Isotope Fractionation Research Articles

Spatial heterogeneity in nutrient utilization during the end-Devonian ocean anoxic event: a case study of the Western Canada sedimentary basin

The Devonian-Carboniferous (D-C; 359 Ma) boundary is marked by widespread deposition of organic-matter-rich black shales associated with the Hangenberg mass extinction event. The Exshaw Formation spans the D-C boundary in the Western Canada Sedimentary Basin (WCSB) and includes the basal Exshaw Shale deposited under broadly anoxic waters. The sediments at the base of the Exshaw Shale were deposited synchronously during a transgressive event across the WCSB, spanning the geographic variability of the basin. The variable Corg content of the shale was affected by local nutrient upwelling and paleotectonic features impacting water depth and circulation. To characterize the link between paleogeography and nutrient cycling, geographic (N = 20 locations) and stratigraphic (N = 6 locations) trends of δ13Corg and δ15Nbulk were examined throughout the WCSB, representing a range of depositional settings. The δ15Nbulk values range between 0.0 and 6.3‰ and δ13Corg from −29.5 to −26.8‰. Phytoplankton production in focused upwelling zones acquired a relatively 15N-depleted signature through isotopic fractionation during nutrient assimilation, and the residual nutrient pool was 15N-enriched. The advection of surface waters away from the location of upwelling supported additional phytoplankton growth and the deposition of sediments with higher δ15N values. The stratigraphic sections include black laminated and burrowed mudrock sequences that record changes in paleoredox conditions, water depth, and tectonism over time. Up-core from the base of the Exshaw, the Corg content decreases and simultaneously δ15Nbulk increases, suggesting a decrease in eutrophic conditions. Variable δ13Corg and δ15Nbulk trends demonstrate that there is no “type” isotopic profile spanning the D-C boundary in the WCSB.

Metabolic mechanism exploring tea nutrients based on stable isotope fractionation and element accumulation

Metabolic mechanism exploring tea nutrients based on stable isotope fractionation and element accumulation

Corundum ± magnesium‐deltalumite ± hibonite‐bearing objects in the CH chondrite Sayh al Uhaymir 290

AbstractIsolated corundum grains and corundum ± Mg‐deltalumite [(Al,Mg)(Al,◻)2O4] ± hibonite assemblages were investigated in the CH3.0 metal‐rich carbonaceous chondrite Sayh al Uhaymir (SaU) 290. Although very refractory inclusions containing abundant Zr‐ and Sc‐rich oxides and silicates, hibonite, grossite, or perovskite have been previously described in CH chondrites, this is the first discovery of corundum and Mg‐deltalumite in CHs and the first discovery of Mg‐deltalumite in nature. Magnesium‐deltalumite can be indexed by the Fd3m spinel‐type structure and gives a perfect fit to the synthetic Al‐rich spinel cells. Corundum‐Mg‐deltalumite grains, 5–20 μm in size, are occasionally rimmed by a thin layer of hibonite replacing corundum. Some corundum grains contain tiny inclusions of ultrarefractory Zr,Sc‐rich minerals and platinum‐group element (PGE) nuggets. All corundum, hibonite, and Mg‐deltalumite grains studied have 16O‐rich compositions (average Δ17O ± 2SD = −22 ± 3‰). Two corundum grains show evidence for significant mass‐dependent fractionation of oxygen isotopes: Δ18O ~ +34‰ and ~ +19‰. We suggest that the SaU 290 corundum‐rich objects were formed by evaporation and/or condensation in a hot nebular region close to the proto‐sun where the ambient temperature was close to the condensation temperature of corundum. A corundum grain with tiny inclusions of Zr‐ and Sc‐rich phases and PGE metal nuggets recorded formation temperatures higher than the condensation temperature of corundum. Two corundum‐rich objects with highly fractionated oxygen isotopes must have crystallized from a melt that experienced evaporation. Corundum grains corroded by hibonite recorded gas–solid interaction in this region during its cooling. The Mg‐deltalumite ± corundum ± hibonite objects were formed by rapid crystallization of high‐temperature (>2000°C) refractory melts. The lack of minerals with condensation temperatures below those of corundum and hibonite in the SaU 290 corundum‐rich objects suggests that after formation, these objects were rapidly removed from the hot nebular region by disk wind and/or by turbulent diffusion and disk spreading.

Organic petrography, biomarkers, and stable isotope (δ13C, δD, δ15N, δ18O) compositions of liptinite-rich coals

