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1.
Lake Vida, in the Victoria Valley of East Antarctica, is frozen, yet harbors liquid brine (~20% salt, >6 times seawater) intercalated in the ice below 16 m. The brine has been isolated from the surface for several thousand years. The brine conditions (permanently dark, ?13.4 °C, lack of O2, and pH of 6.2) and geochemistry are highly unusual. For example, nitrous oxide (N2O) is present at a concentration among the highest reported for an aquatic environment. Only a minor 17O anomaly was observed in N2O, indicating that this gas was predominantly formed in the lake. In contrast, the 17O anomaly in nitrate () in Lake Vida brine indicates that approximately half or more of the present is derived from atmospheric deposition. Lake Vida brine was incubated in the presence of 15N‐enriched substrates for 40 days. We did not detect microbial nitrification, dissimilatory reduction of to ammonium (), anaerobic ammonium oxidation, or denitrification of N2O under the conditions tested. In the presence of 15N‐enriched nitrite (), both N2 and N2O exhibited substantial 15N enrichments; however, isotopic enrichment declined with time, which is unexpected. Additions of 15N– alone and in the presence of HgCl2 and ZnCl2 to aged brine at ?13 °C resulted in linear increases in the δ15N of N2O with time. As HgCl2 and ZnCl2 are effective biocides, we interpret N2O production in the aged brine to be the result of chemodenitrification. With this understanding, we interpret our results from the field incubations as the result of chemodenitrification stimulated by the addition of 15N‐enriched and ZnCl2 and determined rates of N2O and N2 production of 4.11–41.18 and 0.55–1.75 nmol L?1 day?1, respectively. If these rates are representative of natural production, the current concentration of N2O in Lake Vida could have been reached between 6 and 465 years. Thus, chemodenitrification alone is sufficient to explain the high levels of N2O present in Lake Vida.  相似文献   

2.
Soils are predicted to exhibit significant feedback to global warming via the temperature response of greenhouse gas (GHG) production. However, the temperature response of hydromorphic wetland soils is complicated by confounding factors such as oxygen (O2), nitrate () and soil carbon (C). We examined the effect of a temperature gradient (2–25 °C) on denitrification rates and net nitrous oxide (N2O), methane (CH4) production and heterotrophic respiration in mineral (Eutric cambisol and Fluvisol) and organic (Histosol) soil types in a river marginal landscape of the Tamar catchment, Devon, UK, under non‐flooded and flooded with enriched conditions. It was hypothesized that the temperature response is dependent on interactions with ‐enriched flooding, and the physicochemical conditions of these soil types. Denitrification rate (mean, 746 ± 97.3 μg m?2 h?1), net N2O production (mean, 180 ± 26.6 μg m?2 h?1) and net CH4 production (mean, 1065 ± 183 μg m?2 h?1) were highest in the organic Histosol, with higher organic matter, ammonium and moisture, and lower concentrations. Heterotrophic respiration (mean, 127 ± 4.6 mg m?2 h?1) was not significantly different between soil types and dominated total GHG (CO2eq) production in all soil types. Generally, the temperature responses of denitrification rate and net N2O production were exponential, whilst net CH4 production was unresponsive, possibly due to substrate limitation, and heterotrophic respiration was exponential but limited in summer at higher temperatures. Flooding with increased denitrification rate, net N2O production and heterotrophic respiration, but a reduction in net CH4 production suggests inhibition of methanogenesis by or N2O produced from denitrification. Implications for management and policy are that warming and flood events may promote microbial interactions in soil between distinct microbial communities and increase denitrification of excess with N2O production contributing to no more than 50% of increases in total GHG production.  相似文献   

