Stable Isotope Signatures Research Articles

Conspicuous parasite modifies appearance and energetics of a marine copepod

Abstract Parasitism is an important driver of ecosystem processes. Copepods are fundamental trophic links in marine food webs and harbour many microeukaryotic parasites, but unreliable access to infected individuals limits quantitative studies of parasite infection costs. Calanus spp., (helgolandicus or finmarchicus), infected with the Yellow-Hyphal Parasite become pigmented and are found near the surface, suggesting predator-mediated dispersal. Conventional markers prevented phylogenetic inference but confirmed that the parasite is not Ichthyophonus hoferi, as previously thought. We identified the pigments, quantified the pigment content and respiration rate, and derived stable isotope signatures of infected and uninfected Calanus spp. to examine costs of infection. We found that the pigments were astaxanthin and β-carotene, associated with the host and parasite, respectively. Parasitized hosts had increased astaxanthin content, reduced respiration rate, and lower lipid content. Ultrastructure imaging revealed parasitic cells associated with lipids in the haemocoel. The changes to host phenotype have detrimental impacts on energetics and the ecology of Calanus. We discuss the role of pigments in parasite-host interactions and suggest that the parasite produces β-carotene pigment for its physiological benefits. The trade-off between physiological benefits of pigments and conspicuousness for parasites is relevant in zooplankton-host systems, as zooplankton rely heavily on transparency for survival.

Stable Isotope Analysis of Planktonic Lower Food Webs of Lakes Erie, Huron, Michigan and Superior

Historical plankton samples from the St. Lawrence Great Lakes were subjected to taxon-specific 15N analysis to test the hypothesis that the changes recorded in zooplankton communities during the 21st Century are related to changes in the trophic positions of large-bodied carnivorous copepods. Daphnia mendotae was used as the reference herbivore for trophic-level comparisons. The results were that Limnocalanus macrurus, Diaptomus (Leptodiaptomus) sicilis as well as the cladoceran Bythotrephes cederstroemi show evidence of elevated carnivory compared to data from the 20th Century. The large diaptomid Diaptomus (Leptodiaptomus) sicilis has a stable isotope signature that is significantly more carnivorous in Lake Superior than in Lakes Michigan and Huron by approximately one-half trophic level. Differences were found in 10 cases out of 15 for Limnocalanus (Huron, Michigan Superior), 6 cases out of 15 for Diaptomus (Huron, Michigan) and in 1 out of 1 for Senecella (Superior). We did not find evidence to support the theory that large-bodied calanoid copepods may have improved their representation in the food webs of the upper Great Lakes by shifting their trophic position downward. Instead, large-bodied Calanoida have increased their trophic positions in parallel with their increased relative abundance. More research is thus needed to explain the driving forces for changing food web dynamics in the Great Lakes.

Stable silicon isotope fractionation reflects the routing of water through a mesoscale hillslope

Concentration - isotope Ratio - Discharge (C-R-Q) relationships offer a promising means of disentangling the underlying hydrologic, geochemical, and ecological factors that produce variations in stream solute chemistry across a variety of critical zone systems. However, natural environments are both temporally and spatially complex, and prevailing interpretations of these C-R-Q patterns remain difficult to validate. Here we employ three replicate artificially constructed hillslopes at the Landscape Evolution Observatory (LEO) in Tucson, Arizona as simplified analogs to natural catchments. LEO allows us to record silicon stable isotope (δ30Si) signatures of fluid discharge under a controlled irrigation schedule in a system devoid of vegetation. This unique meso‑scale experiment enables, for the first time, evaluation of metalloid stable isotope signatures at the scale of natural hillslopes constrained to known fluid transit time distributions (TTDs) and limited to fractionation in association with secondary mineral formation. We report δ30Si in discharge samples collected over three randomized storm events of varying intensity. The data reflect consistent enrichment in the fluid phase between +1.00 and +2.07 ‰ across the three hillslopes, despite highly variable irrigation scenarios, reflecting substantial loss of SiO2 from solution due to secondary mineral precipitation. We compare results from an isotope-enabled Reactive Transport Model (RTM) and the discharge measurements from LEO to constrain the contributions of both characteristic watershed TTDs and fractionation pathways in emergent δ30Si signatures. Our study confirms and expands upon recent work in natural systems attributing intra-site variability in silicon stable isotope signatures to the routing of fluid through catchments.

