryophytes as recorders of ancient CO₂ levels: experimental evidence and a Cretaceous case study. Global Biogeochem. Cycles19, GB3012]. Here, we establish a theoretical basis for the proxy by developing an extended model of bryophyte carbon isotope fractionation (BRYOCARB) that integrates the biochemical theory of photosynthetic CO₂ assimilation with controls on CO₂ supply by diffusion from the atmosphere. The BRYOCARB model is evaluated against measurements of the response of liverwort photosynthesis and Δ¹³C to variations in atmospheric O₂, temperature and irradiance at different CO₂ concentrations. We show that the bryophyte proxy is at least as sensitive to variations in atmosphere CO₂ as the two other leading carbon isotope-based approaches to estimating palaeo-CO₂ levels (δ¹³C of phytoplankton and of paleosols). Mathematical inversion of BRYOCARB provides a mechanistic means of estimating atmospheric CO₂ levels from fossil bryophyte carbon that can explicitly account for the effects of past differences in O₂ and climate.  相似文献   

A comparison of isotope fractionation of carbon and hydrogen from paddy field rice roots and soil bacterial enrichments during CO₂/H₂ methanogenesis   总被引：1，自引：0，他引：1  

Amnat Chidthaisong  Kuk-Jeong ChinDavid L. Valentine  Stanley C. Tyler 《Geochimica et cosmochimica acta》2002,66(6):983-995

To better understand the isotope biogeochemistry of paddy field CH₄, we investigated carbon and hydrogen isotope fractionation during CO₂ reduction by a methanogenic community enriched from California paddy field soil and rice plants. Results from analyses of terminal restriction fragment length polymorphism (T-RFLP) and sequences of the archaeal small-subunit (SSU) rRNA-encoding genes (rDNA) showed a difference in methanogenic community structure between the soil (dominated by Methanobacteriaceae) and roots (dominated by Methanospirillaceae) which was essentially the same for sampling dates 15 and 99 days after flooding (DAF). CO₂/H₂ methanogenesis by these microbial communities produced CH₄ with different isotope ratios and fractionation factors (α factors). The carbon isotope α factors in an open system with a continuous supply of 0.5% H₂ were 1.050 ± 0.002 and 1.057 ± 0.001 for soil and root enrichment cultures at 15 DAF, and 1.052 ± 0.0.002 and 1.059 ± 0.002 for soil and root enrichment cultures at 99 DAF, respectively. These α factors are similar to, but distinct from values previously obtained from cultures of mesophilic methanogens and are larger than calculated values (1.045) for paddy soil. Fractionation of hydrogen isotopes was also studied in a closed system under 80% H₂. The difference in α factors between soil and root enrichment cultures remained clear. The hydrogen isotope fractionations between culture water and the product CH₄ were −327 ± 14‰ and −319 ± 18‰ for soil enrichments, and −389 ± 17‰ and −382 ± 21‰ for root enrichments at 15 DAF and 99 DAF, respectively.  相似文献   

The rise of trees and their effects on Paleozoic atmospheric CO₂ and O₂     

Robert A. Berner 《Comptes Rendus Geoscience》2003,335(16):1173-1177

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).  相似文献   

Oxygen isotope exchange between H₂O and CO₂ at elevated CO₂ pressures: Implications for monitoring of geological CO₂ storage     

G. Johnson  B. Mayer 《Applied Geochemistry》2011,26(7):1184-1191

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.  相似文献   

Groundwater N speciation and redox control of organic N mineralization by O₂ reduction to H₂O₂     

John W. Washington  Robert C. Thomas  Katherine L. Schroer 《Geochimica et cosmochimica acta》2006,70(14):3533-3548