3.
Microbial sulfur cycling in marine sediments often occurs in environments characterized by transient chemical gradients that affect both the availability of nutrients and the activity of microbes. High turnover rates of intermediate valence sulfur compounds and the intermittent availability of oxygen in these systems greatly impact the activity of sulfur‐oxidizing micro‐organisms in particular. In this study, the thiosulfate‐oxidizing hydrothermal vent bacterium Thiomicrospira thermophila strain EPR85 was grown in continuous culture at a range of dissolved oxygen concentrations (0.04–1.9 mM) and high pressure (5–10 MPa) in medium buffered at pH 8. Thiosulfate oxidation under these conditions produced tetrathionate, sulfate, and elemental sulfur, in contrast to previous closed‐system experiments at ambient pressure during which thiosulfate was quantitatively oxidized to sulfate. The maximum observed specific growth rate at 5 MPa pressure under unlimited O2 was 0.25 hr?1. This is comparable to the μmax (0.28 hr?1) observed at low pH (<6) at ambient pressure when T. thermophila produces the same mix of sulfur species. The half‐saturation constant for O2 () estimated from this study was 0.2 mM (at a cell density of 105 cells/ml) and was robust at all pressures tested (0.4–10 MPa), consistent with piezotolerant behavior of this strain. The cell‐specific was determined to be 1.5 pmol O2/cell. The concentrations of products formed were correlated with oxygen availability, with tetrathionate production in excess of sulfate production at all pressure conditions tested. This study provides evidence for transient sulfur storage during times when substrate concentration exceeds cell‐specific and subsequent consumption when oxygen dropped below that threshold. These results may be common among sulfur oxidizers in a variety of environments (e.g., deep marine sediments to photosynthetic microbial mats).  相似文献   

4.
All life on Earth seems to be made of the same chemical elements in relatively conserved proportions (stoichiometry). Whether this stoichiometry is conserved in settings that differ radically in physicochemical conditions (extreme environments) from those commonly encountered elsewhere on the planet provides insight into possible stoichiometries for putative life beyond Earth. Here, we report measurements of elemental stoichiometry for extremophile microbes from hot springs of Yellowstone National Park (YNP). Phototrophic and chemotrophic microbes were collected in locations spanning large ranges of temperature (24 °C to boiling), pH (1.6–9.6), redox (0.1–7.2 mg L?1 dissolved oxygen), and nutrient concentrations (0.01–0.25 mg L?1 , 0.7–12.9 mg L?1 , 0.01–42 mg L?1 NH4+, 0.003–1.1 mg L?1 P mostly as phosphate). Despite these extreme conditions, the microbial cells sampled had a major and trace element stoichiometry within the ranges commonly encountered for microbes living in the more moderate environments of lakes and surface oceans. The cells did have somewhat high C:P and N:P ratios that are consistent with phosphorus (P) limitation. Furthermore, chemotrophs and phototrophs had similar compositions with the exception of Mo content, which was enriched in cells derived from chemotrophic sites. Thus, despite the extraordinary physicochemical and biological diversity of YNP environments, life in these settings, in a stoichiometric sense, remains much the same as we know it elsewhere.  相似文献   

5.
Increasing atmospheric reactive nitrogen (N) deposition due to human activities could change N cycling in terrestrial ecosystems. However, the differences between the fates of deposited and are still not fully understood. Here, we investigated the fates of deposited and , respectively, via the application of 15NH4NO3 and NH415NO3 in a temperate forest ecosystem. Results showed that at 410 days after tracer application, most was immobilized in litter layer (50 ± 2%), while a considerable amount of penetrated into 0–5 cm mineral soil (42 ± 2%), indicating that litter layer and 0–5 cm mineral soil were the major N sinks of and , respectively. Broad‐leaved trees assimilated more 15N under NH415NO3 treatment compared to under 15NH4NO3 treatment, indicating their preference for –N. At 410 days after tracer application, 16 ± 4% added 15N was found in aboveground biomass under treatment, which was twice more than that under treatment (6 ± 1%). At the same time, approximately 80% added 15N was recovered in soil and plants under both treatments, which suggested that this forest had high potential for retention of deposited N. These results provided evidence that there were great differences between the fates of deposited and , which could help us better understand the mechanisms and capability of forest ecosystems as a sink of reactive nitrogen.  相似文献   

