Marked negative δ
13C excursions in Ediacaran-age carbonate sediments have been identified in several sections globally, but are not recognized in all sections of similar age. The presence of δ
13C
...carb values as low as −12‰ has been interpreted as recording fundamentally different processes in the global carbon cycle than those recognized today. The δ
13C
carb anomalies are strongly correlated with δ
18O
carb values but are not represented in δ
13C
org records. While no primary depositional processes have been identified that can produce the correlated δ
18O–δ
13C arrays, simulations show that fluid–rock interaction with high-
pCO
2 fluids is capable of producing such arrays at geologically reasonable
pCO
2 and water–rock ratios. Variations in the Mg/Ca ratio and sulfate concentration of the altering fluid determine the extent of dolomite vs. calcite and anhydrite in the resulting mineral assemblage. Incorporation of an initially aragonitic mineralogy demonstrates that high Sr, low Mn/Sr and modest alteration of
87Sr/
86Sr in ancient carbonates are all compatible with a burial diagenesis mechanism for generation of the δ
13C anomalies, and do not necessarily imply preservation of primary values. The profound Ediacaran negative δ
13C anomalies can be adequately explained by well-understood diagenetic processes, conflated with the difficulty of correlating Precambrian sections independently of chemostratigraphy. They are not a record of primary seawater variations and need not have independent stratigraphic significance.
The minor extent of sulfur isotope fractionation preserved in many Neoarchean sedimentary successions suggests that sulfate-reducing microorganisms played an insignificant role in ancient marine ...environments, despite evidence that these organisms evolved much earlier. We present bulk, microdrilled, and ion probe sulfur isotope data from carbonate-associated pyrite in the ~2.5-billion-year-old Batatal Formation of Brazil, revealing large mass-dependent fractionations (approaching 50 per mil) associated with microbial sulfate reduction, as well as consistently negative Δ33S values (~ −2 per mil) indicative of atmospheric photochemical reactions. Persistent 33S depletion through ~60 meters of shallow marine carbonate implies long-term stability of seawater sulfate abundance and isotope composition. In contrast, a negative Δ33S excursion in lower Batatal strata indicates a response time of ~40,000 to 150,000 years, suggesting Neoarchean sulfate concentrations between ~1 and 10 μM.
Targeted tandem mass spectrometry (LC-MS/MS) has been extremely useful for profiling small molecules extracted from biological sources, such as cells, bodily fluids and tissues. Here, we present a ...protocol for analysing incorporation of the non-radioactive stable isotopes carbon-13 (
C) and nitrogen-15 (
N) into polar metabolites in central carbon metabolism and related pathways. Our platform utilizes selected reaction monitoring (SRM) with polarity switching and amide hydrophilic interaction liquid chromatography (HILIC) to capture transitions for carbon and nitrogen incorporation into selected metabolites using a hybrid triple quadrupole (QQQ) mass spectrometer. This protocol represents an extension of a previously published protocol for targeted metabolomics of unlabeled species and has been used extensively in tracing the metabolism of nutrients such as
C-labeled glucose,
C-glutamine and
N-glutamine in a variety of biological settings (e.g., cell culture experiments and in vivo mouse labelling via i.p. injection). SRM signals are integrated to produce an array of peak areas for each labelling form that serve as the output for further analysis. The processed data are then used to obtain the degree and distribution of labelling of the targeted molecules (termed fluxomics). Each method can be customized on the basis of known unlabeled Q1/Q3 SRM transitions and adjusted to account for the corresponding
C or
N incorporation. The entire procedure takes ~6-7 h for a single sample from experimental labelling and metabolite extraction to peak integration.
Spatio‐temporal heterogeneity in soil water content is recognized as a common phenomenon, but heterogeneity in the hydrogen and oxygen isotope composition of soil water, which can reveal processes of ...water cycling within soils, has not been well studied. New advances are being driven by measurement approaches allowing sampling with high density in both space and time. Using in situ soil water vapour probe techniques, combined with conventional soil and plant water vacuum distillation extraction, we monitored the hydrogen and oxygen stable isotopic composition of soil and plant waters at paired sites dominated by grasses and Gambel's oak (Quercus gambelii) within a semiarid montane ecosystem over the course of a growing season. We found that sites spaced only 20 m apart had profoundly different soil water isotopic and volumetric conditions. We document patterns of depth‐ and time‐explicit variation in soil water isotopic conditions at these sites and consider mechanisms for the observed heterogeneity. We found that soil water content and isotopic variability were damped under Q. gambelii, perhaps due in part to hydraulic redistribution of deep soil water or groundwater by Q. gambelii in these soils relative to the grass‐dominated site. We also found some support for H isotope discrimination effects during water uptake by Q. gambelii. In this ecosystem, the soil water content was higher than that at the neighbouring Grass site, and thus, 25% more water was available for transpiration by Q. gambelii compared with the Grass site. This work highlights the role of plants in governing soil water variation and demonstrates that they can also strongly influence the isotope ratios of soil water. The resulting fine‐scale heterogeneity has implications for the use of isotope tracers to study soil hydrology and evaporation and transpiration fluxes to improve understanding of water cycling through the soil–plant–atmosphere continuum.