Liptinite-rich coals were evaluated using organic petrography, biomarkers, and stable isotopes to investigate their origin and paleoenvironmental significance, particularly, to explore fractionation characteristics of stable isotopes (δ13C, δD, δ15N, and δ18O) between bulk coal, extractable organic matter (EOM), and extracted coal residue (ER). The samples were collected from Cenozoic coal seams from the Yunnan and Liaoning Provinces in China. The samples are characterized by the enrichment of different types of liptinite. The late Pliocene sample YNP (liptinite = 73.5%) is dominated by sporinite and bituminite, whereas the late Pliocene sample YND (liptinite = 65.5%) is characterized by isolated resinite particles and amorphous resinite. The liptinite in the Eocene sample SB (46.0%) is represented by blocky resinite with homogeneous morphology. The differences in distribution and morphology of liptinite are due to the different coal-forming plants and depositional environments, as indicated by the biomarker compositions. Biomarker results indicated that the sample YNP was formed mainly by Pinaceae and angiosperms under oxidizing conditions with bacterial/fungal degradation, whereas the sample YND was derived from the woody parts of gymnosperms with lower contributions of angiosperms under reducing conditions with low microbial activity. The sample SB predominantly originated from Cupressaceae/Pinaceae under reducing conditions with a lack of bacterial/fungal degradation.The fractionations of δ13C, δD, δ15N, and δ18O between bulk coal, EOM, and ER in the liptinite-rich coals are different. The δ13C values of bulk coal, EOM, and ER are mostly controlled by precursor paleovegetation and isotopic composition of CO2. The lower δ13C values of samples YNP and YND from the late Pliocene compared to that of the Eocene sample SB resulted from the change of palaeoconditions (e.g., δ13C of atmospheric CO2, cooling, and decrease of CO2 concentration). The δ13C values of EOM in the samples YNP and YND are about 3‰ lower than δ13C values of bulk coal/ER, whereas δ13C fractionation between EOM and bulk coal/ER is small (< 0.8‰) in the sample SB, probably due to the very limited microbial/fungal degradation. The δD values of EOM are 50 to 90‰ lower than that of bulk coal/ER within the same sample, reflecting different isotopic compositions of monomeric compounds compared to the macromolecular matrix of kerogen most probably due to differences in H-isotope fractionation during biosynthesis. The δ15N of bulk coal and ER show limited fractionation (< 0.5‰) and are mainly controlled by precursor paleovegetation and microbial induced degradation processes. The studied liptinite-rich coals yield higher δ18O values than those detected in humic coals. The differences of δ18O values (bulk coal, EOM, ER) between the samples YNP/YND and the corresponding δ18O values of the sample SB indicate that this isotope parameter is mostly controlled by the δ18O value of source water. The weaker fractionation of oxygen isotope between EOM and bulk coal/ER compared to δ13C and δD may be attributed to the fact that oxygen-containing compounds within EOM did not experience a cleavage or any change of the O-containing bonds. The calculated δ18O and δD values of source rain waters fall in the range of modern rain waters at different sites.

Decoding paleomire conditions of paleogene superhigh-organic-sulfur coals

Superhigh-organic‑sulfur (SHOS) coals (coals with organic sulfur content >4 wt%) are unique coal deposits found at a few notable locations in the world. Specific peat accumulation and preservation conditions must be met to form SHOS coals. Organic sulfur is a major constituent of such coals, and it may have various sources depending on the prevailing paleomire conditions. Understanding such paleomire conditions sheds light on the formation mechanisms of SHOS coals. This investigation decodes the paleomire conditions of the Paleogene SHOS coals from Meghalaya, India, using sulfur isotopic compositions (δ34S) of organic sulfur (δ34SOS) and pyritic sulfur (δ34SPy) along with organic petrography, pyrite morphology and trace element ratios. Thirty coal samples were collected from the Jaintia Hills in the east, Khasi Hills in the middle, and Garo Hills in the west of Meghalaya. The organic sulfur content in the Garo, Khasi, and Jaintia coals varies from 1.0 to 3.3 wt%, 1.4 to 13.8 wt%, and 1.0 to 7.2 wt%, respectively. Further, after separation from pyritic sulfur and sulfate sulfur phases, the organic sulfur content ranges from 54.4 to 69.2%, 63.8 to 79.9%, and 59.3 to 73.8%, in the Garo, Khasi, and Jaintia Hills, respectively, suggesting the SHOS nature of these coal samples. The δ34SPy varies from −29.3 ‰ to +5.7 ‰, −21.3 ‰ to +27.3 ‰, and −12.1 ‰ to −4.3 ‰, in the Jaintia, Khasi, and Garo Hills, respectively, while the δ34SOS fluctuates from −4.6 ‰ to +3.7 ‰, −9.3 ‰ to +7.8 ‰, and − 9.0 ‰ to −5.0 ‰, respectively. The δ34S values of pyrite and organic sulfur (OS) in Jaintia coals are 34S depleted compared to seawater sulfate (+22 ‰), leading to fractionations in the range of −51.3 ‰ to −16.3 ‰ (mean − 31.6 ‰) and − 26.6 ‰ to −18.3 ‰ (mean − 23.1 ‰) for pyritic and organic sulfur (OS), respectively. Pyrite in Khasi coals show a relatively heavier δ34S composition averaging at −20.5 ‰, whereas organic sulfur (OS) isotope compositions range from −31.3 ‰ to −14.2 ‰ with a mean of −22.6 ‰. Pyrite and OS in the Garo coals are depleted compared to seawater sulfate. Isotope variations in the Jaintia, Khasi, and Garo coals indicate microbial sulfate reduction (MSR) of seawater sulfate. Large isotopic fractionations between Eocene seawater sulfate and pyritic sulfur (Δ34SSO4Eocene – pyrite = up to −51.3 ‰; mean − 31.6 ‰) in Jaintia coals indicate their possible formation in the water column/near the sediment-seawater interface (open system) and also hint toward dissimilatory sulfate reduction pathways that prevailed under anoxic redox conditions. However, mean values of Δ34SSO4Eocene – pyrite (−20.5 ‰) in the Khasi coals imply pyrite formation deeper in the sediments (more closed system) under dysoxic conditions. The dominance of OS over pyritic sulfur, framboidal pyrite, and its microcrystal size distributions in Jaintia coals may suggest syngenetic pyrite formation in open water reducing/anoxic conditions under paralic environments. Elevated Sr/Ba and U/Th values in these coals further confirm the anoxic conditions. Nevertheless, the presence of euhedral pyrite with the alleviated pyrite framboids in the Khasi coals and their complete absence in the Garo coals may suggest dysoxic-suboxic and suboxic-oxic depositional conditions, respectively. The isotopic signatures of the Garo coals suggest sulfur contribution from the parent paleobiota and MSR under a freshwater-oxic environment. Insignificant fractionations between δ34SPy and δ34SOS indicate limited iron and sulfate availability for additional sulfur cycling and disproportionation reactions, typical of oxic conditions. The absence of framboidal pyrite, elevated sulfate concentration, and mean Sr/Ba and U/Th values of 0.5 and 0.3, respectively, further suggest the freshwater peat deposition in the Garo Hills under limnotelmatic to telmatic freshwater conditions. Moreover, high inertinite content (Immf = 9.77–33.16 vol%), possibly induced by atmospheric peat exposure, supports the interpretation of suboxic-oxic paleomire conditions in Garo Hills. Gradually decreasing mineral matter content from Jaintia (mean 13.6 vol%) to Garo coals (mean 7.4 vol%) additionally projects a transition from mesotrophic brackish to freshwater limnotelmatic environment, complementing the shift in the paleomire condition from eastern (Jaintia) to western (Garo) Meghalayan Hills.