6.
Nitrate‐reducing, Fe(II)‐oxidizing bacteria were suggested to couple with enzymatic Fe(II) oxidation to nitrate reduction. Denitrification proceeds via intermediates (, NO) that can oxidize Fe(II) abiotically at neutral and particularly at acidic pH. Here, we present a revised Fe(II) quantification protocol preventing artifacts during acidic Fe extraction and evaluate the contribution of abiotic vs. enzymatic Fe(II) oxidation in cultures of the nitrate‐reducing, Fe(II) oxidizer Acidovorax sp. BoFeN1. Sulfamic acid used instead of HCl reacts with nitrite and prevents abiotic Fe(II) oxidation during Fe extraction. Abiotic experiments without sulfamic acid showed that acidification of oxic Fe(II) nitrite samples leads to 5.6‐fold more Fe(II) oxidation than in anoxic samples because the formed NO becomes rapidly reoxidized by O2, therefore leading to abiotic oxidation and underestimation of Fe(II). With our revised protocol using sulfamic acid, we quantified oxidation of approximately 7 mm of Fe(II) by BoFeN1 within 4 days. Without addition of sulfamic acid, the same oxidation was detected within only 2 days. Additionally, abiotic incubation of Fe(II) with nitrite in the presence of goethite as surface catalyst led to similar abiotic Fe(II) oxidation rates as observed in growing BoFeN1 cultures. BoFeN1 growth was observed on acetate with N2O as electron acceptor. When adding Fe(II), no Fe(II) oxidation was observed, suggesting that the absence of reactive N intermediates (, NO) precludes Fe(II) oxidation. The addition of ferrihydrite [Fe(OH)3] to acetate/nitrate BoFeN1 cultures led to growth stimulation equivalent to previously described effects on growth by adding Fe(II). This suggests that elevated iron concentrations might provide a nutritional effect rather than energy‐yielding Fe(II) oxidation. Our findings therefore suggest that although enzymatic Fe(II) oxidation by denitrifiers cannot be fully ruled out, its contribution to the observed Fe(II) oxidation in microbial cultures is probably lower than previously suggested and has to be questioned in general until the enzymatic machinery‐mediating Fe(II) oxidation is identified.  相似文献   

7.
The weathering of volcanic rocks contributes significantly to the global silicate weathering budget, effecting carbon dioxide drawdown and long‐term climate control. The rate of chemical weathering is influenced by the composition of the rock. Rock‐dwelling micro‐organisms are known to play a role in changing the rate of weathering reactions; however, the influence of rock composition on bio‐weathering is unknown. Cyanobacteria are known to be a ubiquitous surface taxon in volcanic rocks. In this study, we used a selection of fast and slow growing cyanobacterial species to compare microbial‐mediated weathering of bulk crystalline rocks of basaltic and rhyolitic composition, under batch conditions. Cyanobacterial growth caused an increase in the pH of the medium and an acceleration of rock dissolution compared to the abiotic controls. For example, Anabaena cylindrica increased the linear release rate () of Ca, Mg, Si and K from the basalt by more than fivefold (5.21–12.48) and increased the pH of the medium by 1.9 units. Although A. cylindrica enhanced rhyolite weathering, the increase in was less than threefold (2.04–2.97) and the pH increase was only 0.83 units. The values obtained with A. cylindrica were at least ninefold greater with the basalt than the rhyolite, whereas in the abiotic controls, the difference was less than fivefold. Factors accounting for the slower rate of rhyolite weathering and lower biomass achieved are likely to include the higher content of quartz, which has a low rate of weathering and lower concentrations of bio‐essential elements, such as, Ca, Fe and Mg, which are known to be important in controlling cyanobacterial growth. We show that at conditions where weathering is favoured, biota can enhance the difference between low and high Si‐rock weathering. Our data show that cyanobacteria can play a significant role in enhancing rock weathering and likely have done since they evolved on the early Earth.  相似文献   

8.
Throughout most of the sedimentary record, the marine carbon cycle is interpreted as being in isotopic steady state. This is most commonly inferred via isotopic reconstructions, where two export fluxes (organic carbon and carbonate) are offset by a constant isotopic fractionation of ~25 (termed ). Sedimentary deposits immediately overlying the Marinoan snowball Earth diamictites, however, stray from this prediction. In stratigraphic sections from the Ol Formation (Mongolia) and Sheepbed Formation (Canada), we observe a temporary excursion where the organic matter has anomalously heavy C and is grossly decoupled from the carbonate C. This signal may reflect the unique biogeochemical conditions that persisted in the aftermath of snowball Earth. For example, physical oceanographic modeling suggests that a strong density gradient caused the ocean to remain stratified for about 50,000 years after termination of the Marinoan snowball event, during which time the surface ocean and continental weathering consumed the large atmospheric CO2 reservoir. Further, we now better understand how C records of carbonate can be post‐depostionally altered and thus be misleading. In an attempt to explain the observed carbon isotope record, we developed a model that tracks the fluxes and isotopic values of carbon between the surface ocean, deep ocean, and atmosphere. By comparing the model output to the sedimentary data, stratification alone cannot generate the anomalous observed isotopic signal. Reproducing the heavy C in organic matter requires the progressively diminishing contribution of an additional anomalous source of organic matter. The exact source of this organic matter is unclear.  相似文献   

