Apparent Fractionation Factor Research Articles

Antimony isotopic fractionation during Sb(III) oxidation to Sb(V): Biotic and abiotic processes

Oxidation of antimonite (Sb(III)) to antimonate (Sb(V)) plays an important role in the control of Sb mobility in aquatic systems. Fractionation of Sb isotopes (123Sb/121Sb) during Sb(III) oxidation has been investigated in the present study at concentrations relevant to mining environments. The isotopic composition (δ123Sb) of dissolved Sb(III) and Sb(V) species was analysed during biotic oxidation of Sb(III) at pH 6 and ∼ 0.1 mM Sb. Biotic experiments used a aioA gene carrier bacterial strain of the genus Ensifer isolated from Sb-rich river sediments. Chemical oxidation experiments with H2O2 were also conducted either in NaNO3 or HCl medium. During biotic oxidation, the Sb(V) produced was enriched in the light isotope compared to Sb(III), with an apparent fractionation factor Δ123SbSb(V)-Sb(III) of −0.20 ± 0.07 ‰. The Δ123Sb value was independent of the oxidation kinetics within the range 0.03 to 0.05 μmol.L−1.min−1; the fractionation observed was rather attributed to kinetic effect that weakens over time in the experiments, although this hypothesis would require further investigation. During abiotic experiments in NaNO3 medium, the Sb(V) produced was not isotopically fractionated relatively to Sb(III), while in HCl medium, the Sb(V) produced was enriched with the heavier isotope relatively to Sb(III), with a Rayleigh fractionation factor ε123Sb of +0.30 ± 0.05 ‰. These differences were attributed to different reaction pathways involving multi-step reactions and either hydroxy- or chloride-Sb species. Altogether, these results showed a low fractionation of Sb isotopes during Sb(III) oxidation, although significant variability occurred according to experimental conditions. Further experimental research and confrontation with natural systems is necessary before applying Sb isotopes as process tracer in water.

Carbon isotope effects in the sorption of chlorinated ethenes on biochar and activated carbon

As an alternative to activated carbon, biochar is a promising, environmentally friendly sorbent that can be used to remove organic groundwater pollutants, such as chlorinated ethenes (CEs). Stable isotope fractionation in biofilters is used to quantify pollutant degradation and to distinguish degradation from pollutant sorption on e.g. biochar. However, the sorption of CEs on biochar, and the potential abiotic fractionation processes remain to be tested. The sorption process of CEs and ethene on activated carbon and biochar was investigated with regard to the isotope effects for the differentiation from microbial degradation processes. Results from physical and chemical characterization of biochar indicated that biochar feedstock and pyrolysis conditions determined sorption performance depending on the surface chemistry and the pore size distribution of the coarse sorbent particles. The sorption capacity of the activated carbon was significantly higher with highly chlorinated ethenes, but similar to the biochars with low chlorination. Apparent carbon isotope fractionation factors (ε) of +0.1 to −4.4 ‰ were found above measurement uncertainties of GC/IRMS. The extent of isotope enrichment of the 13C bearing isotopologues in the residual aqueous phase (ε < 0) was characteristic for individual pairs of pollutant and sorbent material and could be related to pore-filling processes limited by the micropore size distribution of sorbent materials and the chemical properties of sorbed pollutants. Especially the large isotope fractionation during the sorption of ethene led to the assumption that diffusion processes within the pore matrix of the sorbent particles contributed to the observed isotope effects, but should still be considered a property of sorption. Concluding on the results indicated that sorption processes can have a significant contribution to carbon isotope fractionation in CEs and ethene. These should not be neglected in the evaluation of biofilters for groundwater purification, in which CEs are simultaneously degraded by microbes.

Hydrogen isotope biogeochemistry of plant waxes in paired lake catchments

Studies of plants in modern catchment systems can serve to improve the level of understanding of sedimentary plant wax hydrogen isotope (δ2H) data by directly investigating the link between local climate conditions, plant source water, leaf water, and plant lipids for individual plant species. Here we present such an application to compare two lake catchments with different basin morphologies in Estonia. We sampled leaf and xylem water, as well as leaf waxes from the seven common plant species in each catchment, and soil water. We then measured the δ2H values of all waters, and of n-alkanes (δ2Hn–alk) from the plant waxes, as well as surface lake sediments. We applied a Péclet modified Craig-Gordon leaf water model using local precipitation isotope and climate data to characterize the δ2H values of the biosynthetic source water pool throughout the entire growth season. The data and model results provide a detailed view of how the input hydro-climatic signals from the precipitation δ2H values were modified by environmental and plant physiological conditions and ultimately by the biosynthetic isotope fractionation associated with n–alkane production by each plant species. We report both average apparent (εapp = –92 ± 21 ‰) and biosynthetic (εbio = –132 ± 19 ‰) hydrogen isotope fractionation factors of all species from the studied catchments. This information serves as a foundation for sedimentary organic geochemistry and paleoclimate studies, which allows for more direct and quantitative links to be made between sedimentary plant wax δ2H values and the climate signal contained in plant source water.