Using mercury and lead stable isotopes to assess mercury, lead, and trace metal source contributions to Great Salt Lake, Utah, USA

Great Salt Lake is a critical habitat for migratory birds that is threatened by elevated metal concentrations, including mercury (Hg) and lead (Pb), and is subject to severe hydrologic changes, such as declining lake level. When assessing metal profiles recorded in Great Salt Lake sediment, a large data gap exists regarding the sources of metals within the system, which is complicated by various source inputs to the lake and complex biogeochemistry. Here, we leverage Hg and Pb stable isotopes to track relative changes in metal source contributions to Great Salt Lake over time. Mercury and Pb concentrations increase in sediments deposited after 1920 and peak between 1965 and 1995, following closure of several local smelters and the onset of increased emission controls. The nominal associations above are confirmed via Hg stable isotopes in pre-1920 background sediments, which reflect atmospheric inputs from regional and global origin, whereas Hg and Pb stable isotopes together indicate that elevated metal concentrations in mid-late 20th century sediments reflect increased mining/smelting inputs. The observed minimal rebound towards pre-1920 Pb isotope signatures in 21st century sediments indicates that mining/smelting inputs, though reduced, remain a primary source of Pb to Great Salt Lake. In contrast, the more pronounced rebound of Hg stable isotope signatures to pre-1920 values indicate a greater contribution of atmospheric inputs of regional/global origin to current Hg inputs, though Hg concentrations are ~10 times greater than pre-1920 background values due to global increases in atmospheric Hg concentrations or possibly slow recovery from local contamination. The importance of regional/global Hg sources to the system suggests that reductions in Hg bioaccumulation in the open water food webs of Great Salt Lake are more dependent on national and global reductions in Hg emissions and management strategies to limit methylmercury production within system. This work highlights the utility of using coupled Hg and Pb stable isotope values to assess trace metal pollution sources and pathways in aquatic systems.

A Tale of Two Storms: Inter‐Storm Variability of Stable Water Isotopes in a Solute Transport Model

ABSTRACTStable isotopic methods in hydroclimate monitoring are powerful for improving water resources management, but applications are limited, especially in semi‐arid regions where such management is needed most. Here, we show that we can address shortcomings related to the lack of a seasonal signal using stable water isotopic signatures measured in precipitation over the East San Francisco Bay area, California, during two contrasting events sampled at more than 20 locations in the winter of 2023. The observed range in δ18O in the rain samples is similar for both storms. However, the distributions do not overlap—the mean air temperature and δ18O during Winter Storm Olive (February 2023) were 2°C and − 12‰, respectively, while a warm atmospheric river event (March 2023) had a mean temperature of 9°C and δ18O of −6‰, close to the long‐term average δ18O measured in local precipitation. The Winter Storm showed expected trends in δ18O related to geography (i.e., lower with greater distance inland and elevation), while the atmospheric river δ18O pattern was more spatially uniform. We use hydrometric data from a gaged watershed in the study area and isotopic signatures of rain sampled during the two storm events and apply a solute transport model (StorAge selection) with a travel‐time approach to examine predicted watershed responses and potential water tracing applications. In this virtual experiment, we find that event size exerts a strong control on the relative amounts of runoff versus pre‐event water in the stream, while uncertainty in stream hydrograph separation is related to the degree of contrast between precipitation/runoff and pre‐event water. Key to flood prediction, adaptation, and mitigation, especially in coastal urban areas, is knowledge of the contributing water sources and timing of stream flow. The strong contrast in stable isotopes between these two events, close in time and over the same area, illustrates the potential to use stable isotope signatures to track the transport and mixing of events through natural and engineered watersheds that are threatened by climate whiplash events.

Metabolic Profiling and Stable Isotope Analysis of Wines: Pilot Study for Cross-Border Authentication.

