Isotope Fractionation Processes Research Articles

Measuring the 34S and 33S Isotopic Ratios of Volatile Sulfur during Planet Formation

Stable isotopic ratios constitute powerful tools for unraveling the thermal and irradiation history of volatiles. In particular, we can use our knowledge of the isotopic fractionation processes active during the various stages of star, disk, and planet formation to infer the origins of different volatiles with measured isotopic patterns in our own solar system. Observations of planet-forming disks with the Atacama Large Millimeter/submillimeter Array (ALMA) now readily detect the heavier isotopologues of C, O, and N, while the isotopologue abundances and isotopic fractionation mechanisms of sulfur species are less well understood. Using ALMA observations of the SO and SO2 isotopologues in the nearby, molecule-rich disk around the young star Oph-IRS 48 we present the first constraints on the combined 32S/34S and 32S/33S isotope ratios in a planet-forming disk. Given that these isotopologues likely originate in relatively warm gas (>50 K), like most other Oph-IRS 48 volatiles, SO is depleted in heavy sulfur, while SO2 is enriched compared to solar system values. However, we cannot completely rule out a cooler gas reservoir, which would put the SO sulfur ratios more in line with comets and other solar system bodies. We also constrain the S18O/SO ratio and find the limit to be consistent with solar system values given a temperature of 60 K. Together these observations show that we should not assume solar isotopic values for disk sulfur reservoirs, but additional observations are needed to determine the chemical origin of the abundant SO in this disk, inform on what isotopic fractionation mechanism(s) are at play, and aid in unraveling the history of the sulfur budget during the different stages of planet formation.

Inter- and Intra-Annual Variations in Oak Tree Ring δ13C Values across Different Elevations and Their Climatic Responses in Qinling Mountains

The Qinling Mountains, serving as a natural geographical and climatic boundary in China, require comprehensive climatic records to elucidate the trends in climate changes across the country. While stable isotopes in tree rings are widely employed to indicate historical environmental changes, investigations into tree ring isotopes in the Qinling Mountains, particularly within the widespread broad-leaf oaks, remain limited. In this study, we investigated both intra- and inter-annual variations in the δ13C values of tree rings and their correlations with climatic signals over the past two decades for Quercus aliena var. acuteserrata, a dominant species among oak trees on the main peak of the Qinling Mountains. Our results reveal that responses to climate differ among altitudes and individual trees, with trees at higher altitudes exhibiting higher sensitivity to extreme climate, which is low temperatures and rainfall fluctuations during the growth period in intra-annual δ13C variations. Furthermore, the positive correlations are observed between temperature during growing season and both tree growth and the inter-annual δ13C variations. However, the climate signal appears to be hampered by oak-specific factors, such as intense competition among individuals and the age of trees. Therefore, we suggest a more rigorous selection of sampling and propose further investigations into isotopic fractionation processes in oaks for future studies.

Stable carbon isotope evolution of formaldehyde on early Mars

Organic matter in the Martian sediments may provide a key to understanding the prebiotic chemistry and habitability of early Mars. The Curiosity rover has measured highly variable and 13C-depleted carbon isotopic values in early Martian organic matter whose origin is uncertain. One hypothesis suggests the deposition of simple organic molecules generated from 13C-depleted CO derived from CO2 photochemical reduction in the atmosphere. Here, we present a coupled photochemistry-climate evolution model incorporating carbon isotope fractionation processes induced by CO2 photolysis, carbon escape, and volcanic outgassing in an early Martian atmosphere of 0.5–2 bar, composed mainly of CO2, CO, and H2 to track the evolution of the carbon isotopic composition of C-bearing species. The calculated carbon isotopic ratio in formaldehyde (H2CO) can be highly depleted in 13C due to CO2-photolysis-induced fractionation and is variable with changes in atmospheric CO/CO2 ratio, surface pressure, albedo, and H2 outgassing rate. Conversely, CO2 becomes enriched in 13C, as estimated from the carbonates preserved in ALH84001 meteorite. Complex organic matter formed by the polymerization of such H2CO could explain the strong depletion in 13C observed in the Martian organic matter. Mixing with other sources of organic matter would account for its unique variable carbon isotopic values.