Enrichment of heavy calcium isotopes in saprolite due to secondary mineral formation

Calcium stable isotopes were analyzed in well-characterized saprolite samples developed on a Mesozoic metadiabase dike near Cayce, South Carolina, to determine the degree and sense of isotopic fractionation during chemical weathering. The δ44/40Ca values (relative to NIST SRM 915a) of the saprolites, measured using double-spike TIMS, vary significantly (0.91‰ to 1.26‰), and are generally higher than the δ44/40Ca value of the unweathered metadiabase (0.98‰), which overlaps, within analytical uncertainties, with the δ44/40Ca estimate of the bulk silicate Earth. The δ44/40Ca values of the saprolites negatively correlate with bulk density, and Ti-normalized calcium concentrations, and positively correlate with chemical index of alteration (CIA) values. These trends reflect loss of light Ca isotopes to the hydrosphere during metadiabase weathering. Using insoluble incompatible elements ratios (e.g., Th/Nb) we estimate that the influence of aeolian dust is minimal (3% - 11%) and therefore unable to explain the observed variation in δ44/40Ca values of the saprolites. Selective weathering of rock-forming minerals like plagioclase and clinopyroxene cannot explain the high δ44/40Ca values (> 1 ‰) of the saprolites based on mass balance constraints. Samples with higher kaolinite/smectite ratio have higher δ44/40Ca values and lower concentrations of Ca, which suggests the loss of Ca from smectite-rich clays during progressive weathering. In this case, the lighter isotopes are preferentially lost, leaving the residual clays enriched in heavier isotopes of Ca. The δ44/40Ca values of saprolites correlate positively with δ26Mg and negatively with δ7Li values of the same samples, which further suggests that Ca stable isotopic variability of the Cayce metadiabase saprolites is controlled by formation of clay minerals and progressive loss of Ca during saprolitization. The enrichment of heavy Ca isotopes in saprolites with progressive loss of Ca can be modeled using Rayleigh distillation, with apparent fractionation factors between saprolites and fluid (α) of 1.00005 to 1.00015.

Stable Barium Isotope Fractionation in Pore Waters of Estuarine Sediments

AbstractThe development of stable barium (Ba) isotope measurements provides a novel tool to investigate the geochemical cycling of Ba in the ocean and its sediments. In sediment pore waters, gradients of dissolved Ba concentrations result from various diagenetic processes. The distribution and fractionation of Ba isotopes in the pore waters are expected to further improve our understanding of these early diagenetic control mechanisms. Here, we present pore water profiles of dissolved stable Ba isotopic signatures (δ138Bapw) from shallow water sediments covering the entire Pearl River Estuary (PRE) in Southern China. We find pronounced depth‐dependent Ba isotope variations generally showing a shift from heavy to light δ138Bapw signatures from the sediment surface down to 15 cm depth. These gradients are well reproduced by a diffusion‐reaction model, which generates an apparent fractionation factor (138ε) of −0.60 ± 0.10‰ pointing to preferential removal of low‐mass Ba isotopes from the pore water during solution‐solid phase interactions. Consequently, the combined diagenetic processes induce the highest δ138Bapw values of +0.5 to +0.7‰ in the pore waters of the topmost sediment layer. Although the detrital fraction dominates the Ba content in the PRE surface sediments, the determined gradients of pore water Ba isotopes, together with concentration variations of Ba and other redox‐sensitive elements such as manganese (Mn), show that non‐detrital excess Ba carriers including Mn oxides and authigenic barite clearly affect the post‐depositional Ba dynamics. Stable Ba isotopes are thus a potentially powerful tracer of Ba geochemistry during early sediment diagenesis in estuarine depositional environments.

