Stable Hydrogen Isotope Research Articles

Hydrogen isotope fractionation during aromatization to form alkylnaphthalene: Insights from pyrolysis experiments of 1-n-butyldecalin

Alkylnaphthalene homologues are important components of aromatic fraction in sedimentary organic matter and contain significantly geochemical information relative to formation and evolution of the host organic matter. They mainly originate from hydrocarbon aromatization reaction which involves the dehydrogenation of aliphatic rings resulting in the fractionation of stable hydrogen isotopes between aromatic hydrocarbons and their precursors. To examine these processes, this study thermally pyrolysed 1-n-butyldecalin (BD) at different time intervals under 360 °C/50 MPa to study the aromatization and hydrogen isotope fractionation during alkylnaphthalene formation and evolution. The relative content of aromatic products, such as naphthalene (N) and 1-methylnaphthalene (1-MN), increases with increasing aromatization. Sulfur enhanced the degree of aromatization during BD thermal evolution, resulting in greater N and 1-MN formation. For the compounds with the same carbon skeleton, i.e. tran-1-methyldecalin (1-MD), 5-methyltetraline (5-MT) and 1-MN, the 2H enrichment follows the order δ2H1-MD < δ2H5-MT < δ2H1-MN during the low thermal conversion of BD. However, the order was subsequently destroyed with increasing aromatization. The results indicate that hydrocarbon aromatization can enrich aromatic hydrocarbon in 2H, resulting in a higher δ2H value of higher aromatic-ring-number hydrocarbon than that of a lower aromatic-ring-number at low aromatization. However, 2H enrichment will decrease and even result in a reverse order with enhanced aromatization. Our findings are beneficial for understanding genetic mechanism and hydrogen isotope fractionation effect during the formation and evolution of aromatic hydrocarbons.

Decoupling of Tree‐Ring Cellulose δ18O and δ2H Highlighted by Their Contrasting Relationships to Climate and Tree Intrinsic Variables

ABSTRACTOxygen (δ18O) and hydrogen (δ2H) stable isotope ratios are tightly coupled in precipitation and, albeit damped, in leaf water, but are often decoupled in tree‐ring cellulose. The environmental and physiological conditions in which this decoupling occurs are not yet well understood. We investigated the relationships between δ18O and δ2H and tree‐ring width (TRW), tree crown volume, tree age and climate in silver fir and Douglas‐fir and found substantial differences between δ18O and δ2H. Overall, δ18O–δ2H correlations were weak to absent but became significantly negative under high summer vapour pressure deficit (VPD). δ18O and δ2H had positive and negative nonlinear relationships with TRW, respectively, with clear relationships at the site and tree levels for silver fir and, to a lesser extent, for Douglas‐fir. Age trends for silver fir were weakly negative in δ18O but positive in δ2H. Tree crown volume and δ18O or δ2H had no significant relationships. Most strikingly, δ18O strongly depended on spring climate (precipitation and VPD), whereas δ2H depended on summer climate (temperature and VPD) for both species. Our study shows that the δ18O–δ2H decoupling in tree‐ring cellulose in two temperate conifer species could be highlighted by their contrasting relationships to climate and tree intrinsic variables (TRW, age).

Identification and prevention of gas source in goaf: Stable carbon hydrogen isotope tracer method and numerical simulation of gas flow field

Identification and prevention of gas source in goaf: Stable carbon hydrogen isotope tracer method and numerical simulation of gas flow field

Seasonal variations and altitude effect of oxygen and hydrogen stable isotope ratios of precipitation and spring water in an island of Seto Inland Sea

Seasonal variations and altitude effect of oxygen and hydrogen stable isotope ratios of precipitation and spring water in an island of Seto Inland Sea

Use of stable isotope combined with intact cell lipidomic by routine MALDI mass spectrometry analysis for rapid drug susceptibility assay in mycobacteria.