From grape to wine: A thorough compound specific isotopic, enantiomeric and quali-quantitative investigation by means of gas chromatographic analysis

In this study, multiple analytical approaches, including simultaneous enantiomeric and isotopic analysis, were employed to thoroughly investigate the volatile fraction in Moscato giallo grape berries and wines. For the qualitative and quantitative profiling, a fast GC-QqQ/MS approach was successfully utilized. However, prior to isotopic analysis, the extracts underwent an additional concentration step, necessitating an assessment of isotopic fractionation during the concentration process. Once the absence of carbon isotopic fractionation was confirmed, this research aimed to develop a suitable gas chromatographic method for the simultaneous detection of both enantiomeric and isotopic ratios of target monoterpenoids in Moscato giallo samples. To address the limitations associated with a one-dimensional approach, multidimensional gas chromatography was employed to enhance separation before IRMS and qMS detections. Utilizing a Deans switch transfer device, the coupling of an apolar column in the first dimension and a chiral cyclodextrin-based stationary phase in the second dimension proved effective for this purpose. The data obtained from the analysis of Moscato giallo samples allowed for the assessment of natural isotopic and enantiomeric distributions in grapes and wines for the first time in the literature. Significant enantiomeric excesses were observed for the target terpenoids investigated. Regarding isotopic distribution, a consistent trend was observed for all detected target terpenols, including the linalool enantiomers. To date, this study represents the first investigation of simultaneous δ13C and chiral investigation of the main terpenoids in oenological products in the literature.

Zinc isotope fractionation during coprecipitation with amorphous iron (hydr)oxides

Coprecipitation facilitates the incorporation of Zn into the lattice of Fe (hydr)oxide, which is a crucial mechanism causing low Zn bioavailability in widespread Zn-deficient soils. Zn isotopes are a potential indicator of the coprecipitation of Zn and Fe (hydr)oxides in soils. However, the Zn isotope fractionation caused by coprecipitation with amorphous Fe (hydr)oxides (e.g., ferrihydrite) and the impact of environmentally relevant conditions remain unknown. Here, the molecular mechanism and impact factor of Zn isotope fractionation during Zn2+-Fe3+ coprecipitation under natural soil conditions (including different pH values and initial Zn/Fe ratios) were investigated by combining isotope ratio measurements, extended X-ray absorption fine structure (EXAFS) analyses, and density functional theory (DFT) geometry optimization. The results show that aqueous Zn (Znaq) can be complexed on the ferrihydrite surface (Znads) with positive isotope fractionation (Δ66Znads–aq = 0.42 ± 0.09 ‰) or directly incorporated into the ferrihydrite lattice with slightly negative isotope fractionation (Δ66Znstru-aq = −0.08 ± 0.03 ‰). In addition, over time, the surface-complexed Zn can further transform to a layered structure on the surface but exhibits limited Zn isotope fractionation. According to Zn K-edge EXAFS, the Zn isotope fractionation of surface complexation and incorporation of Znaq are related to the decrease in the Zn–O bond strength in the order surface complexed Zn (RZn–O = 2.00 Å) > aqueous Zn (RZn–O = 2.08 Å) > directly incorporated Zn (RZn–O = 2.06–2.07 Å with slight distortion). The limited Zn isotope fractionation associated with the transformation of Znads is related to the reconfiguration of Znads during the nucleation of octahedral Zn layer structures. Furthermore, the primary process controlling Zn isotope fractionation is different under varying experimental conditions, leading to distinct Zn isotope fractionation between the bulk solid and solution during Zn–Fe coprecipitation. Low pH values (5.0–6.0) and initial Zn/Fe ratios (0.01–0.02) favor the direct precipitation of Znaq, resulting in slightly negative Zn isotope fractionation between the bulk solid and solution. In contrast, high pH values (7.0–7.5) and initial Zn/Fe ratios (0.1–0.2) favor surface complexation and the transformation of Znads, leading to heavy Zn isotope enrichment in the bulk solid. These findings offer novel insights into the primary mechanism through which Fe (hydr)oxides regulate Zn bioavailability in Zn-deficient soils and provide experimental evidence supporting the potential application of Zn isotopes as an indicator for comprehending the fate of Zn controlled by Fe (hydr)oxides in soils.