Diverse Orbital‐Scale Variations of Precipitation Oxygen Isotopes in the Northern Hemisphere Mid‐Latitudes: A Comparative Study Between East Asia and North America

AbstractThe oxygen isotope (δ18O) records of paleo‐precipitation contain abundant information on past climate changes. Nevertheless, at the orbital scale, our current understanding about the characteristics and mechanisms of precipitation oxygen isotope (δ18Op) variations in the Northern Hemisphere (NH) mid‐latitudes remains limited due to the lack of abundant long‐term geological records. In this study, based on a 300‐ka transient simulation involving stable isotope fractionation processes, we systematically analyzed the characteristics of the orbital‐scale δ18Op variations and their potential mechanisms, especially in two representative regions: mid‐latitude East Asia (MEA) and mid‐latitude North America (MNA) located in the Eastern and Western Hemispheres respectively. Our findings reveal that the MEA δ18Op is dominated by a 23‐ka cycle, ultimately driven by the precession‐induced insolation variation; while the MNA δ18Op primarily exhibits a 100‐ka glacial‐interglacial cycle and is eventually governed by the ice volume forcing. The δ18Op changes in these two regions not only present diverse dominant cycles and forcing factors, but also involve distinct physical processes. In MEA, water vapor transport by the westerly circulation during the rainy season (May–August) is the key process linking the April–July boreal insolation with the annual/rainy‐season δ18Op variations. In contrast, the annual δ18Op changes in MNA mainly depend on the water vapor transport processes triggered by the expansion and retreat of the North American ice sheet, albeit with certain influence of the temperature effect as well. These results suggest that the dominant periodicities and forcing mechanisms of the orbital‐scale δ18Op variations across the NH mid‐latitudes are complex and varied.

Dietary and homeostatic controls of Zn isotopes in rats: a controlled feeding experiment and modeling approach.

The stable isotope composition of zinc (δ66Zn), which is an essential trace metal for many biological processes in vertebrates, is increasingly used in ecological, archeological, and paleontological studies to assess diet and trophic level discrimination among vertebrates. However, the limited understanding of dietary controls and isotopic fractionation processes on Zn isotope variability in animal tissues and biofluids limits precise dietary reconstructions. The current study systematically investigates the dietary effects on Zn isotope composition in consumers using a combined controlled feeding experiment and box-modeling approach. For this purpose, 21 rats were fed one of seven distinct animal- and plant-based diets and a total of 148 samples including soft and hard tissue, biofluid, and excreta samples of these individuals were measured for δ66Zn. Relatively constant Zn isotope fractionation is observed across the different dietary groups for each tissue type, implying that diet is the main factor controlling consumer tissue δ66Zn values, independent of diet composition. Furthermore, a systematic δ66Zn diet-enamel fractionation is reported for the first time, enabling diet reconstruction based on δ66Zn values from tooth enamel. In addition, we investigated the dynamics of Zn isotope variability in the body using a box-modeling approach, providing a model of Zn isotope homeostasis and inferring residence times, while also further supporting the hypothesis that δ66Zn values of vertebrate tissues are primarily determined by that of the diet. Altogether this provides a solid foundation for refined (paleo)dietary reconstruction using Zn isotopes of vertebrate tissues.

Integrating paleolimnological hydrogen and oxygen isotope records during the Holocene on the Tibetan Plateau

Stable isotopes are effective proxy indicators for past climate and environment changes. Paleolimnological hydrogen and oxygen isotopes have been used to reconstruct changes in precipitation isotopes and continental climates. However, the stable hydrogen and oxygen isotope records from lakes are rarely compared and integrated directly to study past changes in climate and environment due to their different fractionation pathways. Combined studies on hydrogen and oxygen isotopes would provide much more information than single isotope records. Here, we reanalyzed published lacustrine hydrogen and oxygen isotope records across the Tibetan Plateau, to investigate how both isotope records reveal the influences of the Indian summer monsoon and the westerlies on the Plateau throughout the Holocene. Principal component analysis (PCA) shows that the first principal component (PC1) of 16 lacustrine hydrogen isotope records resembles that of 28 oxygen isotope records. The PC1s of the hydrogen and oxygen isotope records were generally low at 12–6 ka BP, followed by gradual increase since 6 ka BP, suggesting the influence of the Indian summer monsoon. Reconstruction of Holocene precipitation isotopes showed that the slopes of segmented precipitation isotope lines generally followed changes in monsoon intensity. The PC2s for hydrogen and oxygen isotope records remained relatively low at ∼8–4 ka BP, coinciding with moisture variation in westerlies dominated regions. The millennial-scale variations in both hydrogen and oxygen isotope records, revealed by the PC3-PC6, likely responded to the ice drift events in the North Atlantic Ocean, as well as differences in the isotope fractionation pathways at specific sites. The reanalysis of stable hydrogen and oxygen records across the Tibetan Plateau suggests that the water vapor source is the most important factor affecting the isotope variation, though the isotopic fractionation processes may differ significantly. Our results revealed nonlinear variations of monsoon and westerlies on the Tibetan Plateau during the Holocene. This review shows that integration of the stable hydrogen and oxygen isotope records would provide comprehensive understanding of the atmospheric circulation on the Tibetan Plateau.