Rapid, accurate, and easy-to-perform diagnostic assays are required to address the current need for the diagnosis of resistant pathogens. That is particularly the case for mycobacteria, such as the human pathogen Mycobacterium tuberculosis, which requires up to 2weeks for the determination of the drug susceptibility profile using the conventional broth microdilution method. To address this challenge, we investigated the incorporation of deuterium, the stable isotope of hydrogen, into lipids as a read out of the drug susceptibility profile. Deuterium is incorporated into newly synthesized proteins or lipids in place of hydrogen as bacterial cells grow, increasing the mass of the macromolecules, which can then be observed via matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS). As proof-of-concept, we used the non-pathogenic Mycobacterium smegmatis mc2155 strain, which is susceptible to the aminoglycoside antibiotic kanamycin, and M.smegmatis mc2155 containing the empty vector pVV16, which is kanamycin-resistant. Bacteria were incubated in a culture medium containing 50% of deuterium oxide (D2O) and either 1 or 2 times the minimal inhibitory concentration (MIC50) of kanamycin. Lipids were then analyzed using the MBT lipid Xtract matrix combined with routine MALDI mass spectrometry in the positive ion mode to evaluate the changes in the lipid profile. Using this approach, we were able to distinguish susceptible from resistant bacteria in less than 5h, a process that would take 72 h using the conventional broth microdilution method. We therefore propose a solution for the rapid determination of drug susceptibility profiles using a phenotypic assay combining D2O stable isotope labelling and lipid analysis by routine MALDI mass spectrometry.

Exploring hydrogen isotope fractionation in lipid biomolecules of freshwater algae: implications for ecological and paleoenvironmental studies

ABSTRACT Understanding the stable hydrogen isotope (δ 2H) composition and fractionation in lipid biomolecules of primary producers, such as terrestrial and aquatic plants, is crucial for deciphering past environmental conditions, as well as applying compound-specific stable isotope analysis for the study of metabolic and ecological processes. We conducted a new tracer experiment to explore the δ 2H composition of algal fatty acid biomarkers, focusing on freshwater algae, which form the base of aquatic food webs. We selected a range of algal species widely found in freshwater ecosystems and cultivated them under controlled conditions. First, we added 2H2O to ambient water as a tracer to investigate the net hydrogen isotope fractionation during algal lipid synthesis at isotopic equilibrium, which is particularly informative for paleo-geochemical studies. Then, we conducted kinetic experiments to quantify the time needed for algal fatty acids to achieve isotopic steady-state conditions in response to the change in ambient water δ 2H values. Our findings revealed substantial variability in hydrogen isotope fractionation among different algal taxa and various fatty acids. Based on taxa, different fatty acids exhibited faster integration of water hydrogen than others, but they were not necessarily in the order of the biosynthetic pathway. This experiment underscores the complexity of hydrogen isotope fractionation and the requirement for controlled laboratory studies to properly apply compound-specific stable H isotope analysis techniques in ecological and paleo-environmental studies.

Hydrogen isotope labeling unravels origin of soil-bound organic contaminant residues in biodegradability testing

Biodegradability testing in soil helps to identify safe synthetic organic chemicals but is still obscured by the formation of soil-bound ‘non-extractable’ residues (NERs). Present-day methodologies using radiocarbon or stable (13C, 15N) isotope labeling cannot easily differentiate soil-bound parent chemicals or transformation products (xenoNERs) from harmless soil-bound biomolecules of microbial degraders (bioNERs). Hypothesizing a minimal retention of hydrogen in biomolecules, we here apply stable hydrogen isotope – deuterium (D) – labeling to unravel the origin of NERs. Soil biodegradation tests with D- and 13C-labeled 2,4-D, glyphosate and sulfamethoxazole reveal consistently lower proportions of applied D than 13C in total NERs and in amino acids, a quantitative biomarker for bioNERs. Soil-bound D thus mostly represents xenoNERs and not bioNERs, enabling an efficient quantification of xenoNERs by just measuring the total bound D. D or tritium (T) labeling could thus improve the value of biodegradability testing results for diverse organic chemicals forming soil-bound residues.