Barium isotope behavior during interaction between serpentinite-derived fluids and metamorphic rocks in the continental subduction zone

Serpentinites in subduction zones are important fluid reservoirs for crust-mantle interaction and arc magma formation. The serpentinite-derived fluids can carry fluid-mobile elements such as Ba and potentially affect the geochemical composition of the metamorphic rocks in the subduction zones. However, the Ba isotope behavior during interaction between serpentinite-derived fluids and metamorphic rocks is still poorly understood. The whiteschists of the Dora-Maira Massif in the Western Alps have experienced fluid infiltration by serpentinite-derived fluids during deep subduction. Here we report the Ba isotope data of the whiteschist and its protolith metagranite to investigate the Ba isotope behavior during fluid-rock interaction. The metagranites, which have experienced ultrahigh-pressure metamorphism, have a small variation of δ138Ba (−0.25 to 0.26‰), while the whiteschists display a large Ba isotope variation from −0.99‰ to 0.48‰. Such a large variation in whiteschists cannot be explained by chemical weathering, protolith heterogeneity, or kinetic effects. Instead, considering the negative correlations of δ138Ba with Ba and other fluid-mobile elements (e.g., Sr, Cs, Zn, and Cu) and the geochemical composition features of serpentinite-derived fluids, the large Ba isotope variation in whiteschists is inferred to be induced by the interaction between serpentinite-derived fluid and metagranite during intense fluid infiltration. This is consistent with the observation that the whiteschists with low Ba contents tend to exhibit heavier Mg-Fe isotope compositions but lighter Li isotope compositions, which indicates that the related fluids were derived from the dehydration of mantle wedge serpentinite. The fluid infiltrating process is well explained by a numerical model with high fluid-rock ratios of 4 to 12. Our modeling further suggests that serpentinite-derived fluid has a distinctly higher δ138Ba value than the depleted upper mantle. During fluid-rock interaction, heavy Ba isotopes prefer to be infiltrated into fluids with an apparent fractionation factor (Δ138Barock-fluid) of mostly −0.5‰ to −0.1‰ but can be down to −0.8‰ to −0.7‰ required for a few samples. A two-stage dehydration and metasomatism model at different depths can well explain the formation of Dora-Maira whiteschists. Whereas the Ba isotope composition of mantle wedge serpentinite is mainly dictated by crust-derived fluids from the subducting slab, an interaction between the serpentinite-derived fluids and the metagranite protolith resulted in a large Ba isotope variation of whiteschists. In case of a general involvement of serpentinites in subduction zones, serpentinite-derived fluids would significantly affect the Ba isotope compositions of subarc mantle peridotites and also arc lavas.

Magnesium isotope fractionation between calcite and aqueous solutions under elevated temperatures of 98–170 °C

The incomplete understanding of Mg isotope fractionation behavior between calcite and aqueous solutions has limited the interpretation and application of Mg isotope data in natural carbonates. In this study, we performed a series of aragonite-to-calcite conversion experiments under hydrothermal conditions to investigate the effects of temperature and organic ligands on elemental and isotopic partitioning of Mg between calcite and aqueous solutions. The experiments produced magnesian calcite via a dissolution-and-precipitation process. The Mg distribution coefficients between solid and aqueous solution (DMg, 0.08 to 0.21) showed negative correlations with Sr distribution coefficients (DSr, 0.04 to 0.48), as well as the proportion of calcite in the bulk solid, which indicates mixing of calcite (Mg-rich and Sr-poor) and aragonite (Sr-rich and Mg-poor) in the solid phases. The apparent Mg isotope fractionation factors between solid and aqueous solutions (Δ26Mgsolid-soln) show a positive correlation with reaction temperatures, where Δ26Mgsolid-soln increases from ca. −1.84 ‰ at 98 °C to −1.35 ‰ at 170 °C. In addition, the presence of oxalate contributed to slightly lower Δ26Mgsolid-soln values, which is interpreted to be related to the isotopic effect of Mg-oxalate speciation. Based on the experimental results, we propose a temperature-dependent function for Mg isotope fractionation between calcite and free Mg-aquo ions (i.e., Mg(H2O)62+): Δ26Mgcal-Mg(aq) = (−0.17 ± 0.01) × 106/T2- (0.52 ± 0.08). This equation is applicable to a wide range of temperatures, especially at hydrothermal conditions, thus enabling interpretations of Mg isotope data from calcite of hydrothermal and burial origin.