9.
Calmodulin (CaM) functions depend on interactions with CaM‐binding proteins, regulated by . Induced structural changes influence the affinity, kinetics, and specificities of the interactions. The dynamics of CaM interactions with neurogranin (Ng) and the CaM‐binding region of /calmodulin‐dependent kinase II (CaMKII290−309) have been studied using biophysical methods. These proteins have opposite dependencies for CaM binding. Surface plasmon resonance biosensor analysis confirmed that and CaM interact very rapidly, and with moderate affinity ( ). Calmodulin‐CaMKII290−309 interactions were only detected in the presence of , exhibiting fast kinetics and nanomolar affinity ( ). The CaM–Ng interaction had higher affinity under ‐depleted ( and k −1 = 1.6 × 10−1s−1) than ‐saturated conditions ( ). The IQ motif of Ng (Ng27−50) had similar affinity for CaM as Ng under ‐saturated conditions ( ), but no interaction was seen under ‐depleted conditions. Microscale thermophoresis using fluorescently labeled CaM confirmed the surface plasmon resonance results qualitatively, but estimated lower affinities for the Ng ( ) and CaMKII290−309( ) interactions. Although CaMKII290−309 showed expected interaction characteristics, they may be different for full‐length CaMKII. The data for full‐length Ng, but not Ng27−50, agree with the current model on Ng regulation of /CaM signaling.  相似文献   

10.
The fixation of new deleterious mutations is analyzed for a randomly mating population of constant size with no environmental or demographic stochasticity. Mildly deleterious mutations are far more important in causing loss of fitness and eventual extinction than are lethal and semilethal mutations in populations with effective sizes, Ne, larger than a few individuals. If all mildly deleterious mutations have the same selection coefficient, s against heterozygotes and 2s against homozygotes, the mean time to extinction, , is asymptotically proportional to for 4Nes > 1. Nearly neutral mutations pose the greatest risk of extinction for stable populations, because the magnitude of selection coefficient that minimizes is about ? = 0.4/Ne. The influence of variance in selection coefficients among mutations is analyzed assuming a gamma distribution of s, with mean and variance . The mean time to extinction increases with variance in selection coefficients if is near ?, but can decrease greatly if is much larger than ?. For a given coefficient of variation of , the mean time to extinction is asymptotically proportional to for . When s is exponentially distributed, (c = 1) is asymptotically proportional to . These results in conjunction with data on the rate and magnitude of mildly deleterious mutations in Drosophila melanogaster indicate that even moderately large populations, with effective sizes on the order of Ne = 103, may incur a substantial risk of extinction from the fixation of new mutations.  相似文献   

11.
Rising atmospheric CO2 concentrations are expected to increase nitrous oxide (N2O) emissions from soils via changes in microbial nitrogen (N) transformations. Several studies have shown that N2O emission increases under elevated atmospheric CO2 (eCO2), but the underlying processes are not yet fully understood. Here, we present results showing changes in soil N transformation dynamics from the Giessen Free Air CO2 Enrichment (GiFACE): a permanent grassland that has been exposed to eCO2, +20% relative to ambient concentrations (aCO2), for 15 years. We applied in the field an ammonium‐nitrate fertilizer solution, in which either ammonium () or nitrate () was labelled with 15N. The simultaneous gross N transformation rates were analysed with a 15N tracing model and a solver method. The results confirmed that after 15 years of eCO2 the N2O emissions under eCO2 were still more than twofold higher than under aCO2. The tracing model results indicated that plant uptake of did not differ between treatments, but uptake of was significantly reduced under eCO2. However, the and availability increased slightly under eCO2. The N2O isotopic signature indicated that under eCO2 the sources of the additional emissions, 8,407 μg N2O–N/m2 during the first 58 days after labelling, were associated with reduction (+2.0%), oxidation (+11.1%) and organic N oxidation (+86.9%). We presume that increased plant growth and root exudation under eCO2 provided an additional source of bioavailable supply of energy that triggered as a priming effect the stimulation of microbial soil organic matter (SOM) mineralization and fostered the activity of the bacterial nitrite reductase. The resulting increase in incomplete denitrification and therefore an increased N2O:N2 emission ratio, explains the doubling of N2O emissions. If this occurs over a wide area of grasslands in the future, this positive feedback reaction may significantly accelerate climate change.  相似文献   