Globalization and free market dynamics have significantly impacted state economies, particularly in the wine industry. These forces have introduced greater diversity in wine products but have also heightened the risk of food fraud, especially in high-value commodities like wine. Due to its market value and the premium placed on quality, wine is frequently subject to adulteration. This issue is often addressed through regulatory trademarks on wine labels, such as Protected Designation of Origin (PDO) and Protected Geographic Indication (PGI). In this context, the metabolic profiles (organic acids, carbohydrates, and phenols) and stable isotope signatures (δ13C, δ18O, D/HI, and D/HII) of red and white wines from four agroclimatically similar regions were examined. The study explored how factors such as grape variety, harvest year, and geographical origin affect wine composition, with a particular focus on distinguishing samples from cross-border areas. Multivariate statistical analysis was used to assess the variability in wine composition and to identify distinct groups of samples. Preliminary results revealed that organic acids and volatile compounds were found in lower concentrations than carbohydrates but were significantly higher than phenols, with levels ranging between 1617 mg/L and 6258 mg/L. Carbohydrate content in the wines varied from 8285 mg/L to 14662 mg/L. Principal Component Analysis (PCA) indicated certain separation trends based on the variance in carbohydrates (e.g., fructose, glucose, galactose) and isotopic composition. However, Discriminant Analysis (DA) provided clear distinctions based on harvest year, variety, and geographical origin.

Exploring marine zooplankton dynamics through carbon stable isotope signatures in a recently marine submarine volcano

Submarine emissions of gases from hydrothermal vents alter the surrounding chemical environment, influencing species responses to the resulting environmental gradients. The 2011 underwater eruption of the Tagoro volcano off the coast of El Hierro in the Atlantic Ocean changed the physical and chemical conditions, impacting the distribution of pelagic fauna. Post-eruptive stages from 2013 to 2018 revealed changes in both benthic and pelagic communities, with continuous eruptions further affecting local carbon cycle through shifts in nutrient concentrations and isotopic composition. The lowest δ13C values in zooplanktonic primary consumers were found in areas directly influenced by the Tagoro submarine volcano. Although the mixing model results show that phytoplankton is the primary carbon source for copepods, contributing an average of 28.3% of their carbon, magmatic CO2 and seawater dissolved inorganic carbon each account for approximately 17–18%. The isotopic signatures reveal a gradient of enrichment in copepods, reflecting the influence of inorganic nutrient and gas emissions from the volcano's centre to its periphery within the marine ecosystem. This data is useful for understanding the worldwide significance of environmental stressors such as volcanic eruptions on marine organisms.

Hydrological controls of a riparian wetland based on stable isotope data and model simulations.

Isotopic evidence of groundwater and stream water is frequently used to investigate water exchanges with groundwater. Monthly sampling of rain, stream water, and groundwater was conducted at Tims Branch watershed in South Carolina for the oxygen and hydrogen stable isotope (δ2H and δ18O) measurement, as well as pH and oxidation-reduction potential (ORP). Together with a mass balance perspective, it was determined that it takes a few weeks to one month for groundwater in the hyporheic zone to fully exchange with stream water. From hydrodynamic modelling, we show that substantial (up to 70 %) groundwater exchange occurs at gaining and losing sites. Groundwater exfiltration, i.e. inflow into stream water, contributes up to 4 % to stream water, with the remainder from upstream exfiltration. A 2-4 % per day renewal rate of adjacent groundwater would indirectly indicate a groundwater residence time in the order of half a month to a full month (assuming either a well-mixed case or large dispersion rate in pulse flow case), in agreement with a greatly reduced variability of δ2H and δ18O of groundwater compared to stream water and rain. This reduced variability of stable isotope signal from groundwater confirms our hypothesis that riparian groundwater mixing at Tims Branch is more of a mixed type rather than a pulse flow type. A monthly time scale is sufficient for groundwater to become anoxic at exit points into stream water resulting in the episodic production of natural organic matter- and iron-rich flocs upon oxidation.