Seasonal and multi-decadal zinc isotope variations in blue mussels from two sites with contrasting zinc contamination levels

Zinc (Zn) isotope compositions in soft mussel tissues help identify internal biological processes and track coastal Zn sources in coastal environments, thus aiding in managing marine metal pollution. This study investigated the seasonal and multi-decadal Zn isotope compositions of blue mussels (genus Mytilus) from two French coastal sites with contrasting Zn environmental contamination. Concurrently, we characterized the isotope ratios of sediments and plankton samples at each site to understand the associations between organisms and abiotic compartments. Our primary objective was to determine whether these isotope compositions trace long-term anthropogenic emission patterns or if they reflect short-term biological processes. The multi-decadal isotope profiles of mussels in the Loire Estuary and Toulon Bay showed no isotope variations, implying the enduring stability of the relative contributions of natural and anthropogenic Zn sources over time. At seasonal scales, Zn isotope ratios were also constant; hence, isotope effects related to spawning and body growth were not discernible. The multi-compartmental analysis between the sites revealed that Toulon Bay exhibits a remarkably lower Zn isotope ratio across all studied matrices, suggesting the upward transfer of anthropogenic Zn in the food web. In contrast, the Zn isotope variability observed for sediments and organisms from the Loire Estuary fell within the natural baseline of this element. In both sites, adsorptive geogenic material carrying significant amounts of Zn masks the biological isotope signature of plankton, making it difficult to determine whether the Zn isotope ratio in mussels solely reflects the planktonic diet or if it is further modified by biological homeostasis. In summary, Zn isotope ratios in mussels offer promising avenues for delineating source-specific isotope signatures, contingent upon a comprehensive understanding of the isotope fractionation processes associated with the trophic transfer of this element through the plankton.

Source‐sink patterns on coffee trees related to annual climate variability: An approach through stable isotopes analysis

AbstractStable isotopic determination constitutes a useful tool to identify the processes that control the dynamics of the carbon and nitrogen flow in plants, unravelling the mechanisms of their differential investment under different environments. This work aimed to evaluate the spatiotemporal variation of source‐sink patterns of coffee trees under field conditions in response to climatic conditions through the assessment of stable isotopes. For this purpose, stems, leaves, and fruit samples from coffee trees were collected following a temporal pattern based on the region's climatic characteristics and the plant's phenology and a spatial pattern considering different parts of the canopy. The carbon and nitrogen percentage content, the C/N ratio, and the carbon and nitrogen isotopic compositions (δ13C and δ15N) were determined for all samples. The basal portion of the orthotropic branch was also considered for the isotopic analysis of the tree's growth rings. The results obtained were correlated with the climatic variables of the region through a Pearson correlation analysis (p < .05). Coffee plants showed traditional δ13C values of C3 plants. Temporal δ13C variation was associated with the different growth rates between phenological stages and the use of substrates produced at different times under different environmental conditions leading to differences in photosynthetic discrimination. Spatial δ13C variation was observed with heterotrophic tissues isotopically heavier than leaves, with a significant decrease trend in δ13C values from the top (upper third) to the bottom (lower third), associated with ecophysiological differences between the canopy, isotopic fractionation processes downstream of photosynthetic carbon discrimination, and the fixation of C from other pools. Temporal δ15N variation was associated with the precipitation rates in the region and the fertilization distribution across the tree, while the spatial variation was with the plant's nitrogen assimilation and translocation patterns. The tree growth rings isotopic analyses showed isotopic differences between growth rings of the same plant addressed by the climatic conditions, with precipitation being the primary climatic determinant influencing the fixation and discrimination against 13C. Our results highlight the importance of using stable isotope analysis as a reference point for coffee ecophysiological studies to characterize how the temporal and spatial patterns of δ13C and δ15N emerge and signal the influence of climate on the source‐sink relationship of coffee trees under field conditions.