Excess N from agriculture induces eutrophication in major river systems and hypoxia in coastal waters throughout the world. Much of this N is from headwaters far up the watersheds. In turn, much of the N in these headwaters is from ground-water discharge. Consequently, the concentrations and forms of N in groundwater are important factors affecting major aquatic ecosystems; despite this, few data exist for several species of N in groundwater and controls on speciation are ill-defined. Herein, we report N speciation for a spring and well that were selected to reflect agricultural impacts, and a spring and well that show little to no agricultural-N impact. Samples were characterized for NO₃⁻, NO₂⁻, N₂O, NH₄⁺, urea, particulate organic N(), and dissolved organic N(). These analytes were monitored in the agricultural spring for up to two years along with other analytes that we reported upon previously. For all samples, when oxidized N was present, the dominant species was NO₃⁻ (88-98% of total fixed N pool) followed by (<4-12%) and only trace fractions of the other N analytes. In the non-agriculturally impacted well sample, which had no quantifiable NO₃⁻ or dissolved O₂, comprised the dominant fraction (68%) followed by NH₄⁺ (32%), with only a trace balance comprised of other N analytes. Water drawn from the well, spring and a wetland situated in the agricultural watershed also were analyzed for dissolved N₂ and found to have a fugacity in excess of that of the atmosphere. H₂O₂ was analyzed in the agricultural spring to evaluate the O₂/H₂O₂ redox potential and compare it to other calculated potentials. The potential of the O₂/H₂O₂ couple was close in value to the NO₃⁻/NO₂⁻ couple suggesting the important role of H₂O₂ as an O₂-reduction intermediate product and that O₂ and NO₃⁻ are reduced concomitantly. The O₂/H₂O₂ and NO₃⁻/NO₂⁻ couples also were close in value to a cluster of other inorganic N and Fe couples indicating near partial equilibrium among these species. Urea mineralization to NO₂⁻ was found to approach equilibrium with the reduction of O₂ to H₂O₂. By modeling as amide functional groups, as justified by recent analytical work, similar thermodynamic calculations support that mineralization to NO₂⁻ proceeds nearly to equilibrium with the reduction of O₂ to H₂O₂ as well. This near equilibration of redox couples for urea- and -oxidation with O₂-reduction places these two couples within the oxidized redox cluster that is shared among several other couples we have reported previously. In the monitored agricultural spring, [NO₃⁻] was lower in the summer than at other times, whereas [N₂O] was higher in the summer than at other times, perhaps reflecting a seasonal variation in the degree of denitrification reaction progress. No other N analytes were observed to vary seasonally in our study. In the well having no agricultural-N impact, C_org/N_org = 5.5, close to the typical value for natural aqueous systems of about 6.6. In the agricultural watershed C_org/N_org varied widely, from ∼1.2 to ?9.  相似文献   

Effects of speciation on equilibrium fractionations and rates of oxygen isotope exchange between (PO₄)_aq and H₂O   总被引：1，自引：0，他引：1  

James R O’Neil  Torsten W Vennemann 《Geochimica et cosmochimica acta》2003,67(17):3135-3144

The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H₃PO₄ and H₂PO₄⁻ that are dominant at relatively low pH and species like PO₄³⁻ and ion pairs like KHPO₄⁻ that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, ¹⁸O/¹⁶O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates ¹⁸O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects.  相似文献   

Diurnal and vertical variability of pH, [O₂], and E_h in the Novosibirsk water reservoir     

V.I. Belevantsev  A.P. Ryzhikh  B.S. Smolyakov 《Russian Geology and Geophysics》2008,49(9):673-681

In situ data on the daily dynamics of pH, [O₂], and E_h values at five water layer depths were obtained. Some regularities have been established: All these parameters are characterized by significant diurnal fluctuations and their daily cyclic recurrence; the diurnal cycles of pH and [O₂] nearly coincide (they show close extreme points on the time scale); the E_h cycles are less distinct and antisymbatic to the pH and [O₂] cycles, but typical E_h extremes sometimes lag by 2–3 h. These data were analyzed using the principle of equilibrium locality and partiality. The main flows of O₂ and CO₂ in the system have been revealed with regard to the water layer–atmosphere gas exchange, absorption of CO₂ by phytoplankton in the photic layer, breathing of phyto- and zooplankton, birth and die-off of biota, settling of mortomass, and redistribution of detailed components within the water layer as well as between it and the bottom sediments. On the basis of the results obtained, the known technique for estimating the content of primary photosynthesis products (Bruevich's method) was corrected. The used generalized algorithm of chemical thermodynamic analysis of the substance state in aqueous systems can be applied to waters of different classes as well as any surficial waters if E_h, pH, and [O₂] are taken into account.  相似文献   

CTR diffraction and grazing-incidence EXAFS study of U(VI) adsorption onto α-Al₂O₃ and α-Fe₂O₃ (11?02) surfaces     

Jeffrey G. Catalano  Thomas P. Trainor  Glenn A. Waychunas 《Geochimica et cosmochimica acta》2005,69(14):3555-3572