Palaeogeographical and eodiagenetic settings of host‐replacing phreatic calcrete intervals developed in mud deposits of the Famennian Kinnesswood Formation in the Pennyseorach Subbasin of south‐west Scotland

ABSTRACTIn the Pennyseorach Subbasin of south‐west Scotland, the Famennian Kinnesswood Formation of the Inverclyde Group includes several, ca 1 to 3 m thick erosional remnants of host‐replacing phreatic calcrete hardpans developed in mud deposits. The latter are most unusual hosts for such calcretes due to their relative impermeability, which would normally prevent them from sufficiently accommodating the circulation of an aquifer. In previously documented phreatic calcretes, mud deposits clearly acted as aquicludes that sharply constrained calcrete development. In the Kinnesswood Formation at Pennyseorach, tall desiccation fissures allowed groundwater to circulate in thick, semi‐consolidated mud deposits. Because of the inferred development of an adjacent evaporitic basin, the mixing of fresh and evaporitic groundwaters raised the pH enough for the replacement of phyllosilicates by calcite to occur along the fissure walls, forming ‘fissure calcretes’. The latter gradually expanded and eventually coalesced into mature, ‘columnar host‐replacing phreatic calcrete hardpans’ in which 90 to 100% of the muddy host material was replaced by calcrete. At Pennyseorach, host‐replacing phreatic calcrete hardpan formation not only affected the transition zone between the Doughend Sandstone and Foul Port Members of the Kinnesswood Formation (the Dunagoil Calcrete interval), as in other localities of south‐west Scotland, but also affected the uppermost part of the formation, which is marked by several erosion surfaces downcutting into columnar host‐replacing phreatic calcrete hardpan intervals in association with the episodic rise and fall of base‐level. These newly recorded host‐replacing phreatic calcrete hardpan intervals from the upper part of the Kinnesswood Formation have a tightly constrained stable isotopic signature that is distinct from that of both the Dunagoil Calcrete and the successive host‐replacing phreatic calcrete hardpans of the Visean Clyde Sandstone Formation within the same group, underlining their potential as stratigraphic markers and palaeoenvironmental indicators.

Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation.

Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B12 and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of 13C and 37Cl was observed in all abiotic reactions, with εC,bulk and εCl,bulk values ranging from -4.3 ± 0.4‰ to -2.3 ± 0.2‰ and from -2.6 ± 0.4‰ to -1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C10-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify in situ chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).

Effects of urbanization on diet in eastern chipmunks (Tamias striatus) as determined by stable isotopes

Urban environments offer wildlife a consistent supply of anthropogenic food waste, divergent from natural food sources in nutrient composition. This study investigates the dietary impact of urbanization on eastern chipmunks (Tamias striatus (Linnaeus, 1758)) by analyzing stable isotope signatures (∂13C and ∂15N) in their hair. The hypothesis posits that chipmunks in urban locales consume more corn-based and high-protein foods, reflected in elevated isotopic signatures compared to their rural counterparts. Sampling encompassed 20 sites across Sudbury, Ontario, varying in urbanization levels. Urbanization was gauged via surveys capturing human activity and sources of anthropogenic food waste. Contrary to expectations, chipmunks did not exhibit δ13C signatures indicative of substantial corn consumption from human food waste. However, δ15N signatures positively correlated with urbanization, suggesting heightened animal protein intake in urban habitats. Elevated δ15N signatures may also result from the use of fertilizers in urban areas . Future avenues involve using stable isotope mixing models to pinpoint dietary sources and exploring the health and reproductive ramifications of urban diets, including effects on gut microbiome composition.

Quantifying mass-dependent isotope fractionation and nuclear field shift effects for the light rare Earth elements in hydrous systems