Leaf wax biomarkers of a high-mountain lake area in western iberia—Implications for environmental reconstructions

Leaf wax n-alkane biomarkers are widely used to infer past vegetation dynamics and hydroclimate changes. The use of these compounds strongly relies on the characterization of modern plants. However, few studies have explored leaf waxes of modern plants and their application to reconstructing climate and environmental changes in the Iberian Peninsula, a region known for its high vulnerability to climate change. In this study, we characterize the distributions and compound-specific isotopic compositions of the leaf waxes of dominant plants in the vegetation cover, soil, and surface sediment of the Lake Peixão area, a high-mountain glacial lake in Serra da Estrela (central Portugal). Our results show that the modern oro-Mediterranean (subalpine) vegetation of the study area is dominated by C3 grasses/herbs and shrubs that preferentially produce long-chain leaf waxes (≥C27). The C31n-alkane display the overall highest concentration, produced by some grasses and shrubs, but especially Erica sp (heather), which is highlighted as a major source for the total n-alkane pool in the lake sediments. C29 is the second-most abundant and the most equally produced n-alkane of the vegetation cover; C25 and C27 homologs are mainly associated with aquatic-related grasses/herbs, while C33 and C35 are particularly linked to cold-drought tolerant Juniperus sp. shrubs. Shrubs show higher but proportional values than grasses/herbs in the isotopic space, suggesting a directly proportional physiological adaptation of the two ecological forms to the prevailing climatic and environmental factors of the study area. C29 is pointed as the most representative (or less plant-biased) leaf wax n-alkane in the lake sediments. Thus, δD of C29n-alkane is interpreted as a robust terrestrial hydrological indicator (δDterr), which signal is believed to be strongly influenced by the mean air temperature and/or precipitation amount. Despite the sparse vegetation and small catchment area, the apparent hydrogen fractionation factor, determined from δDterr of the lake surface sediment, is in line with the modeled global mean values for the latitude of the study area. The different molecular and compound-specific signatures of the studied oro-Mediterranean species have the potential to support future interpretations of leaf wax biomarkers in the Iberian Peninsula.

Potassium isotope fractionation during granitic magmatic differentiation: Mineral-pair perspectives

To constrain the behavior of K isotopes during granitic magmatic differentiation, we present high-precision K isotope data for bulk granitoids and their K-bearing minerals from Dabie and Himalayan orogens in China. Plagioclase displays extremely large K isotopic variation, with δ41K ranging from −0.56 to 1.91‰. Other minerals also have heterogeneous K isotopic compositions, with δ41K varying from −0.56 to −0.24‰ in hornblende, from −0.72 to −0.39‰ in biotite, from −0.79 to −0.47‰ in K-feldspar, and from −0.74 to −0.61‰ in muscovite. The general trend of 41K enrichment follows the order of plagioclase ≫ hornblende > biotite ≈ K-feldspar ≥ muscovite, which can be attributed to the difference in KO bond strengths. Both δ41K of plagioclase and K isotope fractionation factors between plagioclase and other minerals are negatively correlated with K concentration in plagioclase, suggesting a compositional control on isotope fractionations. Inter-mineral K isotope fractionations among other minerals are roughly temperature-dependent. Potassium isotopic compositions of whole rocks display measurable variations (δ41K = –0.69 to −0.28‰), which are correlated with proxies for plagioclase fractionation (e.g., Sr and Rb/Sr). The correlation indicates that fractional crystallization may account for the whole-rock K isotopic variations observed in high-silica igneous rocks, which is supported by modeling of fractional crystallization using the apparent isotope fractionation factors determined in this work. Our study demonstrates the existence of large K isotope fractionation during granitic magmatism, making K isotopes a potential tool for studying differentiation of felsic magmas.

Mid- and long-chain leaf wax δ2H values in modern plants and lake sediments from mid-latitude North America

Compound-specific δ2H values of leaf wax n-alkanes are increasingly being used to infer past hydroclimates. However, differences in n-alkane production and apparent fractionation factors (εapp) among different plant groups complicate the relationships between n-alkane δ2H values and those of environmental water. Mid- and long-chain n-alkanes in sedimentary archives (i.e., n-C23 and n-C29) are thought to derive from aquatic and terrestrial plants, respectively, and track the isotopic composition of either lake water or precipitation. Yet, the relationship between n-C23 δ2H values and lake water δ2H values is not well constrained. Moreover, recent studies show that n-alkane production is greater in terrestrial plants than in aquatic plants, which has the potential to obscure n-alkane aquatic inputs to sedimentary archives. Here, we investigated n-alkane contributions to sedimentary archives from both aquatic and terrestrial plants by analyzing n-alkane δ2H values in plants and lake sediments at 29 sites across mid-latitude North America. We find that both aquatic and terrestrial plants synthesize n-C23 and that sedimentary n-C23 δ2H values parallel those of terrestrial plants and differ from those of aquatic plants. Our results indicate that across mid-latitude North America, both mid- and long-chain n-alkanes in lake sediments commonly derive from terrestrial higher plants challenging the assumption that submerged aquatic plants produce the n-C23-alkane preserved in lake sediments. Moreover, angiosperm and gymnosperm plants exhibit similar εapp values between n-C29 and mean annual precipitation (MAP) δ2H values across North America. Therefore, vegetation shifts between angiosperm and gymnosperm plants do not strongly affect εapp values between n-C29 and MAP. Our results show that both mid- and long-chain n-alkanes track the isotopic composition of MAP in temperate North America.