Multifunctional Roles of Zinc in Cadmium Transport in Soil-Rice Systems: Novel Insights from Stable Isotope Fractionation and Gene Expression.

The effect of Zn on Cd accumulation in rice varies under flooding and drainage conditions, and the underlying mechanism during uptake and transport from the soil to grains remains unclear. Isotope fractionation and gene expression were investigated using pot experiments under distinct water regimes and with Zn addition to gain a deeper understanding of the molecular effects of Zn on Cd uptake and transport in rice. The higher OsHMA2 expression but constitutively lower expression of zinc-regulated, iron-regulated transporter-like protein (ZIP) family genes in roots under the drainage regime than the flooding regime caused the enrichment of nonheavy Zn isotopes in the shoots relative to roots but minimally affected Cd isotopic fractionation. Drainage regime seem to exert a striking effect on the root-to-shoot translocation of Zn rather than Cd, and increased Zn transport via OsHMA2. The changes in expression patterns in response to Zn addition were similar to those observed upon switching from the flooding to drainage regime, except for OsNRAMP1 and OsNRAMP5. However, soil solution-to-rice plants and root-to-shoot fractionation toward light Zn isotopes with Zn addition (Δ66Znriceplant-soilsolution = -0.49 to -0.40‰, Δ66Znshoot-root = -0.36 to -0.27‰) indicated that Zn transport occurred via nonspecific uptake pathways and OsHMA2, respectively. Accordingly, the less pronounced and minimally varied Cd isotope fractionation suggested that OsNRAMP5 and OsHMA2 are crucial for Cd uptake and root-to-shoot transport, respectively, facilitating Cd accumulation in grains. This study demonstrated that a high Zn supply promotes Cd uptake and root-to-shoot transport in rice by sharing distinct pathways, and by utilizing a non-Zn-sensitive pathway with a high affinity for Cd.

Iron isotope fractionation between metal and silicate during core-mantle differentiation in rocky bodies

Fe isotope variations in rocky bodies reveal fundamental information about planetary evolution. However, experimental results have come to contradictory conclusions on the equilibrium Fe isotope fractionation between metal and silicate during core-mantle differentiation. Many different processes, including evaporation, core formation, partial melting and disproportion of mantle silicate, have been consequently proposed to explain the observed Fe isotope variations in rocky solar system bodies. Here we perform ab initio molecular dynamics simulations and find that the anharmonicity in iron strongly decreases the force constant of Fe at low pressures (<∼50 GPa), which even reverses the equilibrium Fe isotope fractionation between metal and silicate. We conclude that pyrolitic melt is always enriched in heavy Fe isotopes relative to liquid Fe-alloys, no matter what pressure. Therefore core-mantle differentiation will play a significant role in explaining the heavy Fe isotope compositions of the mantles of some rocky bodies (e.g., Earth, the ureilite parent body, and possibly the asteroid Vesta). As all previously proposed processes for Fe isotope fractionation can only enrich the mantle-derived rocks in heavy Fe isotopes, the near/sub-chondritic Fe isotope signatures of Mars and the aubrite parent body thus imply that iron sulfide enriched in light Fe isotopes may significantly contribute to the iron components of those meteoritic samples.