Origin of carbonatites and associated silicate rocks revealed by Mg triple-isotope approach

Carbonatites are rare carbonate-rich igneous rocks derived from carbon and carbonate-rich regions of Earth's mantle. Although a number of igneous processes are recognized to have controlled their compositions, the origin of the carbonate-rich nature of these magmas remains debated and has been linked to various mantle-related processes, including subduction and plume–lithosphere interaction. High-precision isotope measurements can provide insights into carbonatite petrogenesis, including the identification of subducted crustal material in their source region. In particular, combining mass-dependent and kinetically corrected Mg isotope data, also known as the triple-isotope approach, provides insights into mass fractionation processes driving mass dependent fractionation, which in turn allows to distinguish between equilibrium and kinetic processes. In this work, we report high-precision Mg stable isotope data for 59 carbonatites and associated silicate rocks from different localities and ages ranging from 3000 Ma to present-day, as well as C and O isotopic analysis for 38 carbonatites and Sr isotopic analysis for 41 carbonatites and silicate rocks. In addition, we also report Mg isotope data for 17 Phanerozoic carbonate rocks, with the aim of identifying the isotopic signature of carbonate-rich material potentially recycled to the carbonatite mantle source regions. Collectively, the data reveal a range of stable Mg isotope compositions from δ25/24MgDTS-2 = −1.20 ± 0.01‰ to +0.08 ± 0.01‰. We observe positive residual deviations after kinetic mass fractionation correction of the Mg isotope data for our carbonatites; an isotope signal that is also present in Phanerozoic carbonates. This observation establishes that a component of the Mg present in these samples experienced mass-dependent equilibrium isotopic fractionation processes, which are significantly larger at low temperatures. Given that the Mg results do not covary with C and O isotopic signals, the magnitude of the fractionation following the equilibrium law observed in carbonatites provides strong evidence for recycled material from the Earth's surface in the mantle source of Ca- and Mg-rich carbonatites. Furthermore, associated silicate rocks present mantle-like Mg isotopic compositions in contrast with the genetically linked carbonatites - based on the Sr isotopes - for some complexes, which is best explained if the carbonatites and associated silicate rocks represent distinct generation of partial melts of a mantle source containing recycled carbonate.

Different B[sbnd]Mo isotopic fractionation processes controlled by redox conditions in the subduction zone

The control of redox conditions on the geochemical recycling process in subduction zones is still poorly understood due to large uncertainties in oxygen fugacity (fO2) for subducted slabs. We present the first systematic geochemical and B-Mo-Sr-Nd-Hf-Pb isotopic data for continental arc basalts (CABs) and back-arc basalts (BABs) from Sumatra to investigate the relationships between oxygen fugacity and BMo isotopic fractionation processes during subduction. The Sumatran CABs and BABs yield high FeOT/MgO ratios and low K2O contents (0.48–1.42 wt%) and can be classified as tholeiitic. They have variable Sr-Nd-Hf-Pb isotopic compositions, consistent with the input of different amounts of melt from subducted terrigenous sediments into mantle sources. The BAB samples show much lower δ11B (−9.0‰ to −7.3‰) values than the CABs (δ11B = −7.0‰ to +0.17‰), reflecting significant B isotopic fractionation during multistage melting of subducted sediments. This is distinct from the similar δ98/95Mo values for the Sumatran CABs (−0.21‰ to −0.01‰) and BABs (−0.17‰ to −0.08‰), suggesting limited Mo isotopic fractionation during subduction. The Sumatran CABs show low V/Yb ratios, suggesting that melts from subducted sediments were possibly generated at fO2 values lower than FMQ + 1.5. The limited Mo isotopic fractionation could be induced by the relatively low fO2 during melting of subducted sediments, which would significantly decrease the mobility of Mo but have no influence on B. Alternatively, rocks from highly oxidized arcs, such as the Izu arc (e.g., >FMQ + 3), exhibit across-arc lightening trends for both B and Mo isotopes, which is consistent with enhanced Mo isotopic fractionation due to elevation of fO2 during subduction. Thus, the BMo isotopes of arc rocks could provide diagnostic indicators for distinct geochemical recycling processes controlled by changes in redox conditions in subduction zones.