Robinia pseudoacacia Quickly Adjusts Its Water Uptake after Rainfall in Seasonally Dry Regions

Precipitation is a key factor affecting plant growth and development in seasonally arid regions. However, most of the traditional hydrological methods mainly select typically sunny days for sampling, and the immediate water absorption strategy of plants during and after rainfall is still unclear. This study used stable hydrogen and oxygen isotope technology to study the soil moisture absorption rates of Robinia pseudoacacia and the soil moisture content at different soil layers at different sampling times (0, 6, 12, 18 and 24 h) after rainfall. The results showed that the moisture content of the shallow soil layer decreased, while that of the deep soil layer increased over time after rainfall. R. pseudoacacia mainly utilized water from the 0–20 and 20–40 cm soil layers at 6 h after rainfall, which accounted for 36.52% and 22.25% of the rainfall, respectively. At 24 h, the 40–60, 60–80 and 80–100 cm soil layers contributed 25.25%, 18.44% and 24.45% of the water content, respectively. The shallow soil layer retained more rainfall within 6 h after rain fell, and the water retention ratio of the medium–shallow soil layer (0–60 cm) increased to 48.4%, retaining more water at 14–20 h. At 12 h, the medium–shallow soil layer (0–60 cm), runoff and groundwater constituted 37.1%, 14.4% and 15.7% of the precipitation, respectively, and rainfall retained in the deep soil layer (60–100 cm) accounted for 32.8%. In summary, R. pseudoacacia tends to use a large amount of shallow soil water in seasonally arid regions when precipitation supplements the surface soil moisture content and it utilizes deep soil water when the rainfall infiltrates and recharges the deep soil layer. Since R. pseudoacacia is sensitive to precipitation, it can quickly adjust its water absorption depth range during the short-term rainfall period to absorb as much precipitation as possible.

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.

Causes for overestimation of the moisture recycling in an alpine meadow ecosystem of the Shule River Basin, Tibetan Plateau, China

Terrestrial moisture recycling is an essential hydrological component and a significant source of the atmosphere’s humidity budget in arid and semi-arid inland regions. Investigations on moisture recycling using the stable hydrogen and oxygen isotopes is currently a focal point in hydrologic research. However, the direct quantification of recycling ratio based on isotopic composition of evapotranspiration vapor is lacking. So, this causes challenges to compare studies, based in the same region and time period but with different methodologies. In this study, we measured the isotopic compositions of evapotranspiration vapor (δ18OET/δDET) from June to September 2018 in an alpine meadow ecosystem at the Shule River Basin by combining the Keeling plot model and in-situ chamber measurement. Using this data, the moisture recycled rate (mrr) was assessed based on the two-component (Model A) and three-component isotopic mixing models (Model B), respectively. Based on Model A and δ18OET, the analysis revealed that the mean recycled rate for the entire observation period was 35 %, while it was 26 % during the westerly period (the months dominated by the north branch of prevailing westerlies) and 44 % during the monsoon period (when subtropical moisture from the Indian monsoon penetrated the region). The recycled rate based on Model A and δDET was slightly larger with a mean value of 41 % during the entire observation period. The recycled rate based on Model B was also significantly higher in comparison with Model A, while the causes for this difference could be the assumption of substituting xylem water for transpiration vapor and the plant water source δD offset. The contribution of recycled moisture was notable lower for heavy rainfall comparing with light rainfall. Our findings provided a new perspective for the investigations of alpine meadow ecosystem hydrological processes.

Broad geographic variation in age- and sex-dependent origin of harvested eurasian wigeon (Mareca penelope) revealed by stable-hydrogen (δ2H) isotope analyses of feathers

Migratory waterfowl are a harvested resource shared among multiple European countries, exposing them to potential overexploitation. Management of take is challenging since the life cycle of migratory waterfowl consists of several stages distributed among several locations, with possible spatio-temporal overlap among populations with differing population trends. Successful harvest management in such situations requires knowledge about the connections between breeding and non-breeding locations, and where birds are harvested. Breeding populations of Eurasian wigeon (Mareca penelope) are declining in Finland, underlining the need for more effective harvest management. Relative proportions and temporal distribution of local breeding birds and migrants from a larger Russian breeding population within the Finnish hunting bag has been unknown to date. We studied spatio-temporal origins of Finnish harvested wigeon by measuring stable-hydrogen (δ2H) isotope values from legally harvested birds. We modelled the changes in δ2H values of the feather samples within the hunting season using Gaussian processes and found that the origin of harvested wigeon in Finland changed during the hunting season and differed by age and sex. In juveniles and adult females but not in adult males, origin of harvested birds shifted from local and possibly western Russian birds to more long-distance migratory birds during the harvest season. These patterns likely reflected sex- and age-specific differences in migratory behaviour of Eurasian wigeon in the East Atlantic flyway, which can be used to guide future management and conservation of this species through the implementation of spatio-temporal harvest regulation.