12.
The possibility of low but nontrivial atmospheric oxygen (O2) levels during the mid‐Proterozoic (between 1.8 and 0.8 billion years ago, Ga) has important ramifications for understanding Earth's O2 cycle, the evolution of complex life and evolving climate stability. However, the regulatory mechanisms and redox fluxes required to stabilize these O2 levels in the face of continued biological oxygen production remain uncertain. Here, we develop a biogeochemical model of the C‐N‐P‐O2‐S cycles and use it to constrain global redox balance in the mid‐Proterozoic ocean–atmosphere system. By employing a Monte Carlo approach bounded by observations from the geologic record, we infer that the rate of net biospheric O2 production was Tmol year?1 (1σ), or ~25% of today's value, owing largely to phosphorus scarcity in the ocean interior. Pyrite burial in marine sediments would have represented a comparable or more significant O2 source than organic carbon burial, implying a potentially important role for Earth's sulphur cycle in balancing the oxygen cycle and regulating atmospheric O2 levels. Our statistical approach provides a uniquely comprehensive view of Earth system biogeochemistry and global O2 cycling during mid‐Proterozoic time and implicates severe P biolimitation as the backdrop for Precambrian geochemical and biological evolution.  相似文献   

13.
In freshwaters, algal species are exposed to different inorganic nitrogen (Ni) sources whose incorporation varies in biochemical energy demand. We hypothesized that due to the lesser energy requirement of ammonium ()‐use, in contrast to nitrate ()‐use, more energy remains for other metabolic processes, especially under CO2‐ and phosphorus (Pi) limiting conditions. Therefore, we tested differences in cell characteristics of the green alga Chlamydomonas acidophila grown on or under covariation of CO2 and Pi‐supply in order to determine limitations, in a full‐factorial design. As expected, results revealed higher carbon fixation rates for ‐grown cells compared to growth with under low CO2 conditions. ‐grown cells accumulated more of the nine analyzed amino acids, especially under Pi‐limited conditions, compared to cells provided with . This is probably due to a slower protein synthesis in cells provided with . In contrast to our expectations, compared to ‐grown cells ‐grown cells had higher photosynthetic efficiency under Pi‐limitation. In conclusion, growth on the Ni‐source did not result in a clearly enhanced Ci‐assimilation, as it was highly dependent on Pi and CO2 conditions (replete or limited). Results are potentially connected to the fact that C. acidophila is able to use only CO2 as its inorganic carbon (Ci) source.  相似文献   

14.
The microbial communities thriving in deep‐sea brines are sustained largely by energy rich substrates supplied through active seepage. Geochemical, microbial activity, and microbial community composition data from different habitats at a Gulf of Mexico brine lake in Alaminos Canyon revealed habitat‐linked variability in geochemistry that in turn drove patterns in microbial community composition and activity. The bottom of the brine lake was the most geochemically extreme (highest salinity and nutrient concentrations) habitat and its microbial community exhibited the highest diversity and richness indices. The habitat at the upper halocline of the lake hosted the highest rates of sulfate reduction and methane oxidation, and the largest inventories of dissolved inorganic carbon, particulate organic carbon, and hydrogen sulfide. Statistical analyses indicated a significant positive correlation between the bacterial and archaeal diversity in the bottom brine sample and inventories. Other environmental factors with positive correlation with microbial diversity indices were DOC, H2S, and DIC concentrations. The geochemical regime of different sites within this deep seafloor extreme environment exerts a clear selective force on microbial communities and on patterns of microbial activity.  相似文献   

15.
Switchgrass (Panicum virgatum L.) production has the potential to improve soils and the environment. However, little is known about the long‐term future assessment of soil and environmental impacts associated with switchgrass production. In this study, soil organic carbon (SOC), soil nitrate (), water‐filled pore space (WFPS), carbon dioxide (CO2) and nitrous oxide (N2O) fluxes, and biomass yield from switchgrass field were predicted using DAYCENT models for 2016 through 2050. Measured data for model calibration and validation at this study site managed with nitrogen fertilization rates (N rates) (low, 0 kg N ha?1; medium, 56 kg N ha?1; and high, 112 kg N ha?1) and landscape positions (shoulder and footslope) for switchgrass production were collected from the previously published studies. Modeling results showed that the N fertilization can enhance SOC and soil NO3?, but increase soil N2O and CO2 fluxes. In this study, medium N fertilization was the optimum rate for enhancing switchgrass yield and reducing negative impact on the environment. Footslope position can be beneficial for improving SOC, , and yield, but contribute higher greenhouse gas (GHG) emissions compared to those of the shoulder. An increase in temperature and decrease in precipitation (climate scenarios) may reduce soil , WFPS, and N2O flux. Switchgrass production can improve and maintain SOC and , and reduce N2O and CO2 fluxes over the predicted years. These findings indicate that switchgrass could be a sustainable bioenergy crop on marginally yielding lands for improving soils without significant negative impacts on the environment in the long run.  相似文献   