Evaluation of the long-term health risks of uranium contamination in soils, sediments, and groundwater requires a fundamental understanding of the various processes affecting subsurface transport of uranium, including adsorption processes at mineral/water interfaces. In this study, the sites of binding and surface complexation of U(VI) adsorbed on the (11?02) surfaces of α-Al₂O₃ and α-Fe₂O₃ have been determined using crystal truncation rod (CTR) diffraction and grazing incidence extended X-ray absorption fine structure (GI-EXAFS) spectroscopy. The available binding sites on the (11?02) surfaces were constrained through bond valence and steric analyses. On both surfaces, U(VI) forms uranyl-carbonato ternary complexes to surface oxygens that are singly coordinated to aluminum or iron. On the α-Al₂O₃ (11?02) surface, a monodentate complex results, whereas on the α-Fe₂O₃ (11?02) surface, the binding is bidentate to adjacent singly coordinated oxygen sites (i.e., binuclear). Differences in protonation of the singly coordinated oxygen atoms, surface charging, U(VI) aqueous speciation, substrate structure, or the electronic structure of surface functional groups may be the cause of these differences in adsorption geometry. Both XPS and CTR diffraction reveal higher U(VI) surface coverages on the α-Fe₂O₃ (11?02) surface than on the α-Al₂O₃ (11?02) surface. This difference cannot be the result of differences in defect concentration alone as CTR diffraction is not sensitive to U(VI) sorbed to defect sites, implying that the α-Fe₂O₃ (11?02) surface has an intrinsically higher affinity for U(VI). The surface complexes observed in this study are different from the bidentate, mononuclear complexes typically derived for U(VI) on powdered aluminum- and iron-(oxyhydr)oxides and clay minerals using U L_III-edge EXAFS spectroscopy. However, the presence of monodentate, mononuclear and bidentate, binuclear complexes may have been overlooked in past EXAFS studies on such substrates, as these complexes have U-Al or U-Fe interatomic distances that are too large to be easily detected by EXAFS spectroscopy.  相似文献   

The isotopic ratios O/O and O/O in molecular oxygen and their significance in biogeochemistry     

Boaz Luz  Eugeni Barkan 《Geochimica et cosmochimica acta》2005,69(5):1099-1110

Recently, a new method has been introduced for the estimation of photosynthetic oxygen production from the triple isotope composition (δ¹⁷O and δ¹⁸O) of dissolved O₂ in the ocean and of air O₂ in ice cores. This method is based on the deviations (¹⁷Δ) from mass dependent respiratory fractionation, the major process affecting the isotopic composition of air O₂. To apply this method, the slope in the ¹⁷O/¹⁶O vs. ¹⁸O/¹⁶O relationship used for ¹⁷Δ calculation must be known with high accuracy. Using numerical simulations and closed system experiments, we show how the respiratory slope is manifested in the ¹⁷Δ of O₂ in situations where respiration is the only process affecting oxygen isotopic composition (kinetic slope), and in systems in steady state between photosynthesis and respiration (steady state slope). The slopes of the fractionation line in these two cases are different, and the reasons of this phenomenon are discussed. To determine the kinetic respiratory slope for the dominant O₂ consumers in aquatic systems, we have conducted new experiments using a wide range of organisms and conditions and obtained one universal value (0.5179 ± 0.0006) in ln(δ¹⁷O + 1) vs. ln(δ¹⁸O + 1) plots. It was also shown that the respiratory fractionations under light and dark are identical within experimental error. We discuss various marine situations and conclude that the kinetic slope 0.518 should be used for calculating ¹⁷Δ of dissolved O₂. In contrast, a steady state fractionation slope should be used in global mass balance calculations of triple isotope ratios of O₂ in air records of ice cores.  相似文献   

Oxygen isotope partitioning during oxidation of pyrite by H₂O₂ and its dependence on temperature     

Liliana Lefticariu  Arndt Schimmelmann  Edward M. Ripley 《Geochimica et cosmochimica acta》2007,71(21):5072-5088

A detailed experimental study was conducted to investigate mechanisms of pyrite oxidation by determining product yields and oxygen isotopic fractionation during reactions between powdered pyrite (FeS₂) with aqueous hydrogen peroxide (H₂O₂). Sealed silica-tube experiments utilized aliquots of pyrite that were reacted with 0.2 M H₂O₂ for 7 to 14 days at 4 to 150 °C. No volatile sulfur species were detected in any experiment. The only gaseous product recovered was elemental oxygen inferred to result from decomposition of H₂O₂. Aqueous sulfate (S_aq) was the only sulfur product recovered from solution. Solid hydrated ferric iron sulfates (i.e., water-soluble sulfate fraction, S_ws) were recovered from all experiments. Ferric oxide (hematite) was detected only in high temperature experiments.Reactants were selected with large differences in initial δ¹⁸O values. The oxygen isotopic compositions of oxygen-bearing reactants and products were analyzed for each experiment. Subsequent isotopic mass-balances were used to identify sources of oxygen for reaction products and to implicate specific chemical reaction mechanisms. δ¹⁸O of water did not show detectable change during any experiment. δ¹⁸O of sulfate was similar for S_aq and S_ws and indicated that both H₂O and H₂O₂ were sources of oxygen in sulfate. Low-temperature experiments suggest that H₂O-derived oxygen was incorporated into sulfate via Fe³⁺ oxidation, whereas H₂O₂-derived oxygen was incorporated into sulfate via oxidation by hydroxyl radicals (HO). These two competing mechanisms for oxygen incorporation into sulfate express comparable influences at 25 °C. With increasing reaction temperatures from 4 to 100 °C, it appears that accelerated thermal decomposition and diminished residence time of H₂O₂ limit the oxygen transfer from H₂O₂ into sulfate and enhance the relative importance of H₂O-derived oxygen for incorporation into sulfate. Notably, at temperatures between 100 and 150 °C there is a reversal in the lower temperature trend resulting in dominance of H₂O₂-derived oxygen over H₂O-derived oxygen. At such high temperatures, complete thermal decomposition of H₂O₂ to water and molecular oxygen (O₂) occurs within minutes in mineral-blank experiments and suggests little possibility for direct oxidation of pyrite by H₂O₂ above 100 °C. We hypothesize that a Fe-O₂ mechanism is responsible for oxygenating pyrite to sulfate using O₂ from the preceding thermal decomposition of H₂O₂.  相似文献   