Estimation of Surface and Groundwater Interaction by Stable Isotopic Techniques – A Case Study of Chengalpattu District, OMR Region

Isotopes are atoms of an element having the same atomic number but different mass numbers. Isotopes in hydrology and water resources are used for identifying its occurrence, movement, residence times, recharge, and discharge process. Stable isotopes of hydrogen(δ2H) and oxygen(δ2O) are used for identifying the surface and groundwater interactions as they constitute hydrogen and oxygen. In this study oxygen and hydrogen stable isotopes are used to identify surface and groundwater interaction in Old Mahabalipuram Road (OMR) regions of Chengalpattu district. The precipitation, lake, surface, and groundwater were collected during pre-monsoon, monsoon, and post-monsoon seasons. The collected sample is analyzed for stable isotopic compositions of oxygen and hydrogen seasonal-wise. The measured stable isotopic compositions during pre-monsoon season of stable oxygen are -4.29 to -2.00 and stable hydrogen are -29.39 to -24.67. The isotopic compositions during monsoon season range from -4.72 to -4.00 and for hydrogen ranges from -29.39 to -23.50. During monsoon season the depletion of isotopic composition is seen and the enrichment of isotopic composition is observed during pre-monsoon season. The variation in stable isotopic composition of oxygen and hydrogen are observed. A Groundwater Water Meteoric Water Line (GMWL) is developed for the study area, and it is compared with a Local Meteoric Water Line (LMWL) for better interpretation of the results. A slight deviation is observed from that of GMWL to LMWL mostly due to isotopic depletion and evaporation effects. From the analysis, a good correlation exists between precipitation and surface water in the study area indicating about recharge mechanism existing in the study area. The groundwater recharge is observed during monsoon seasons and discharge is more towards the pre-monsoon seasons.

Understanding the Source and Evolution of Precipitation Stable Isotope Composition across O‘ahu, Hawai‘i

Abstract Pacific Islands present unique challenges for water resource management due to their environmental vulnerability, dynamic climates, and heavy reliance on groundwater. Quantifying connections between meteoric, ground, and surface waters is critical for effective water resource management. Analyses of the stable isotopes of oxygen and hydrogen in the hydrosphere can help illuminate such connections. This study investigates the stable isotope composition of rainfall on O‘ahu in the Hawaiian Islands, with a particular focus on how altitude impacts stable isotope composition. Rainfall was sampled at 20 locations from March 2018 to August 2021. The new precipitation stable isotope data were integrated with previously published data to create the most spatially and topographically diverse precipitation collector network on O‘ahu to date. Results show that δ18O and δ2H values in precipitation displayed distinct isotopic signatures influenced by geographical location, season, and precipitation source. Altitude and isotopic compositions were strongly correlated along certain elevation transects, but these relationships could not be extrapolated to larger regions due to microclimate influences. Altitude and deuterium excess were strongly correlated across the study region, suggesting that deuterium excess may be a reliable proxy for precipitation elevation in local water tracer studies. Analysis of spring, rainfall, and fog stable isotope composition from Mount Ka‘ala suggests that fog may contribute up to 45% of total groundwater recharge at the summit. These findings highlight the strong influence of microclimates on the stable isotope composition of rainfall, underscore the need for further investigation into fog’s role in the water budget, and demonstrate the importance of stable isotope analysis for comprehending hydrologic dynamics in environmentally sensitive regions.