Lipid biomarkers and stable isotopes uncover paleovegetation changes in extremely species-rich forest-steppe ecosystems, Central Europe

The historical development of the vegetation of semi-dry grasslands in Central Europe is not satisfactorily understood. Long-term continuity of open vegetation or, conversely, deep-past forest phases are considered possible sources of the current extreme species diversity of these ecosystems. We aimed to reveal the trajectory of paleovegetation development in these ecosystems through detailed analysis of terrestrial in-situ soil geoarchives. We measured the bulk soil carbon and nitrogen contents, lipid molecular distribution, and compound-specific stable carbon and hydrogen isotopic signatures of mid- and long-chain n-alkanes extracted from soil and modern plant material tissues (i.e., deciduous and Pinus leaves and grass/herbaceous species).The C23–C33 n-alkane homologues were identified in soils with different abundances. Normally, C27 and C29 n-alkanes were the most abundant homologues in tree-leaf samples, while grass-derived n-alkanes were mostly C31 and C33 homologues. Soils were largely dominated by C29 and C31 n-alkanes. Odd-numbered C27–C33 soil n-alkane δ13C values ranged from −36.2‰ to −23.2‰, whereas their δ2H values showed a wider range of variability that fluctuated from −224‰ to −172‰. Molecular distribution in combination with radiocarbon analysis of soil organic matter (SOM) and δ13C and δ2H values of n-alkanes revealed a large contribution of C3 trees (both deciduous and coniferous trees/pine trees) as the main source of n-alkanes between the late Pleistocene and early Holocene (ca 15,000–8200 calibrated year before present/cal year BP). A clear shift toward more grassy/herbaceous vegetation was observed from the early Holocene (ca 11,700–8200 cal year BP) onwards. Distribution patterns of lipids and soil geochemical parameters showed that plants are the main source of SOM and that biodegradation and kinetic isotope fractionation are not the main reasons for 13C enrichment in soil profiles. Past C3 vegetation shifts as well as paleoclimate changes (i.e., aridity) can have played a role in the observed 13C depth profiles.

Identification of processes in Cu-ore heap leaching using Cu isotopes and leachate chemistry at Tschudi mine, northern Namibia

Copper isotopic fractionation (in δ65Cu) and leachate characterization were studied in the context of heap leaching at the Tschudi copper mine in northern Namibia. The leached solution is of Mg-SO4 type with high Al and Fe concentrations. The source of Mg and Al in the leachate can be from the alteration of micas such as Mg-bearing muscovite confirmed by X-ray diffraction and scanning electron microscopy; however, the source of Mg cannot be determined with certainty. The principal secondary minerals identified in the leached ore are gypsum and jarosite. The value of pH in leachate is ∼1.21 and the concentration of dissolved Cu, occurring mostly as CuSO40 and Cu2+, is about 2 g/L. In comparison with unleached ore (avg. δ65Cu −1.47 ‰), leached ore exhibits lighter isotopic values (avg. δ65Cu −6.01 ‰) with apparent isotopic fractionation Δ65Culeached ore-unleached ore of about −4.54 ‰. In contrast, there is isotopic enrichment of leachate in heavier 65Cu isotope (leachate δ65Cu 0.34 ‰) with apparent isotopic fractionation Δ65Culeachate-unleached ore value of +1.81 ‰. These results are in good agreement with Cu isotopic fractionation and depletion in heavier 65Cu isotope reported for dissolution experiments in laboratory and groundwater linked to the porphyry copper ore deposits around the world. The leaching of heaps can be considered an analogy of upper part of gossans, but here the supergene enrichment zone is missing due to extremely low pH and oxidizing conditions.

Controls on Li partitioning and isotopic fractionation in inorganic calcite

The δ7Li of marine carbonates has been interpreted as an archive of the evolution of seawater δ7Li, and therefore continental weathering, through geological time. However, little is known about the incorporation of Li into calcium carbonate minerals and, consequently, the controls on Li partitioning (DLi) and isotopic fractionation (Δ7Lisolid-fluid) associated with Li incorporation. Crucially, we lack a fundamental understanding of how Li partitioning and Δ7Lisolid-fluid change in response to the chemical and physical conditions of crystal formation. Here, we present DLi and Δ7Lisolid-fluid data from a series of inorganic calcite precipitation experiments where temperature, and solution pH and dissolved inorganic carbon (DIC) were independently varied. We find DLi values in the range 0.8–1.5 × 10−3, which show no relationship with temperature, a strong positive correlation with pH, and a weak positive correlation with DIC. At face value, these patterns are inconsistent with the results of previous precipitation studies. However, the correlations with pH and DIC are consistent with a strong precipitation rate control on DLi that aligns well with previous data, with a likely secondary influence from the incorporation of Li-HCO30 ion pairs from solution. We find Δ7Lisolid-fluid values in the range −6 to −2 ‰, which show no relationship with temperature or pH, and a weak positive correlation with DIC and crystal precipitation rate. These results do not agree with previously published data. Considered alongside previously published data, we observe no consistent relationship between Δ7Lisolid-fluid and any reported physical or chemical experimental parameter, highlighting the need for substantial further work to determine whether systematic controls on Li isotopic fractionation exist in carbonate minerals, and whether they may be environmentally significant.