Fate of herbicides in cropped lysimeters: 1. Influence of different processes and model structure on vadose zone flow

AbstractUnderstanding transport and fate processes in the subsurface is of fundamental importance to identify the leaching potentials of herbicides or other compounds to groundwater resources. HYDRUS‐1D was used to simulate water flow and solute transport in arable land lysimeters. Simulations were compared to observed drainage rates and stable water isotopes (δ18O) in the drainage. Four different model setups were investigated and statistically evaluated for their model performance to identify dominant processes for water flow characterization in the vadose zone under similar cultivation management and climatic conditions. The studied lysimeters contain soil cores dominated by sandy gravel (Ly1) and clayey sandy silt (Ly2), both cropped with maize located in Wielenbach, Germany. First, a single‐porosity setup was chosen. For Ly1, modeling results were satisfactory, but for Ly2, the damping observed in the isotope signature of the drainage could not be fully covered. By considering immobile water with a dual‐porosity setup for Ly2, model performance improved. This could be due to a higher fraction of fine pores in Ly2 available for water storage, leading to mixing processes of isotopically enriched summer precipitation and lighter winter water. Accounting for isotopic evaporation fractionation processes in both model setups did not lead to improved model performance. Consequentially, the difference in soil hydraulic properties between the two lysimeters seems to impact water flow processes. Knowledge of such differences is crucial to prevent contamination and mitigate potential risks to soil and groundwater.

Geological control on carbon isotope equilibrium and kinetic fractionation of CH4-CO2-HCO3− in microbial coalbed and shale gas systems

Microbial coalbed gas (CBG) and shale gas (SG), predominately composed of methane (CH4) and carbon dioxide (CO2), are important economic resources and potent greenhouse gases. Although isotopic equilibrium of CH4 and CO2 has been observed in microbial CBG and SG basins, it is difficult to judge under what geological conditions equilibrium is achieved. Moreover, the effects of CO2 dissolution on the isotopic fractionation process need to be considered. We use data from eight microbial CBG and SG basins to discuss the geological conditions in which equilibrium and kinetic isotopic fractionation in CH4-CO2-HCO3− system is achieved. Based on isotopic equilibrium temperatures calculated using computer codes developed in MatLab software, we show that, in deep and closed reservoirs, the CH4-CO2 and CH4-HCO3− are close to carbon isotope equilibrium. In contrast, in shallow and open reservoirs, they are in disequilibrium. The CO2-HCO3− is in disequilibrium in most reservoirs. We propose that both low free energy gradients and long coexisting time of CH4 and CO2/HCO3− are necessary to attain isotopic equilibrium. However, it is difficult to accurately estimate the timescale for attaining isotope equilibrium among them. In general, a closed and deep CBG/SG reservoir is likely to be geologically and geochemically stable over long timescales, favoring isotopic equilibrium of CH4-CO2 and CH4-HCO3−. However, a shallow and open reservoir is unfavourable for their isotopic equilibrium due to shorter timescales for the coexistence of CH4-CO2-HCO3−. Using data from systems close to equilibrium, we estimated the percentage of CO2 in total CH4 and CO2 in CBG reservoirs in various basins to be from 27% to 50%, where methanogenesis is mainly by CO2 reduction. This is significantly higher than the CO2 content (1% to 15%) in gaseous CH4 and CO2 in these basins but is consistent with those (36% to 48%) from culture experiments for coal conversion by methanogenesis. Further study shows that 53–99% of the CO2 formed during CBG generation has dissolved into groundwaters to form dissolved inorganic carbon (DIC) in CBG reservoirs. We propose that CO2 dissolution likely has significantly affect the abundance and isotopic compositions of gaseous CO2 in subsurface.