Footwall refrigeration versus footwall hydration: Reassessing steep thermal gradients below detachment faults with in situ SIMS oxygen isotope analysis

The extensional detachment systems of metamorphic core complexes (MCC) have the potential to facilitate significant fluid movement between Earth's surface and the warm, ductile middle crust. One long-standing and influential detachment fault-fluid interaction model called the “footwall refrigeration hypothesis” (Morrison and Anderson, 1998) postulates that cool meteoric fluids circulating downward along a detachment can facilitate large-scale heat loss at depth before rocks are exhumed by faulting. Stable isotopes of oxygen and hydrogen have long been recognized as potentially useful tracers of surface-to-depth fluid flow in core complexes; however, typical sampling methods and the competing effects between temperature and fluid composition have made oxygen isotope signatures of meteoric fluid infiltration difficult to detect and/or interpret in the rock record.Here, we use in situ δ18O measurements by secondary ion mass spectrometry (SIMS) to address the rock record of meteoric fluid interactions and temperature variation within the Whipple Mountains MCC footwall beneath the Whipple detachment fault (WDF). The micro-scale sampling of SIMS (10 µm diameter x 1–2 µm deep pits) allows investigation of isotope variability as a function of mineral geochemistry and microstructure and enables more accurate interpretation of the causes of isotope variability. In the Whipple footwall mylonites, quartz and epidote show grain-to-grain oxygen-isotope variability within samples and as a function of distance from the main detachment. Approaching the WDF, both quartz and epidote show increasing spread toward low δ18O values. The lowest SIMS-measured δ18O epidote values require exchange with a low δ18O, meteoric fluid at high temperature. However, SIMS data also reveal that meteoric fluid-rock interactions were spatially heterogeneous at the scale of individual grains, resulting in local preservation of metamorphic quartz-epidote oxygen isotope equilibrium unaffected by infiltrating meteoric fluid. Within preserved metamorphic domains at all investigated structural levels of the WDF footwall, quartz and epidote δ18O values are tightly clustered and yield similar fractionations (∆18Oqz-ep). For samples from the longest footwall traverse, these ∆18Oqz-ep values are 4.0 ± 0.4‰, consistent with δ18O equilibrium at 521+43/-37 °C. We conclude that there is no evidence of a large paleo-thermal gradient associated with the Whipple Detachment Fault (i.e., no evidence for footwall refrigeration).

Chironomids regulate long‐chain polyunsaturated fatty acid levels independent of lake nutrient or dissolved organic carbon concentrations

Chironomids are keystone primary benthic consumers with semi‐aquatic life cycles. They support aquatic and terrestrial consumers at higher trophic levels by conveying dietary nutrients, such as fatty acids. In this study, we combined field sampling and laboratory experiments to examine the effects of environmental parameters, including diet, on fatty acid composition and metabolism in chironomid larvae and imagines. Results from 53 lakes showed that lake size, depth, dissolved organic carbon (DOC) concentrations, and trophic state had only marginal effects on the content of long‐chain polyunsaturated fatty acids (LC‐PUFA) in chironomids. Compound‐specific stable hydrogen isotope analyses confirmed that chironomids actively bioconvert dietary fatty acid precursors to LC‐PUFA in all lake types, independent of nutrient or DOC concentrations. Moreover, fatty acid‐specific stable carbon isotope data indicated that the diet of chironomids was subsidized, particularly in oligotrophic lakes in spring, by terrestrial C18 fatty acid precursors that were converted to LC‐PUFA. Data from feeding experiments further confirmed that decreased dietary availability of LC‐PUFA enhanced the conversion of dietary short‐chain precursors to LC‐PUFA. These results suggest that chironomids are PUFA regulators that can sustain LC‐PUFA levels under varying environmental conditions. Furthermore, our results indicate that they bioconvert terrestrial low‐quality material to high‐quality resources, which, via chironomid emergence, support terrestrial food webs. Chironomids are abundant and widespread, and thus, the trophic transfer of LC‐PUFA can have significant implications for the fitness and production of upper trophic level consumers in both aquatic and terrestrial ecosystems.