The improving sensitivity of mass-spectrometers has opened the potential of using stable isotope signatures of the rare Earth elements (REE) as geochemical tracers. However, thus far only limited studies have utilised REE stable isotopes, despite resolvable variations having been observed in a range of systems. An interesting but poorly explored area remains variations in aqueous environments across a range of temperatures including seawater, marine sediments, ion adsorption deposits or hydrothermal systems. Furthermore, the magnitudes and competing effects of mass-dependent isotope fractionation and mass-independent nuclear field shift effects, which can be significant factor for heavy elements especially at high temperatures, remain poorly understood.To contribute to a holistic understanding of REE isotope signatures, we calculated reduced partition function ratios (as 103lnβ) for mass-dependent and nuclear field shift effects for aqueous La, Ce, and Nd complexes from first principles. Theoretical calculations were compared with experimental data, and this demonstrates that calculations involving a combination of two explicit hydration shells and additional implicit solvation effects are required to accurately describe the coordination and molecular vibrations of aqueous complexes. This data was then combined with speciation modelling of seawater and hydrothermal fluids to assess isotope fractionation in hydrous systems. The predicted magnitude of isotope fractionation is significant in low (T = 25 °C) temperature systems (Δ139/138LaMax-Min = 0.20 ‰, Δ142/140CeMax-Min = 0.33 ‰, Δ146/144NdMax-Min = 0.34 ‰) and remains above currently achievable analytical uncertainties even at high (T = 500 °C) temperatures (±0.015 ‰ for δ146/144Nd; ±0.040 ‰ for δ142/140Ce). Unless oxidation occurs, which is only relevant for Ce in terrestrial environments, nuclear field shift effects are negligible even at temperatures up to 500 °C. The large difference in nuclear charge radius between 140Ce and 142Ce strongly enriches the lighter Ce isotope in the higher oxidation state (103lnβCe(IV)-Ce(III) = −0.45 at 25 °C) which almost completely cancels out the opposing mass-dependent effect (103lnβCe(IV)-Ce(III) = +0.46 at 25 °C). This means that variations in δ142/140Ce isotope signatures cannot easily be related to oxidation in ancient or recent environments.

Investigation of the Geochemical Evolution of Groundwater Using Major Ions and Stable Isotopes Signatures: A Case Study in Transboundary Aquifers

Investigation of the Geochemical Evolution of Groundwater Using Major Ions and Stable Isotopes Signatures: A Case Study in Transboundary Aquifers

Source and Origin of Subsurface Brine of the Kongquehe Sag Area in Western Lop Nur, China

The Kongquehe Sag, located in the western Lop Nur, has abundant pore subsurface brine. In order to study the source and origin, we tested and analyzed the hydrochemical composition and stable isotopes of the subsurface brine. The findings reveal that the brine exhibits a moderate to low degree of mineralization, with values ranging from 50.50 g/L to 91.14 g/L. The stable isotope compositions of unconfined and confined waters are different, with the mean values of δD being −8.00‰ and −51.75‰ and the mean values of δ18O being 10.08‰ and −6.01‰. These values are indicative of an intense evaporative environment prevalent in the Kongquehe Sag area. Furthermore, the 87Sr/86Sr ratios vary between 0.710642 and 0.710837, and δ34S values range from 9.2 to 10.7. These data suggest the long-term evolution of sulfur substances, predominantly through dissolution and sedimentation processes, with minimal influence from redox reactions. The data garnered from this research not only offer a novel perspective of the insights gained into the hydrochemical characteristics and the stable isotope signatures of the brines in the Kongquehe Sag area but also enriches the theoretical framework concerning the source and origin of subsurface brines, potentially informing future exploration strategies.

Lacustrine groundwater discharge-derived carbon and nitrogen to regulate biogeochemical processes as revealed by stable isotope signals in a large shallow eutrophic lake

Eutrophic shallow lakes are hotspots of carbon (C) and nitrogen (N) accumulation and transformation, and are increasingly recognized as important sources of greenhouse gases (GHGs: CO2, CH4 and N2O). Lacustrine groundwater discharge (LGD) is a crucial component of the water budget and terrestrial material delivery for lakes, but its interplays with intrinsic CN biogeochemical processes remain less tackled. In this study, C and N ingredients and multiple stable isotopes (δ2H, δ18O, δ13C, and δ15N) were measured seasonally in groundwater, river water and lake water of a large eutrophic shallow lake in eastern China. The results revealed that groundwater is enriched with various forms of C and N that have similar sources and pathways as surface water in the lake and rivers. The isotope balance model also indicated that LGD derived C and N contribute significantly to lake inventories in addition to river runoff. These allochthonous C and N provide extra substrates for related biogeochemical processes, such as algae proliferation, organic matter degradation, methanogenesis and denitrification. Simultaneously, the excess oxygen consumption leads to depletion and hypoxia in the lake, further facilitating the processes of methanogenesis and denitrification. LGD functions not only as an external source of C and N that directly increases GHG saturations, but also as a mediator of internal CN pathways, which significantly affect hypoxia formation, GHG productions and emissions in the eutrophic lake. This study highlights the unrevealed potential regulation of LGD on biogeochemical processes in the eutrophic lake, and underscores the need for its consideration in environmental and ecological studies of lakes both regionally and globally.