Extreme methane clumped isotopologue bio-signatures of aerobic and anaerobic methanotrophy: Insights from the Lake Pavin and the Black Sea sediments

Microbial methane oxidation - or methanotrophy - is a key control of the global methane budget on Earth, and perhaps in other planetary systems. Here, we explore the potential role of mass-18 isotopologues of methane, expressed as Δ13CH3D and Δ12CH2D2 values, in tracking both aerobic and anaerobic methanotrophy in nature. We examine two well documented methanotrophic environments: the Lake Pavin (France) water column, where methane degradation is dominated by aerobic methanotrophy (AeOM), and the Black Sea sediments (offshore Romania), dominated by anaerobic methanotrophy (AOM) coupled to sulfate-reduction. In both settings, lighter isotopologues are preferentially consumed, generating elevated 13CH4/12CH4, 12CH3D/12CH4, 13CH3D/12CH4 and 12CH2D2/12CH4 ratios. This results in increasing of δ13C and δD values in the residual methane for both settings, as observed commonly in systems dominated by methanotrophy. As a result, AeOM and AOM cannot be easily distinguished by the development of δ13C and δD. In contrast, the Δ13CH3D and Δ12CH2D2 (departure from stochastic) values have opposite trajectories, with minimal decreases in the case of the AeOM-dominated system, but dramatic increases in the case of AOM, with Δ13CH3D and Δ12CH2D2 reaching values as high as 15.7 ‰ and 76.6 ‰, respectively. This contrasting behavior of clumped isotopologues signatures illustrates fundamental distinction between the two processes and the way they segregate methane isotopologues. These data demonstrate that both AeOM and AOM have distinctive kinetic isotope effects in natural settings, consistent with preliminary laboratory work. In particular, we find that γ-values (which measure the deviation to the product of ‘normal’ bulk isotope fractionation factors) are close to unity in the case of AeOM (i.e. a negligible clumped isotope effect), but significantly below unity in the case of AOM (i.e. strong clumped isotope effect). In addition, our data also illustrate how AOM under low-sulfate conditions may promote methane isotopologue equilibration. Taken together, we suggest these data and apparent isotopologue fractionation factors extrapolated from these two environments may help refine the potential bio-signatures of methane affected by methanotrophy.

Integrating plant wax abundance and isotopes for paleo-vegetation and paleoclimate reconstructions: a multi-source mixing model using a Bayesian framework

Abstract. Plant wax n-alkane chain length distribution and isotopes have been studied in modern ecosystems as proxies to reconstruct vegetation and climate of the past. However, most paleo-proxies focus on either concentrations or isotopes, whereas both carry complementary information on the mixing sources. We propose a multi-source mixing model in a Bayesian framework that evaluates both chain length distributions and isotopes simultaneously. The model consists of priors that include user-defined source groups and their associated parametric distributions of n-alkane concentration and δ13C. The mixing process involves newly defined mixing fractions such as fractional leaf mass contribution (FLMC) that can be used in vegetation reconstruction. Markov Chain Monte Carlo is used to generate samples from the posterior distribution of these parameters conditioned on both data types. We present three case studies from distinct settings. The first involves n-C27, n-C29, and n-C31 alkanes in lake surface sediments of Lake Qinghai, China. The model provides more specific interpretations on the n-alkane input from aquatic sources than the conventional Paq proxy. The second involves n-C29, n-C31, and n-C33 alkanes in lake surface sediments in Cameroon, western Africa. The model produces mixing fractions of forest C3, savanna C3, and C4 plants, offering additional information on the dominant biomes compared to the traditional two-end-member mixing regime. The third couples the vegetation source model to a hydrogen isotope model component, using biome-specific apparent fractionation factors (εa) to estimate the δ2H of mean annual precipitation. By leveraging chain length distribution, δ13C, and δ2H data of four n-alkane chains, the model produces estimated precipitation δ2H with relatively small uncertainty limits. The new framework shows promise for interpretation of paleo-data but could be further improved by including processes associated with n-alkane turnover in plants, transport, and integration into sedimentary archives. Future studies on modern plants and catchment systems will be critical to develop calibration datasets that advance the strength and utility of the framework.