Drivers of intra-seasonal δ13 C signal in tree-rings of Pinussylvestris as indicated by compound-specific and laser ablation isotope analysis.

Carbon isotope composition of tree-ring (δ13 CRing ) is a commonly used proxy for environmental change and ecophysiology. δ13 CRing reconstructions are based on a solid knowledge of isotope fractionations during formation of primary photosynthates (δ13 CP ), such as sucrose. However, δ13 CRing is not merely a record of δ13 CP . Isotope fractionation processes, which are not yet fully understood, modify δ13 CP during sucrose transport. We traced, how the environmental intra-seasonal δ13 CP signal changes from leaves to phloem, tree-ring and roots, for 7year old Pinus sylvestris, using δ13 C analysis of individual carbohydrates, δ13 CRing laser ablation, leaf gas exchange and enzyme activity measurements. The intra-seasonal δ13 CP dynamics was clearly reflected by δ13 CRing , suggesting negligible impact of reserve use on δ13 CRing . However, δ13 CP became increasingly 13 C-enriched during down-stem transport, probably due to post-photosynthetic fractionations such as sink organ catabolism. In contrast, δ13 C of water-soluble carbohydrates, analysed for the same extracts, did not reflect the same isotope dynamics and fractionations as δ13 CP , but recorded intra-seasonal δ13 CP variability. The impact of environmental signals on δ13 CRing , and the 0.5and 1.7‰ depletion in photosynthates compared ring organic matter and tree-ring cellulose, respectively, are useful pieces of information for studies exploiting δ13 CRing .

Rubidium isotopic fractionation during magmatic processes and the composition of the bulk silicate Earth

Rubidium is a moderately volatile element with high incompatibility and fluid mobility. Its stable isotopes have great potential in tracing various geological processes. For example, lunar rocks are isotopically heavier than terrestrial ones, suggesting volatile loss by evaporation during or following the formation of the Moon. However, these studies rely on a poorly constrained estimate for the composition of the Earth’s mantle and a poor understanding of high-temperature processes which may act to fractionate stable Rb isotopes. It is therefore important to precisely characterize different rock types that sample the Earth’s mantle as well as to evaluate the importance of key isotopic fractionation processes. In order to address these issues, we established a high precision analytical method for Rb isotopic measurements using the Nu Sapphire CC-MC-ICP-MS (collision-cell multi-collector inductively coupled plasma mass spectrometer). In addition, we present a series of Rb isotopic data of volcanic rocks from Hekla volcano (Iceland) and MORB (mid-ocean ridge basalt) samples. We show that our method returns a high Rb sensitivity (∼500 V/μg·g−1 for 85Rb) and a long-term reproducibility of 0.03‰ on δ87Rb (the permil deviation of the 87Rb/85Rb ratio from the SRM 984 standard). This method uses a 2 ng/g Rb solution for analyses, allowing us to consume about 10 times less Rb to achieve similar or better precision than previous studies. Using this method, seven geostandards and one synthetic standard return Rb isotopic data consistent with previous work. Twenty-one Hekla volcanic rocks, spanning compositions from basalt to rhyolite, show limited Rb isotopic variation, with δ87Rb values varying from −0.17‰ to −0.07‰, demonstrating that magmatic evolution has an insignificant effect on Rb isotope ratios. A set of MORB samples (n = 15) from different mid-ocean ridges also span a limited Rb isotopic variation, displaying a range similar to the Hekla rock suite (−0.19 to −0.02‰). Combining our new data together with previously reported OIB data gives an average δ87Rb value of −0.12 ± 0.08‰ (2SD, n = 25), representing the current best estimate of the mantle’s isotopic composition. Considering the δ87Rb values of the upper continental crust (−0.14 ± 0.01‰, 2SE, n = 73), as inferred from recent measurements of granites, loess and sediments, and assuming this value represents the whole crust, the revised Rb isotopic composition of the bulk silicate Earth (and by extension the bulk Earth, assuming no Rb partitioned into the core) is −0.13 ± 0.06‰ (2SD).

Hydrogen isotope fractionation in carbohydrates of leaves and xylem tissues follows distinct phylogenetic patterns: a common garden experiment with 73 tree and shrub species.