Hydrocarbons, Hydrogen, and Organic Acids Generation by Ball Milling and Batch Incubation of Sedimentary Rocks

Pulverized rock samples are widely used in laboratory experiments, e.g., to assess microbial or abiotic processes in batch incubation tests. However, it is unclear if ball-milled samples accurately reflect in-situ conditions and if observed processes are affected by by-products artificially generated during the sample preparation procedure. As such, this study examined the effects of dry ball milling on the release of gases, which include C1-C4 hydrocarbons, carbon dioxide (CO2), hydrogen (H2), and low molecular weight organic acids (LMWOAs) from different sedimentary rocks. The experiments involved pulverization using a gas-tight zirconium oxide planetary ball mill followed by wet and dry batch incubation and thermal desorption up to 200 o C. During milling, all sedimentary rocks, except a low organic carbon sandstone sample, yielded methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H10), H2, CO2, and unsaturated hydrocarbons, e.g., ethene (C2H4). Sandstones only yielded H2, CH4, and CO2. Stable carbon isotope signatures of these products are similar to thermogenic gases. The gases were also detected in subsequent wet incubation experiments (after gases from milling had been removed). Additionally, formate, acetate, and citrate, were detected in all samples except for sandstone. Pyruvate, malate, and succinate were also detected in some samples. Thermal desorption products of powdered limestone, shale, and pyrite concretion samples included organic acids, such as acetate and formate, which were higher in milled samples than in crushed particles (∼1 mm). The original geological thermal maturity of the studied sedimentary rock samples was low (below “oil window”) and, thus, considerably below “gas window”, suggesting that most of the detected gases were generated during ball milling. H2 generated during ball milling may be derived from the reduction of water from fluid inclusion or phyllosilicates, involving the formation of reactive mineral surfaces or radicals. Notably, the concentrations of gaseous hydrocarbons derived from milling are relatively high and comparable to “wet” gases. At the same time, these data indicate that substantial amounts of gases and LWMOAs might be artificially generated during laboratory batch experiments with milled samples. Hence, ball milled rock samples must be used with caution if assessing (bio-)geochemical processes for natural environments.

Elemental and stable isotopic signatures for dynamic traceability of genuine and "bathing" cultured Yangcheng Eriocheir sinensis crabs

This study examines whether the "bathing" culture of Chinese mitten crabs Eriocheir sinensis outside the Yangcheng Lake area converges with the origin characteristics of crabs from Yangcheng Lake and Kunshan Ponds. Inductively coupled plasma mass spectrometry (ICP-MS) and stable isotope ratio mass spectrometry (IRMS) were used to analyze mineral elements and stable isotopes in crabs at various stages of "bathing". The results indicated a dynamic transformation in the origin characteristics of "bathed" crabs; however, full convergence with genuine crabs was not achieved. Notably, disparities persisted between genuine crabs and "bathed" crabs. The combination of mineral elements and stable isotopes exhibited a discrimination accuracy of 95 % and 81.3 % between genuine crabs and "bathed crabs" from Kunshan Ponds and the Yangcheng Lake during each period of “bathing", respectively, which was higher than that using either method alone. This suggests limitations in altering original characteristics through "bathing". The combination of mineral elements and stable isotopes provides promising avenues for origin identification and understanding changes in crab characteristics during the "bathing" process. These findings highlight the complexities of crab culture practices and have implications for quality control and origin authentication in the crab industry.