Iron solid-phase differentiation controls isotopic fractionation during lateritic weathering of basalt

Laterites are important iron (Fe) reservoirs impacting the biogeochemical cycle of Fe at Earth’s surface, and Fe oxides are critical Fe-host minerals in laterites that affect the geochemical behavior of Fe. Whether and how the differentiation of Fe minerals controls Fe isotope fractionation during laterization, however, remains unclear. In this study, the mineralogy, element concentrations, and Fe isotope compositions are reported for a basalt-derived lateritic profile on Hainan Island, China, to investigate the role of Fe solid-phase differentiation in controlling Fe isotope fractionation during lateritic weathering. 57Fe Mössbauer spectroscopy at 13 K is conducted to quantitatively identify the solid-phase Fe, including FeIII-(oxy)hydroxides, FeIII-oxides, and organic/silicate-bound FeIII. The results from soil samples in the lower section show that RMZr,Fe values are positive and that δ56Fe values (−0.01‰ to 0.07‰; 0.05 ± 0.05‰ on average) are identical to those in parent basalt (0.03 ± 0.04‰). The limited variation in δ56Fe values is likely caused by the compaction effect and/or the downward transport of Fe from the upper soils. In contrast, RMZr,Fe values in soils from the upper section are generally negative, and their δ56Fe values (0.01‰ to 0.29‰) display zigzag variations and are linearly correlated with the amount of Fe present in hematite and goethite. The variation in δ56Fe value is likely caused by the atomic distribution of Fe in hematite and goethite, with heavy Fe preferentially incorporated into hematite rather than goethite. Based on the linear regression analysis, we calculated the apparent Fe isotope fractionation factor between hematite and goethite as 0.99 ± 0.18‰ (SD). A comparison of published Fe isotope data shows that the variation in δ56Fe value of silicate-derived soils and rivers may have a potential link with climatic factor (mostly temperature). Our study highlights the importance of Fe-mineral differentiation in controlling Fe isotope fractionation in laterite systems.

Age and chemistry of dissolved organic carbon reveal enhanced leaching of ancient labile carbon at the permafrost thaw zone

Abstract. Climate change will alter the balance between frozen and thawed conditions in Arctic systems. Increased temperatures will make the extensive northern permafrost carbon stock vulnerable to decomposition and translocation. Production, cycling, and transport of dissolved organic carbon (DOC) are crucial processes for high-latitude ecosystem carbon loss that result in considerable export off the Arctic landscape. To identify where and under what conditions permafrost DOC is mobilized in an Arctic headwater catchment, we measured radiocarbon (14C) of DOC and assessed DOC composition with ultraviolet–visible spectroscopy (UV–Vis) of surface waters and shallow and deep subsurface porewaters from 17 drainages in the Barrow Environmental Observatory in Alaska. Samples were collected in July and September 2013 to assess changes in age and chemistry of DOC over time. DOC age was highly variable ranging from modern (19 ‰ Δ14C) to approximately 7000 BP (−583 ‰ Δ14C). DOC age increased with depth, over the summer as the active layer deepened, and with increasing drainage size. DOC quality indicators reflected a DOC source rich in high molecular-weight and aromatic compounds, characteristics consistent with vegetation-derived organic matter that had undergone little microbial processing, throughout the summer and a weak relationship with DOC age. In deep porewaters, DOC age was also correlated with several biogeochemical indicators (including dissolved methane concentration, δ13C, and the apparent fractionation factor), suggesting a coupling between carbon and redox biogeochemistry influencing methane production. In the drained thawed lake basins included in this study, DOC concentrations and contributions of vegetation-derived organic matter declined with increasing basin age. The weak relationship between DOC age and chemistry and consistency in DOC chemical indicators over the summer suggest a high lability of old DOC released by thawing permafrost.

Cr Isotopes and the Engineered Attenuation of Cr(VI)-Rich Runoff.