Recent methodological advancements in determining the nonexchangeable hydrogen isotopic composition (δ2 Hne ) of plant carbohydrates make it possible to disentangle the drivers of hydrogen isotope (2 H) fractionation processes in plants. Here, we investigated the influence of phylogeny on the δ2 Hne of twig xylem cellulose and xylem water, as well as leaf sugars and leaf water, across 73 Northern Hemisphere tree and shrub species growing in a common garden. 2 H fractionation in plant carbohydrates followed distinct phylogenetic patterns, with phylogeny reflected more in the δ2 Hne of leaf sugars than in that of twig xylem cellulose. Phylogeny had no detectable influence on the δ2 Hne of twig or leaf water, showing that biochemistry, not isotopic differences in plant water, caused the observed phylogenetic pattern in carbohydrates. Angiosperms were more 2 H-enriched than gymnosperms, but substantial δ2 Hne variations also occurred at the order, family, and species levels within both clades. Differences in the strength of the phylogenetic signals in δ2 Hne of leaf sugars and twig xylem cellulose suggest that the original phylogenetic signal of autotrophic processes was altered by subsequent species-specific metabolism. Our results will help improve 2 H fractionation models for plant carbohydrates and have important consequences for dendrochronological and ecophysiological studies.

Mass-independent Sn isotope fractionation and radiogenic 115Sn in chondrites and terrestrial rocks

Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In.Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures.Most chondrites show a deficit in 115Sn/120Sn (typically −150 to −200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 115Sn/120Sn data correlate with In/Sn, being consistent with the β− decay of 115In over the age of the solar system. This represents the first evidence of the 115In-115Sn decay system in natural samples. The radiogenic 115Sn signature of the BSE derives from a suprachondritic In/SnBSE, which reflects preferential partitioning of Sn into the Earth’s core.

Unravelling δ13C signal in Scots pine trees for climate change and tree physiology studies

Stable carbon isotope composition (δ13C) recorded in trees responds sensitively to the changing environmental conditions and thus provides a powerful tool for paleoenvironmental reconstructions. The retrospective interpretation of tree δ13C signal depends on comprehensive understanding of how environmental and physiological signals are recorded in δ13C during photosynthesis and how the δ13C signal is modified after photosynthesis. This thesis aims to improve the understanding of photosynthetic and post-photosynthetic isotope fractionation processes, and to examine the suitability of tree ring δ13C for intra-seasonal reconstructions of intrinsic water use efficiency (iWUE). The former goal was studied by combining compound-specific isotope analysis of organic matter with isotope discrimination models and online δ13C measurements of leaf CO2 fluxes for field-grown mature Scots pine (Pinus sylvestris L.). The latter was achieved via comparing 18-year-long intra-seasonal iWUE chronologies estimated from laser ablation derived tree ring δ13C, gas exchange and eddy covariance data. Mesophyll conductance and time-integral effect of leaf assimilates had a clear impact on the intra-seasonal dynamics of leaf sugar δ13C. No significant use of reserves was observed for biomass growth of needles, stem or roots of Scots pine. Unlike sucrose, leaf bulk matters had a significant δ13C offset from new assimilates, leading to a distorted environmental signal documented in their δ13C. The reliability of tree ring δ13C data for intra-seasonal iWUE reconstructions was supported by an agreement of intra-seasonal patterns across the iWUE estimation methods. These results broaden our knowledge of the less well-known photosynthetic and post-photosynthetic isotopic fractionation processes, demonstrate the benefits of analysing sucrose δ13C for understanding plant physiological responses, and show that the tree ring δ13C based iWUE reconstructions can be extended to intra-seasonal scale. This information not only helps to better unravel δ13C signal in trees, but also improves reliable reconstructions of environmental and physiological signals from tree ring δ13C.