Silicon (Si) isotopes are useful tracers for the modern and ancient Si cycle, but their interpretation is limited by inadequate understanding of Si isotope exchange kinetics and fractionation factors ...at low temperature. This study investigated Si isotope exchange and fractionation between aqueous and amorphous Si at circumneutral pH and room temperature through a series of 29Si-spiked isotope-exchange experiments. Four different amorphous Si solids with varied surface areas were reacted with aqueous Si solutions of high ionic strength similar to seawater, or low ionic strength typical of freshwater, under conditions close to chemical equilibrium with respect to amorphous Si solubility. In contrast to the common perception of negligible Si isotope exchange at low temperature, ∼50–85% isotope exchange was achieved between aqueous and amorphous Si within ∼60 days. Larger solid surface areas and higher aqueous ionic strength generally promoted Si isotope exchange. Drying/aging of Si gel, however, impedes Si isotope exchange between amorphous and aqueous Si relative to freshly prepared Si gels. Excluding the experiments that used the aged Si gel, temporal trajectories of Si isotope evolution of the two phases from all other experiments showed significant curvature in three-isotope space (29Si/28Si and 30Si/28Si). These results can be best explained by a model that comprises two Si isotope exchange processes with different exchange rates and fractionation factors during the interactions between aqueous and amorphous Si towards isotope equilibrium. The faster exchange is associated with surface sites, and slower exchange occurs between exterior and interior Si atoms of the solid. Exchange with surface sites tends to partition heavy Si isotopes in the aqueous phase relative to the solid surface, whereas exchange between surface and interior sites in the solid tends to enrich heavy Si isotopes in the interior. Two experiments that achieved >80% isotope exchange provided the best estimates of equilibrium Si isotope fractionation factors between bulk amorphous Si solid and aqueous monomeric silicic acid H4SiO4 (Δ30Siamorphous–aqueous) at 23 °C: +0.52‰ (±0.15‰, 1sd) at seawater ionic strength, and −0.98‰ (±0.12‰) at freshwater ionic strength. The observed “salt effect” on Si isotope exchange kinetics and fractionation factor is interpreted to reflect an influence of cations on Si speciation of solid surfaces. This work highlights the value of three-isotope method in studying both reaction kinetics and isotope fractionation mechanisms. The observed Si isotope exchange between amorphous and aqueous Si at low temperature implies that Si isotope re-equilibration, a previously neglected process, may be important in controlling Si isotope compositions of natural samples.
In batch culture experiments, we examined the isotopic change of nitrogen in nitrate (δ15NNO3), carbon in dissolved inorganic carbon (δ13CDIC), and sulfur in sulfate (δ34SSO4) during heterotrophic ...and autotrophic denitrification of two bacterial strains (Pseudomonas aureofaciens and Thiobacillus denitrificans). Heterotrophic denitrification (HD) experiments were conducted with trisodium citrate as electron donor, and autotrophic denitrification (AD) experiments were carried out with iron disulfide (FeS2) as electron donor. For heterotrophic denitrification experiments, a complete nitrate reduction was accomplished, however bacterial denitrification with T. denitrificans is a slow process in which, after seventy days nitrate was reduced to 40% of the initial concentration by denitrification. In the HD experiment, systematic change of δ13CDIC (from −7.7‰ to −12.2‰) with increase of DIC was observed during denitrification (enrichment factor εN was −4.7‰), suggesting the contribution of C of trisodium citrate (δ13C=−12.4‰). No SO42− and δ34SSO4 changes were observed. In the AD experiment, clear fractionation of δ13CDIC during DIC consumption (εC=−7.8‰) and δ34SSO4 during sulfur use of FeS2–S (around 2‰), were confirmed through denitrification (εN=−12.5‰). Different pattern in isotopic change between HD and AD obtained on laboratory-scale are useful to recognize the type of denitrification occurring in the field.
•Two types of denitrification experiments using two bacterial strains were done.•In heterotrophic denitrification (HD) δ13CDIC changed with the increase of DIC.•In autotrophic denitrification (AD) fractionation of δ13CDIC and δ34SSO4 occurred.•Combined δ15NNO3, δ13CDIC, and δ34SSO4 measurements help to separate HD from AD.
•Smectite clays in soil are not isotopically inert with respect to the soil water.•Mg, Ca, or K adsorbed to smectite fractionate the bulk water in clay-water mixtures.•Isotopic measurement by direct ...equilibration may reflect only portions of soil water.•This isotope effect may be present in natural, high-clay soils and sediments.•These findings are relevant to pedomineralogy, ecohydrology, and climatology.
In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral–water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral–water interactions.
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