The leaching of lateritic soils can result in drainage waters with high concentrations of Cr(VI). Such Cr(VI)-rich waters have developed in streams that drain lateritic soils in Central Sulawesi Island, Indonesia. Chromium in this lateritic drainage system is removed by reduction of Cr(VI) to Cr(III) through two faucets delivering an FeSO4 solution to the drainage waters. Cr stable isotope compositions from both water and sediment samples along the drainage path were used to evaluate the efficacy of this remediation strategy. Overall, dissolved [Cr(VI)] decreased moving downstream, but there was an increase in [Cr(VI)] after the first faucet that was effectively removed at the second faucet. This intermittent increase in [Cr(VI)] was the likely result of oxidative remobilization of sediment Cr(III) through reaction with Mn oxides. Cr isotope distributions reflect near quantitative reduction associated with the FeSO4 faucets but also reveal that Cr isotope fractionation is imparted due to Cr redox cycling, downstream. During this redox cycling, fractionation appeared to accompany oxidation, with the product Cr(VI) becoming enriched in 53Cr relative to the reactant Cr(III) with an apparent fractionation factor of 0.7 ± 0.3‰. This study suggests that while FeSO4 effectively removes Cr(VI) from the drainage, the presence of Mn oxides can confound attenuation and improvements to Cr(VI) remediation should consider means of preventing the back reaction of Cr(III) with Mn oxides.

Mechanisms controlling the Mg isotope composition of hydromagnesite-magnesite playas near Atlin, British Columbia, Canada

The alkaline playas near Atlin, British Columbia, Canada are likely one of the few surface environments on Earth where contemporaneous formation of hydromagnesite and magnesite occurs at temperatures that do not exceed 15 °C. This environment offers a unique opportunity to examine the impact of different formation mechanisms on Mg isotope compositions of Mg-carbonate minerals at low temperature. In this study, we report the Mg isotope composition of ultramafic bedrock, Mg-carbonate sediments, and both surface and ground waters in this geological setting. The composition of hydromagnesite suggests a Rayleigh-type distillation effect on the fluid Mg isotope ratios in unsaturated sediment above the water table. Through this mechanism of formation, hydromagnesite is progressively depleted in 24Mg obtaining δ26Mg values as high as +1.14‰ near the sediment surface. In contrast, magnesite formation is characterized by enrichment of the solid phase in 24Mg. The apparent Mg isotope fractionation factor during magnesite formation at ~10 °C ranges between -0.7 ± 0.1‰ and -1.8 ± 0.1‰. The distinct Mg isotope composition of hydromagnesite in comparison to magnesite supports magnesite formation occurring by precipitation from the fluid, or dissolution-reprecipitation, rather than solid-phase transformation from a hydrous Mg-carbonate precursor. Overall, the results provide insights on low temperature Mg-carbonate mineral formation that has implications for long-term storage of CO2.

Small calcium isotope fractionation at slow precipitation rates in methane seep authigenic carbonates

Natural calcium carbonate minerals express a range of calcium isotope fractionations, with the precipitated mineral typically enriched in the lighter isotopes of calcium relative to source fluids. Experimental and theoretical evidence shows a strong dependence on precipitation rate, although this relationship has not been well quantified over the range of precipitation rates observed in natural settings. Endmember cases show that average marine carbonate precipitation expresses a large fractionation (δ44/40Ca values lower than seawater by approximately 1‰), while diagenetic carbonate phases assumed to have precipitated or recrystallized at very slow rates show negligible fractionation. The limited examples of quantified precipitation rates in natural settings with measurable, non-zero fractionation represents a barrier for applying mechanistic models of calcium isotope fractionation to geological applications. This study examines a methane seep system in the northern Barents Sea south of Svalbard where authigenic carbonate minerals are precipitating, driven by anaerobic oxidation of methane, and where the apparent calcium isotope fractionation factor and precipitation rate can be constrained by measuring properties of the pore fluids. Pore fluid profiles are analyzed in two shallow cores, and authigenic carbonate nodules are analyzed in one of these cores. The pore fluid profiles point to a transitional, non-steady state which approximates a closed system, where the elevation of pore fluid calcium isotope ratios through carbonate precipitation can be modeled as a Rayleigh distillation system. The apparent fractionation factors for 44Ca/40Ca ratios at these sites are α = 0.99985 and 0.9996, although the carbonate nodules suggest a different calcium isotope fractionation factor may have been expressed under past conditions. Precipitation rates at the two sites are estimated to be 1.4 and 3.5 μmol/m2/h, intermediate between those of typical laboratory experiments and the much slower rates of marine diagenesis. Trace element analyses of the nodules (Mg/Ca and Sr/Ca ratios) suggest that both precipitation rate and mineralogy affect nodule composition. These results provide new constraints for the relationship between precipitation rate and calcium isotope fractionation and can inform modeling efforts leading towards mechanistic understanding of calcium isotope fractionation and trace element distributions in carbonate minerals.

Filamentous green algae Spirogyra regulates methane emissions from eutrophic rivers.