Isotope-based source assessment of water flowing from storm sewer systems to a receiving river during dry weather periods

Urban stormwater management systems, particularly storm sewers, are critical for managing runoff in urban areas. These systems are designed to function during wet weather events; however, field-based observations of these systems suggest that they may also be active flow pathways in dry weather conditions, ultimately contributing to streamflow. Unlike dry weather flow in wastewater systems, storm sewer dry weather flow has not been thoroughly explored. This research used stable isotopes of oxygen and hydrogen in water to examine the sources of dry weather flow from storm sewers in a highly urban catchment. A stable isotope mixing model was applied at the outfalls of two stormwater catchments and the receiving Black Creek, located in Toronto, Canada. Findings suggest that during dry periods, storm sewers receive non-stormwater inputs from tap water, wastewater, and groundwater, along with some precipitation, and that these sources may constitute up to 19 % of Black Creek's flow at the watershed scale. Seasonal patterns in flow and water sources were observed for the Black Creek and outfalls. At one outfall, dry weather flow was predominantly from the water distribution system (i.e., tap water and/or wastewater) throughout spring, summer, and fall. In contrast, at the second outfall, groundwater dominated in spring and summer, and groundwater and water distribution were equally proportioned in fall. Black Creek baseflow comprises a dynamic mix of water sources that at times are similar to the sources observed at the stormwater outfalls. Considering these findings, future work should incorporate strategic sampling of additional outfalls, and multiple years of data collection to explore inter-annual variability in these processes and focus on replicating a similar study in other urban watersheds with different climates and/or water infrastructure design. The study findings highlight that our understanding of dry weather flow from storm sewers is relatively limited, emphasizing the need for further exploration of this phenomenon to inform urban hydrological modelling, water quality studies, and urban water management.

Sourcing and long-range transport of particulate organic matter in river bedload: Río Bermejo, Argentina

Abstract. Fluvial transport of organic carbon from the terrestrial biosphere to the oceans is an important term in the global carbon cycle. Traditionally, the long-term burial flux of fluvial particulate organic carbon (POC) is estimated using river suspended sediment flux; however, organic carbon can also travel in river bedload as coarse particulate organic matter (POMBed). Estimates of fluvial POC export to the ocean are highly uncertain because few studies document POMbed sources, flux, and evolution during long-range fluvial transport from uplands to ocean basins. This knowledge gap limits our ability to determine the global terrestrial organic carbon burial flux. In this study we investigate the flux, sources, and transformations of POMBed during fluvial transport over a ∼1300 km long reach of the Río Bermejo, Argentina, which has no tributary inputs. To constrain sourcing of POMBed, we analyzed the composition and stable hydrogen and carbon isotope ratios (δ2H, δ13C) of plant wax biomarkers from POMBed at six locations along the Río Bermejo and compared this to samples of suspended sediment, soil, leaf litter, and floating organic debris (POMfloat) from both the lowland and headwater river system. Across all samples, we found no discernible differences in n-alkane average chain length or nC29 δ13C, indicting a common origin for all sampled POMBed. Leaf litter and POMfloat nC29 δ2H values decrease with elevation, making it a useful proxy for POMBed source elevation. Biomarker δ2H values suggest that POMBed is a mix of distally derived headwater and locally recruited floodplain sources at all sampling locations. These results indicate that POMBed can be preserved during transport through lowland rivers for hundreds of kilometers. However, the POMBed flux decreases with increasing transport distance, suggesting mechanical comminution of these coarse organic particles and progressive transfer into the suspended load. Our provisional estimates suggest that the carbon flux from POMBed comprises less than 1 % of the suspended load POC flux in the Río Bermejo. While this represents a small portion of the river POC flux, this coarse, high-density material likely has a higher probability of deposition and burial in sedimentary basins, potentially allowing it to be more effective in long-term CO2 drawdown relative to fine suspended particles. Because the rate and ratio of POMBed transport versus comminution likely vary across tectonic and climatic settings, additional research is needed to determine the importance of POMBed in the global carbon cycle.

Stable hydrogen isotope evidence of late-Holocene precipitation variability on the Caribbean slope of the Cordillera Central, Costa Rica