16.
In most plants, constitutes the major source of nitrogen, and its assimilation into amino acids is mainly achieved in shoots. Furthermore, recent reports have revealed that reduction of translocation from roots to shoots is involved in plant acclimation to abiotic stress. NPF2.3, a member of the NAXT (nitrate excretion transporter) sub‐group of the NRT1/PTR family (NPF) from Arabidopsis, is expressed in root pericycle cells, where it is targeted to the plasma membrane. Transport assays using NPF2.3‐enriched Lactococcus lactis membranes showed that this protein is endowed with transport activity, displaying a strong selectivity for against Cl?. In response to salt stress, translocation to shoots is reduced, at least partly because expression of the root stele transporter gene NPF7.3 is decreased. In contrast, NPF2.3 expression was maintained under these conditions. A loss‐of‐function mutation in NPF2.3 resulted in decreased root‐to‐shoot translocation and reduced shoot content in plants grown under salt stress. Also, the mutant displayed impaired shoot biomass production when plants were grown under mild salt stress. These mutant phenotypes were dependent on the presence of Na+ in the external medium. Our data indicate that NPF2.3 is a constitutively expressed transporter whose contribution to translocation to the shoots is quantitatively and physiologically significant under salinity.  相似文献   

17.
The potential ecological impacts of switchgrass (Panicum virgatum L.), as a biofuel feedstock, have been assessed under different environmental conditions. However, limited information is available in understanding the integrated analysis of nitrogen (N) dynamics including soil nitrate (), nitrous oxide (N2O) emissions, and leaching under switchgrass land management. The specific objective was to explore N dynamics for 2009 through 2015 in switchgrass seeded to a marginally yielding cropland based on treatments of N fertilization rate (N rate; low, 0; medium, 56; high, 112 kg N ha?1) and landscape position (shoulder, backslope, and footslope). Our findings indicated that N rate impacted soil (0–5 cm depth) and surface N2O fluxes but did not impact leaching during the observed years. Medium N (56 kg N ha?1) was the optimal rate for increasing biomass yield with reduced environmental problems. Landscape position impacted the N dynamics. At the footslope position, soil , soil leaching, and N2O fluxes were higher than the other landscape positions. Soil N2O fluxes and leaching had downward trends over the observed years. Growing switchgrass on marginally yielding croplands can store soil N, reduce N losses via leaching, and mitigate N2O emissions from soils to the atmosphere over the years. Switchgrass seeded on marginally yielding croplands can be beneficial in reducing N losses and can be grown as a sustainable bioenergy crop on these marginal lands.  相似文献   

18.
The ability of micro‐organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18O‐labeled water and closed‐system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to ?17.3‰ to ?25.9‰ for O2 and ?1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide‐associated oxygen derived from water varies significantly (38%–62%) among these bio‐oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral‐bound oxygen from water and O2. Additionally, direct incorporation of molecular O2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of of environmental O2, a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance.  相似文献   

19.
20.
Yen‐Tsung Huang 《Biometrics》2019,75(4):1191-1204
Mediation effects of multiple mediators are determined by two associations: one between an exposure and mediators (‐) and the other between the mediators and an outcome conditional on the exposure (‐). The test for mediation effects is conducted under a composite null hypothesis, that is, either one of the ‐ and ‐ associations is zero or both are zeros. Without accounting for the composite null, the type 1 error rate within a study containing a large number of multimediator tests may be much less than the expected. We propose a novel test to address the issue. For each mediation test , , we examine the ‐ and ‐ associations using two separate variance component tests. Assuming a zero‐mean working distribution with a common variance for the element‐wise ‐ (and ‐) associations, score tests for the variance components are constructed. We transform the test statistics into two normally distributed statistics under the null. Using a recently developed result, we conduct hypothesis tests accounting for the composite null hypothesis by adjusting for the variances of the normally distributed statistics for the ‐ and ‐ associations. Advantages of the proposed test over other methods are illustrated in simulation studies and a data application where we analyze lung cancer data from The Cancer Genome Atlas to investigate the smoking effect on gene expression through DNA methylation in 15 114 genes.  相似文献   

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