Excessive growth of filamentous green algae in rivers has attracted much attention due to their functional importance to primary production and carbon cycling. However, comprehensive knowledge of how filamentous green algae affect carbon cycling, especially the CH4 emissions from river ecosystems, remains limited. In this study, incubation experiments were conducted to examine the factors regulating CH4 emissions from a eutrophic river with dense growth of filamentous green algae Spirogyra through combinations of biogeochemical, molecular biological, and stable carbon isotope analyses. Results showed that although water dissolved oxygen (DO) in the algae+sediment (A+S) incubation groups increased up to 19 mg L-1, average CH4 flux of the groups was 13.09 μmol m-2 day-1, nearly up to two times higher than that from sediments without algae (S groups). The significant increase of sediment CH4 oxidation potential and methanotroph abundances identified the enhancing sediment CH4 oxidation during Spirogyra bloom. However, the increased water CH4 concentration was consistent with depleted water [Formula: see text] and decreased apparent fractionation factor (αapp), suggesting the important contribution of Spirogyra to the oxic water CH4 production. It can thus be concluded that high DO concentration during the algal bloom promoted the CH4 consumption by enhancing sediment CH4 oxidation, while algal-linked oxic water CH4 production as a major component of water CH4 promoted the CH4 emissions from the river. Our study highlights the regulation of Spirogyra in aquatic CH4 fluxes and will help to estimate accurately CH4 emissions from eutrophic rivers with dense blooms of filamentous green algae. Graphical abstract.

Multiple stable isotopic signatures corroborate the predominance of acetoclastic methanogenesis during CH4 formation in agricultural river networks

Methane (CH4) emitted from river networks provides a globally significant, yet poorly constrained barrier for the refinement of national greenhouse gas (GHG) inventories and the global CH4 budget. This study employed three isotopic methodologies, i.e., a simple mixing model, apparent fractionation factor, and dual isotopes (δ13C−CH4 and δD−CH4) to identify the biogenic CH4 production pathway (BMPP) in a typical agricultural river network in subtropical China. The results indicated that the contribution of acetoclastic methanogenesis (AM) to BMPP in the Tuojia River network (TRN) ranged from 85 to 99%, with the first reach (S1) supporting the most biogenic CH4 production. Furthermore, the αC value ranged from 1.00 to 1.039 and increased spatially over the four reaches (S1 to S4), while the αD value varied from 1.393 to 1.394, with S1 having the lowest value. The dual isotopes of δ13C and δD reflected a mixed BMPP. Clearly, the isotopic composition of CH4 corroborated the predominance of AM in the BMPP in the TRN. Additionally, there was a remarkable spatiotemporal variation in δ13C−CH4 and δD−CH4, as well as αC and αD. In combination with the correlation between the two paired isotopic signatures (antipathetic and positive, p < 0.05, respectively), this suggested a change in the BMPP in the TRN. The findings of our study implied that there was great impact of agricultural production and residential activities on environmental behavior of stable isotopes. Consequently, we recommend that multiple isotopic measures, based on long-term in situ isotopologue monitoring, should be applied when the uncertainties of CH4 emissions from river networks are addressed.

Nitrogen and Oxygen Isotope Signatures of Nitrogen Compounds during Anammox in the Laboratory and a Wastewater Treatment Plant.

Isotopic fractionation factors against 15N and 18O during anammox (anaerobic ammonia oxidization by nitrite) are critical for evaluating the importance of this process in natural environments. We performed batch incubation experiments with an anammox-dominated biomass to investigate nitrogen (N) and oxygen (O) isotopic fractionation factors during anammox and also examined apparent isotope fractionation factors during anammox in an actual wastewater treatment plant. We conducted one incubation experiment with high δ18O of water to investigate the effects of water δ18O. The N isotopic fractionation factors estimated from incubation experiments and the wastewater treatment plant were similar to previous values. We also found that the N isotopic effect (15εNXR of –77.8 to –65.9‰ and 15ΔNXR of –31.3 to –30.4‰) and possibly O isotopic effect (18εNXR of –20.6‰) for anaerobic nitrite oxidation to nitrate were inverse. We applied the estimated isotopic fractionation factors to the ordinary differential equation model to clarify whether anammox induces deviations in the δ18O vs δ15N of nitrate from a linear trajectory of 1, similar to heterotrophic denitrification. Although this deviation has been attributed to nitrite oxidation, the O isotopic fractionation factor for anammox is crucial for obtaining a more detailed understanding of the mechanisms controlling this deviation. In our model, anammox induced the trajectory of the δ18O vs δ15N of nitrate during denitrification to less than one, which strongly indicates that this deviation is evidence of nitrite oxidation by anammox under denitrifying conditions.