In Central America and the Caribbean, periods of increased aridity that correspond to the Terminal Classic Drought (TCD; 1200–850 cal yr BP) and the Little Ice Age (LIA; 500–100 cal yr BP) have been documented in many paleoclimate records. Compound-specific hydrogen (δDalkane) and carbon (δ13Calkane) isotopic compositions of n-alkanes in lake sediment can be used to interpret changes in paleoprecipitation and terrestrial paleovegetation, respectively. To assess the climate forcing mechanisms that drove the TCD and LIA, we established a multidecadal to centennial-scale late-Holocene reconstruction of precipitation variability and vegetation change at mid-elevation on the Caribbean slope of Costa Rica, developed from new δDalkane, δ13Calkane, and geochemical analyses and previous pollen and microscopic charcoal analyses from a sediment core from Laguna María Aguilar. Laguna María Aguilar is a freshwater lake located at 770 m elevation on the Caribbean slope of the Cordillera Central. During the TCD, δDalkane data for María Aguilar indicate relatively wet conditions compared to the mean δDalkane value for the entire record. Other proxy records for the TCD indicate that the Pacific slope of Costa Rica and sites above 3400 m near the continental divide experienced generally drier conditions than mid- and low-elevations on the Caribbean slope. We conclude that the TCD may have been driven by both Pacific and Atlantic climate-forcing mechanisms. During the LIA, the Laguna María Aguilar δDalkane record indicates an increase in hydroclimate variability, with some of the highest recorded δDalkane values (driest conditions) during the earliest portions of the LIA, but conditions were not persistently dry for the entirety of the LIA. Based on regional paleoclimate records overall, the LIA drought appears to be more clearly expressed on the Caribbean slope than on the Pacific slope of Costa Rica, indicating that the LIA was perhaps driven primarily by Atlantic Ocean conditions and climate dynamics.

Compound-specific radiocarbon analysis of sedimentary fatty acids: Potential as a dating tool for lake sediments of Mt. Fuji volcanic region, Japan

Compound-specific radiocarbon analysis (CSRA) is a promising tool for dating sediment sequences where traditional dating methods are impractical. However, the applicability of CSRA of short-chain fatty acids as a dating tool remains poorly understood, especially in lacustrine settings. Accordingly, we determined the radiocarbon content (Δ14C) of individual fatty acids in sediments of Lake Yamanaka (central Japan), as well as their stable carbon and hydrogen isotope ratios, to evaluate the potential of CSRA as a dating tool in volcanic lake environments. We found that the Δ14C values of plant-derived (C24, C26, and C28) n-fatty acids (–99‰ to –149‰) were considerably lower than the Δ14C of charred plants (139‰) within the sediments and those of living aquatic plants (–52‰ to –58‰) in Lake Yamanaka, suggesting that contributions from pre-aged terrestrial and aquatic plant materials likely affect these acids. Similarly, the Δ14C of C16n-fatty acid (–95‰) in surface sediments was much lower than the Δ14C of modern aquatic plants (–52‰ to –58‰), as well as the Δ14C of dissolved organic carbon (DIC) in surface water (–48‰). Together with the stable isotope results, we conclude that in addition to autochthonous aquatic sources, contributions from pre-aged terrestrial carbon sources significantly affect the Δ14C of C16n-fatty acids. Comparing fatty acid Δ14C and concentration data across lakes within the Mt. Fuji region suggests that CSRA of the C16 acid provides valid chronological information only when the C16 originates exclusively from autochthonous aquatic sources, with minor allochthonous terrestrial input.

Exploring Ice Cave Biodiversity in Northeastern Italy

The ice stored in caves is a widespread yet neglected cryospheric component. The cold-adapted biodiversity of ice caves has received very little attention from research, despite the potential abundance of endemic troglobiotic and cryophilic species and their consequent sensitivity to the changing climate. In this study, we investigated the invertebrate diversity of two ice caves in Northeastern Italy (Bus delle Taccole and Caverna del Sieson, Veneto Region). During 2022 and 2023, we sampled, using pitfall traps, the invertebrates dwelling at different locations in each cave: the shaft base, an intermediate hall, and the cave bottom. At each cave location, we also collected ice samples, on which we measured the stable isotopes of oxygen and hydrogen (δ18O, δ2H), and monitored the air temperature with data-loggers. The two caves had different invertebrate communities, both dominated by a combination of troglobiotic and cryophilic taxa. Despite a low taxonomic richness, which was higher at Taccole (15 taxa) than at Sieson (11 taxa), both caves hosted rare/endemic species, four of which are not described yet. At each cave, the ice water isotopic signatures differed among cave locations, suggesting the ice had formed under different climatic conditions, and/or resulted from different frequencies of thawing/freezing events. The occurrence of summer melt at both caves suggests that these unique ecosystems will quickly disappear, along with their specialized and unique biodiversity.