Fractionation characteristics of magnesium isotope in the ancient weathering crust

Weathering has always been a concerned around the world, as the first and most important step in the global cycle of elements, which leads to the fractionation of isotopes on the scale of geological age. The Middle Ordovician Majiagou Formation in Daniudi area of the Ordos Basin had experienced weathering for >130 Myr. Through thin section observation, major and trace element analysis, carbon, oxygen, and magnesium isotopes composition analysis, the dolomitization modes and weathering of ancient dolomite in Daniudi area were analyzed in detail. The results showed that the Sabkha and brine-reflux dolomitization modes had developed, and the Mg isotopes in different layers of the karst crust were fractionated by various factors. The vertical vadose zone was affected by weathering, the Mg isotope of dolomite (δ26Mgdol) showed a downward decreasing trend; the horizontal underflow zone was controlled by diagenesis and formation fluid, δ26Mgdol showed a vertical invariance and negative; the main reason for Mg isotope fractionation in the deep slow-flow zone was the brine-reflux dolomitization mode during early burial period, which showed a vertical downward increase. Finally, the Mg isotope characteristic data of the ancient weathering crust were provided and the process of Mg isotope fractionation in the karst crust was explained.

High‐resolution stable isotopic signals of ground ice indicate freeze–thaw history in permafrost on the northeastern Qinghai–Tibet Plateau

AbstractUnderstanding the mechanism of formation of ground ice and the freeze–thaw history of permafrost is essential when assessing the future of permafrost in a changing climate. High‐resolution ground ice records, integrating stable isotopes (δ18O, d‐excess, and δ13C), hydrochemistry (EC and pH) data, and cryostratigraphy at a depth of 4.8 m from two contrasting permafrost profiles (P‐1, P‐2) in the Source Area of the Yellow River (SAYR) on the northeastern Qinghai–Tibet Plateau (QTP), were investigated. The results suggested significant depth variations in the stable isotopes and hydrochemistry of the ground ice. The near‐surface ground ice (NSGI) and deep‐layer ground ice (DLGI) were characterized in terms of variations in stable isotopes and known modern active layer data. By synthesizing the measured δ18O and the modeled isotopic fractionation processes during freezing, we suggest that both the NSGI and DLGI in P‐1 were mainly formed by the segregation mechanism during permafrost aggradation. The NSGI in P‐2, however, exhibited quick freezing origins compared with the predominant ice segregation processes for the DLGI. By combining the evolution of various stable isotopes and hydrochemistry with 14C age data, four historical freeze–thaw stages were identified. Specifically, one thawing–refreezing stage (2.8–2.2 m), one freezing aggradation stage (2.2–1.6 m), and two permafrost aggradation–degradation cycle stages (4.8–2.8 m; 1.6–0.7 m) were differentiated, which emphasize the importance of climate‐induced freeze–thaw transitions and differing permafrost aggradation processes on ground ice formation and resultant isotope hydrochemical behaviors. This study is the first to use high‐resolution data in ground ice to interpret the freeze–thaw history of permafrost in the SAYR. These findings are important for further understanding of past permafrost evolution and projected future permafrost degradation trends on the QTP, and provide an alternative method to explore permafrost history.

Redistribution and isotope fractionation of endogenous Cd in soil profiles with geogenic Cd enrichment

The concentration and speciation of endogenous cadmium (Cd) in soil systems derived from parent materials is continuously altered by rock-soil-plant interactions. Previous studies on the distribution of Cd primarily focused on surface soil at regional scale. However, it lacks a novel approach to provide a new perspective on dynamics and redistribution of Cd in soil profile. Therefore, this study tries to establish the linkage between isotope fractionation and environmental processes of Cd in soil profiles with geogenic Cd enrichment based on Cd isotopes. High Cd concentrations were observed in the profile from forest at accumulation zone and the one from farmland at ridge in a rural area, southwest China. Soil erosion and deposition substantially influence the vertical distribution of total Cd in soil from the accumulation zone. Accordingly, distinct Cd isotope compositions were observed in different layers (δ114/110Cd: −0.087 ‰ to −0.066 ‰ vs −0.325 ‰ to −0.056 ‰). Mineral transformation, pedogenesis and biological activities controlled the dynamics and redistribution of Cd. The mobility of Cd increased during weathering processes, with ~40 % to 60 % of Cd residing in exchangeable fraction in the surface layers. Biological activity is a vital factor that drives Cd isotope fractionation in soil, resulting in depletion of heavy Cd isotopes in surface layers of the studied farmland profile. Contrasting fractionation effects were observed in profiles from forest and farmland due to the variance in soil-plant Cd cycling. Our study revealed the processes that control dynamics and redistribution of endogenous Cd in soil profiles, and proved that Cd isotope is a useful tool to investigate the bio-geochemical processes of Cd in soil systems.