Source identification of organic C and N in suspended particulate matter and sediments in plateau lakes as influenced by trophic status using stable isotopic signatures

Understanding the relationship between suspended particulate matter (SPM), sediment organic C, N stable isotopes, and lake trophic state index (TSI) is essential for managing lake pollution and eutrophication. According to the δ13C, δ15N, and C/N we found that the organic C in SPM and sediment of Caohai Lake primarily originated from macrophytes, while N was sourced from chemical fertilizers, phytoplankton, and aquatic plants. Total nitrogen, total phosphorus, NO3−-N, oxidation reduction potential, and Chl.a were identified as key factors influencing the sources and variations of SPM and sediment organic C and N stable isotopes in Caohai Lake, with a significant linear correlation observed between C, N stable isotopes, and TSI in sediments. To mitigate eutrophication in Caohai Lake, it is recommended that farmers apply fertilizers judiciously to minimize nutrient loss and that aquatic plants be regularly harvested to reduce N release from plant residues.

A review of benthic foraminiferal oxygen and carbon isotopes

Stable isotopes in the calcium carbonate of benthic foraminifera provide important paleoenvironmental information about seawater/sedimentary porewaters that these foraminifera live in. Oxygen isotopes provide essential insights about variations in deep water temperatures and sea-level/ice volume changes, while carbon isotopes provide information about sea-water carbon/nutrient cycling. In this review we look into detail at the direct and indirect mechanisms that contribute to stable oxygen and carbon isotope signals in Rotaliid benthic foraminifera. This includes effects from ontogenetic- and calcification mechanisms, and the impact of methane seeps and post-depositional diagenesis. We conclude our review with an overview of current challenges and provide recommendations for future research endeavors aimed at outstanding knowledge gaps in understanding how these biomineralizers control their stable isotopes.

Theoretical and experimental constraints on hydrogen isotope equilibrium in C1-C5 alkanes

Stable isotope ratios of C1–C5 alkanes, the major constituents of subsurface gaseous hydrocarbons, can provide valuable insights on their origins, transport, and fates. Equilibrium isotope effects are fundamental to interpreting stable isotope signatures, as recognition of them in natural materials indicates reversible processes and constrains the temperatures of equilibrated systems. Hydrogen isotope equilibrium of C1–C5 alkanes is of particular interest because evidence shows that alkyl H can undergo isotopic exchange with coexisting compounds under subsurface conditions. We present the results of a combined experimental and theoretical effort to determine equilibrium hydrogen isotope distributions in mixtures of these hydrocarbon compounds. We created two mixtures: one with C1, C2 and C3 (where C1 indicates methane, C2 ethane, etc., hereinafter called ‘C1–C3 mixture’) and another one with C2, C3, iC4, nC4, iC5 and nC5 (hereinafter called ‘C2–C5 mixture’); in both cases, the mixtures were created to start out of hydrogen isotope equilibrium. We tested the performance of several metal catalysts as aids to H isotopic exchange by exposing these mixtures to different metal catalysts at 100 or 200 °C and analyzing the compound-specific hydrogen isotope ratios of the product gases. The C1–C3 mixture exchanged hydrogen isotopes among the starting gas components rapidly in the presence of Ru/Al2O3 at 200 °C. The isotope ratios reach a steady-state (presumably equilibrium) after 72 h of heating (up to 120 h). The hydrogen isotopic ratios of alkanes in the C2–C5 mixture shifted significantly in the presence of Rh/Al2O3 at 100 °C and C3-C5 compounds approached steady state after 70 h, whereas C2 had not yet reached a steady state D/H ratio after 216 h of heating. We evaluated the reaction progress of isotope exchange for each compound as a function of time with a reaction-network model informed by constraints on chemical kinetics. The model indicates that C3, iC4, nC4, iC5 and nC5 in the C2-C5 mixture reached internal isotope equilibrium after 70 h, hence we used their values to calculate experimental equilibrium results. We also calculated equilibrium isotope fractionations with the Bigeleisen-Mayer theorem using vibrational frequencies computed from the density functional theory (B3LYP/aug-cc-pVTZ). We included torsional conformers and explicit H positions in the calculations. We found that the experimental results from both the 200 ˚C C1–C3 experiment and 100 ˚C C2–C5 experiment are consistent with theoretical equilibrium results within experimental uncertainty. Additionally, our reaction-network model for catalyzed hydrogen isotope exchange between alkanes succeeded in fitting our experimental results. This modeling framework can be adjusted to simulate exchange in natural settings for constraining temperature histories and sources of natural gases.