Optimization of separation and MC-ICP-MS methods for determining Eu isotopic ratios in Si- and Ba-rich fractionated igneous rocks and other natural materials

Eu isotope ratio can be precisely measured by MC-ICP-MS using a Sm isotope pair as spike for normalization. The standard chemical reagent NIST3117a exhibits almost no Eu isotope fractionation regardless of the kind of Sm isotope pairs used in normalization. However, Eu isotope fractionation can appear even in high purity Eu chemical reagents due to Gd and Ba impurities, interference with Sm isotope pair or use of different sample introduction methods. The Eu isotope fractionation in highly fractionated igneous rocks or feldspar minerals can arise from Gd and Ba impurities left by incomplete chemical separation. This study describes a modified, optimal method for accurately and precisely determining the degree of Eu isotope fractionation in highly fractionated Si-rich igneous rocks and Ba-rich feldspar. Ba oxide effects on Sm, Eu and Gd isotopes were monitored by MC-ICP-MS using different wet and dry plasma conditions for sample introduction. The Gd impurities exerts more influence than Ba impurities on Eu isotope ratios. The highly fractionated igneous rocks and feldspar materials showed consistent enrichment in the lighter Eu isotope (151Eu) which becomes a negative Eu isotopic value relative to NIST3117a. Results showed that highly purified Eu solutions from reagents containing no detectable Gd and Ba gave consistent Eu isotopic values regardless of Sm isotope pair (e.g., 147Sm149Sm, 147Sm152Sm, 147Sm154Sm, 149Sm154Sm, 150Sm154Sm) used in normalization. In order to obtain the best estimates of Eu isotope fractionation in different kinds of geological materials (including Si- and Ba-rich materials), Ba and Gd matrix must be completely removed and the Eu isotopic values calculated using four or more Sm spike isotope pairs.

Mercury sources, transport, and transformation in rainfall-runoff processes: Mercury isotope approach

Mercury (Hg) in runoff water poses significant ecological risks to aquatic ecosystems that can affect organisms. However, accurately identifying the sources and transformation processes of Hg in runoff water is challenging due to complex natural conditions. This study provides a comprehensive investigation of Hg dynamics in water from rainfall to runoff. The Hg isotope fractionation in water was characterized, which allows accurate quantification of Hg sources, transport, and transformations in rainfall-runoff processes. Δ200Hg and corrected Δ199Hg values can serve as reliable tracers for identifying Hg sources in the runoff water and the variation of δ202Hg can be explained by Hg transformation processes. During runoff migration processes, Hg from rainfall is rapidly absorbed on the land surface, while terrestrial Hg entering the water by the dissolution process becomes the primary component of dissolved mercury (DHg). Besides the dissolution and adsorption, microbial Hg(II) reduction and demethylation of MeHg were dominant processes for DHg in the runoff water that flows through the rice paddies, while photochemical Hg(II) reduction was the dominant process for DHg in the runoff water with low water exchange rates. Particulate Hg (PHg) in runoff water is dominantly originated by the terrestrial material and derived from the dissolution and adsorption process. Tracking sources and transformations of Hg in runoff water during the rainfall-runoff process provides a basis for studying Hg pollution in larger water bodies under complex environmental factors.

Temperature-dependent carbon isotope fractionation in coccolithophores

Introduction: The stable carbon isotope ratio of long-chain alkenones produced by marine haptophyte phytoplankton has often been used to estimate past variations in atmospheric CO2 throughout the Cenozoic. However, previous experimental studies and surveys of alkenones from surface sediment and suspended particulate matter document additional environmental and physiological influences on carbon isotopic fractionation in alkenones.Methods: To clarify the non-CO2 effects on the alkenone carbon isotope fractionations, an important alkenone producer, Gephyrocapsa oceanica, was cultured in laboratory. To separate effects of different environment parameters, G. oceanica was grown in continuous cultures under a matrix of environmental conditions in order to explore the influence of temperature independently of CO2(aq). Through careful manipulation of the media carbon system, we can control the variation of the media CO2(aq) independently of temperature solubility. Carbon isotope fractionations from alkenones, coccolith, and particulate organic carbon were measured from this steady state system.Results and Discussion: We find εp in alkenones and particulate organic carbon inversely correlates with temperature, and temperature affects εp more strongly than CO2(aq). The magnitude of the temperature effect can be explained by higher growth rates at warmer temperatures with a similar growth rate dependence as observed in previous cultures in which growth rate was regulated by other factors. Where the past temperature influence on growth rate could be constrained using the UK’37 alkenone index in the same samples, our finding offers an approach to deconvolve an important physiological factor affecting ancient alkenones εp, and may therefore improve past pCO2 estimates.

Magnesium isotope fractionation during magmatic differentiation in the lower continental crust

The Mg isotopic compositions display a significant disparity between the lower continental crust and the mantle. However, due to the limited availability of representative samples from the lower crust, our understanding remains incomplete regarding whether Mg isotope fractionation occurred during its formation and its potential influence on the observed isotopic differences. This study addresses this gap by presenting Mg isotopic data for juvenile lower crustal mafic xenoliths from Daoxian, Southeast China, providing new insights into this poorly understood process. The xenoliths, classified as websterites and two-pyroxene granulites, equilibrated at 818–912 °C and 10.6–15.4 kbar. They exhibit high Mg# (77–85), Cr (154–1451 ppm), and Ni (143–312 ppm), as well as trace element patterns resembling those of island arcs and evolved Sr–Nd–Pb isotopic compositions (87Sr/86Sri = 0.7046–0.7071; εNd(t) = −2.44 to +4.62; 206Pb/204Pbi = 18.26–19.03), indicating their derivation primarily from an enriched mantle source. Despite this, these xenoliths display a diverse range of Mg isotopic compositions. Websterite xenoliths exhibit mantle-like δ26Mg values (−0.27‰ to −0.29‰), indicating no influence from hybridized mantle source or pyroxene fractional crystallization/accumulation on their Mg isotopes. In contrast, granulite xenoliths show lower and variable δ26Mg values (−0.26‰ to −0.49‰), which positively correlate with Mg#, Cr, and V, but negatively correlate with Na2O + K2O, indicating that magmatic processes likely influenced Mg isotope fractionation in these samples. Petrological features, coupled with correlations between MgO and CaO/Al2O3, Cr, Co, and Ni, indicate that fractional crystallization and/or accumulation of olivine, spinel, clinopyroxene, orthopyroxene, and plagioclase played crucial roles in the formation of the granulite protoliths. Furthermore, the segregation of spinel during magmatic differentiation could have enriched residual melts in light Mg isotopes inherited by the cumulate Cpx + Opx + Pl (i.e., the granulite protoliths). Overall, the weighted average δ26Mg value of the lower crust in South China is estimated to be −0.34 ± 0.04‰. This finding, together with previous studies on granulite xenoliths in North China and Australia, strongly indicates heterogeneous Mg isotopic compositions in the lower continental crust relative to the mantle.

Composition effects on equilibrium oxygen isotope fractionation factors between garnets and quartz/calcite/olivine: Implication from vibration frequencies of garnets at high temperatures and high pressures

Garnet-group minerals, with their wide range of compositions, play a significant role in Earth's crust and upper mantle, participating in various petrological and geochemical processes. Oxygen isotope fractionation factors between garnets and other minerals hold crucial implications in these contexts. In this work, vibration frequencies were measured via Raman spectra on five garnet mineral samples in the pyrope-almandine-spessartine ternary system and four synthetic pyrope-grossular solid solutions at temperatures up to 1000 °C and pressures up to 17 GPa. Isobaric (γiP) and isothermal (γiT) mode Grüneisen, as well as anharmonic (ai) parameters, were determined for the observed modes. Our study shows that the vibration bands tend to shift to lower frequencies with increasing temperature and to higher frequencies with increasing pressure. Moreover, the anharmonic correction has been found to contribute positively to equilibrium oxygen isotope fractionation β factors in garnets, typically within 0.5 ‰ above 1000 K. The 103∙lnβ(T) factors calculated from vibration spectra (considering Г points only) align closely with those from theoretical calculations (including all frequencies in the Brillouin zone). Contributions from phonon dispersion (including none-Г points) are typically smaller than the uncertainties propagated from frequency measurements. Additionally, the pressure effect on the oxygen isotope fractionation in garnet, evaluated from the isothermal Grüneisen parameters, is found to be insignificant under crustal and upper mantle conditions, consistent with thermodynamic expectations. Using published oxygen isotope fractionation β factors for quartz and calcite, the equilibrium oxygen isotope fractionation factors (103∙lnα) are calculated between garnets of diverse compositions and any of these phases as functions of temperature, pressure and fraction of garnet endmembers. Considering composition effects helps to reduce the discrepancies among experimental and empirical calibrations of oxygen isotope fractionation factors between garnet and quartz. As an example application, oxygen isotope fractionation factors 103∙lnα(P, T) between garnets and forsterite were calculated under upper mantle conditions. Our findings suggest that these fractionation factors are predominantly dependent on temperature and garnet compositions, with minor influence from pressure. Compared with our calculated fractionation factors between garnet and olivine, the oxygen isotope exchange equilibrium may have been reached in some in kimberlite and mantle xenolith samples between garnet and olivine. However, in other samples, the fractionation factors cannot be explained solely by the composition effect, likely due to metasomatism. Our results underscore the importance of considering garnet compositions when interpreting their oxygen isotope compositions.

Iron isotope constraints on the genesis of giant Beiya Au-base metal deposits, Yunnan, Southwest China

The Beiya Au-base metal deposit in southwest China is characterised by a huge amount of iron associated with gold mineralization. The formation of the Beiya deposit is generally thought to be related to Tertiary potassic intrusion, as porphyry- and skarn-type mineralization are the two most important types of mineralization in the region. However, the lack of direct evidence to constrain the source of iron and gold as well as other metals makes it difficult to accurately conceptualise the ore genesis model. In this study, we report high-precision (0.03 ‰; 2sd) Fe isotope data on Fe-bearing minerals including magnetite, pyrite and chalcopyrite, and major igneous rocks exposed in the area, including monzogranite porphyry (MGP), mafic microgranular enclave (MME), lamprophyre and basalt. Magnetites have a wide range of δ Fe from 0.15 to 0.64 ‰, reflecting substantial isotopic fractionation at different mineralization stages. MMEs have heaviest Fe isotopic composition (0.35 ‰ to 0.88 ‰) compared to MGPs (0.19 ‰ to 0.48 ‰), lamprophyre (∼0.2 ‰) and basalt (∼0.0 ‰). A negative correlation between δ56Fe and TFe2O3 is found for both MPGs and MMEs, which indicates the leaching of iron by hydrothermal fluids mobilizes light Fe and leaves behind isotopically heavy Fe in the remaining source rock. Fe isotopic compositions of MPG and MME overlap with those of magnetite, both of which are proposed to be the source of Fe in magnetite. The basalt has δ56Fe value of 0 ± 0.03 ‰, similar to those of global basalts, suggesting a negligible contribution to the formation of iron ores. Therefore, we propose that magmas parental to the MGP and MME may be the main source of iron to form the Beiya deposit; post-magmatism hydrothermal activities play a key role in leaching the metals out and transporting them to the mineralization area.

Experimental determination of Si, Mg, and Ca isotope fractionation during enstatite melt evaporation

Abstract Evaporation of silicate materials from Earth or its precursors may be important in shaping their primordial compositions represented by undifferentiated meteorites, e.g., enstatite chondrites; however, the conditions under which evaporation occurs and the extent of evaporation-induced elemental and isotope fractionation remain uncertain. Here, we experimentally determine the volatility and isotope fractionation of Si, Mg, Ca, Nb, and Ta during enstatite melt evaporation at 2423–2623 K using a high-temperature conical nozzle levitator. Homogenous glasses are recovered after experiments; then we use EPMA and LA-ICP-MS to measure the elemental compositions, MC-ICP-MS to measure the Si and Mg isotopes, and TIMS to measure the Ca isotopes. Our results show that the evaporation rates of Si are larger than Mg, and the mean vapor/melt isotope fractionation factors (α = Rvapor/Rmelt; R = isotope ratio) are 0.99585 ± 0.00002 for 29Si/28Si and 0.98942 ± 0.00130 for 25Mg/24Mg. However, neither evaporative loss of Ca, Nb, and Ta nor Ca isotope fractionation was observed within analytical uncertainty. In conjunction with previous studies, we find that in an evaporation experiment the saturation degree (partial vapor pressure/equilibrium vapor pressure) of Si (SSi) is larger than SMg when Si is more volatile than Mg, and vice versa. If the Mg/Ca and Si/Ca ratios and isotopes in the bulk silicate Earth are attributed to the evaporation of enstatite chondrite-like precursors, evaporation temperatures &amp;gt;5000 K and SSi &amp;lt; SMg are required.

Magmatic degassing and fluid metasomatism promote compositional variation from I-type to peralkaline A-type granite in the late Cretaceous Fuzhou felsic complex, SE China

Abstract A-type granites generally have much lower water, higher temperature, and incompatible element concentrations than I-type granitoids. Yet it remains unclear why I-A-type granitic complexes occur in convergent plate margins. Here we conduct geochemical analyses on apatite and mafic minerals from the late Cretaceous I-A-type granitic complex in Fuzhou area, SE China, aiming to decipher differentiation, fluid metasomatism, and degassing that primarily control the compositional diversity of felsic magmas. Apatites in both rock types are F-rich and show large H2O and δD variations, i.e., 341–3892 ppm H2O and –325 to +336‰ δD in I-type granitoids; 67–1366 ppm H2O and –251 to +1439‰ δD in A-type granites. H2O in apatite is negatively correlated with La/Sm and Sr/Y in the I-type granitoids, whereas it is positively correlated with Ce and total rare earth element (REE) concentrations in the A-type granites. Once H2O increases up to hundreds of ppm, both rock types show a rapid decrease of H2O/Ce, an increase of F/Cl, and extensive H isotope fractionation. Arfvedsonite occurs as a late crystallizing mineral in the A-type granite and has much higher contents of Na2O, K2O, F, and high field strength elements (HFSE) than hornblende in the I-type granitoids, indicating the addition of F-HFSE-rich alkaline fluids during its magmatic evolution. The consumption of arfvedsonite and formation of aegirine further indicate the role of fluid metasomatism and H2 degassing via a reaction of 3Na3Fe5Si8O22(OH)2 + 2H2O = 9NaFeSi2O6 + 2Fe3O4 + 6SiO2+5H2. The combined geochemical data demonstrate that the systematic differences in mineral assemblage, whole-rock composition, magma temperature, H2O content, and δD of apatite between the I- and A-type granites are likely attributed to varying degrees of differentiation, fluid metasomatism and magmatic degassing. The I-type granitoids experienced hornblende, biotite, plagioclase, K-feldspar, and apatite fractionation and close-system degassing. The A-type granite was likely formed from the I-type monzogranitic magma that was metasomatized by the mantle-derived F-HFSE-rich alkaline fluids to produce the peralkaline magma, which further experienced K-feldspar + plagioclase + biotite + apatite fractionation and open-system degassing. Further numerical estimation indicates that the primary magma of Fuzhou granitic complex contained ~3.0 wt% H2O, and the lower water content of A-type granite was likely attributed to strong degassing during its emplacement. Our results indicate that some peralkaline A-type granites can be generated from relatively water-poor I-type granitic magmas by fluid metasomatism and degassing.