N/N and O/O stable isotope ratios of nitrous oxide produced during denitrification in temperate forest soils     

David M. Snider  Sherry L. Schiff 《Geochimica et cosmochimica acta》2009,73(4):877-4688

Anaerobic incubations of upland and wetland temperate forest soils from the same watershed were conducted under different moisture and temperature conditions. Rates of nitrous oxide (N₂O) production by denitrification of nitrate () and the stable isotopic composition of the N₂O (δ¹⁵N, δ¹⁸O) were measured. In all soils, N₂O production increased with elevated temperature and soil moisture. At each temperature and moisture level, the rate of N₂O production in the wetland soil was greater than in the upland soil. The ¹⁵N isotope effect (ε) _{(product − substrate)} ranged from −20‰ to −29‰. These results are consistent with other published estimates of ¹⁵N fractionation from both single species culture experiments and soil incubation studies from different ecosystems.A series of incubations were conducted with ¹⁸O-enriched water (H₂O) to determine if significant oxygen exchange (O-exchange) occurred between H₂O and N₂O precursors during denitrification. The exchange of H₂O-O with nitrite () and/or nitric oxide (NO) oxygen has been documented in single organism culture studies but has not been demonstrated in soils prior to this study. The fraction of N₂O-O derived from H₂O-O was confined to a strikingly narrow range that differed between soil types. H₂O-O incorporation into N₂O produced from upland and wetland soils was 86% to 94% and 64% to 70%, respectively. Neither the temperature, soil moisture, nor the rate of N₂O production influenced the magnitude of O-exchange. With the exception of one treatment, the net ¹⁸O isotope effect (ε_net) _{(product-substrate)} ranged from +37‰ to +43‰.Most previous studies that have reported ¹⁸O isotope effects for denitrification of to N₂O have failed to account for the effect of oxygen exchange with H₂O. When high amounts of O-exchange occur after fractionation during reductive O-loss, the ¹⁸O-enrichment is effectively lost or diminished and δ¹⁸O-N₂O values will be largely dictated by δ¹⁸O-H₂O values and subsequent fractionation. The process and extent of O-exchange, combined with the magnitude of oxygen isotope fractionation at each reduction step, appear to be the dominant controls on the observed oxygen isotope effect. In these experiments, significant oxygen isotope fractionation was observed to occur after the majority of water O-exchange. Due to the importance of O-exchange, the net oxygen isotope effect for N₂O production in soils can only be determined using δ¹⁸O-H₂O addition experiments with δ¹⁸O-H₂O close to natural abundance.The results of this study support the continued use of δ¹⁵N-N₂O analysis to fingerprint N₂O produced from the denitrification of . The utilization of ¹⁸O/¹⁶O ratios of N₂O to study N₂O production pathways in soil environments is complicated by oxygen exchange with water, which is not usually quantified in field studies. The oxygen isotope fractionation observed in this study was confined to a narrow range, and there was a clear difference in water O-exchange between soil types regardless of temperature, soil moisture, and N₂O production rate. This suggests that ¹⁸O/¹⁶O ratios of N₂O may be useful in characterizing the actively denitrifying microbial community.  相似文献   

Oxidation of Sb(III) to Sb(V) by O₂ and H₂O₂ in aqueous solutions     

Ann-Kathrin Leuz  C. Annette Johnson 《Geochimica et cosmochimica acta》2005,69(5):1165-1172

The rates of Sb(III) oxidation by O₂ and H₂O₂ were determined in homogeneous aqueous solutions. Above pH 10, the oxidation reaction of Sb(III) with O₂ was first order with respect to the Sb(III) concentration and inversely proportional to the H⁺ concentrations at a constant O₂ content of 0.22 × 10⁻³ M. Pseudo-first-order rate coefficients, k_obs, ranged from 3.5 × 10⁻⁸ s⁻¹ to 2.5 × 10⁻⁶ s⁻¹ at pH values between 10.9 and 12.9. The relationship between k_obs and pH was: