Hydrogen Isotope Analysis Research Articles

Using hydrochemistry and stable isotopes to character the karst water environment in a cave site, South China

For cave sites located within the seasonal fluctuation zone of groundwater, obtaining a comprehensive understanding of the hydrogeological conditions and hydrochemical environment is of utmost importance in assessing the preservation of cultural deposits. However, due to the heterogeneity of karst development, the hydrochemical environment of the overburden karst water-bearing unit may exhibit complex variations. In this study, the characteristics of the water environment in a foot cave system and its surrounding aquifer were investigated at the Zengpiyan site, employing hydrochemistry, hydrogen and oxygen isotope analysis, as well as sulfate isotope analysis, in conjunction with the hydrogeological background. Based on the exposure of the karst cave and the groundwater flow conditions, the water-bearing medium was categorized into five types. The aquifer exhibited either an oxidation or reduction condition, with a distinct "dissolved oxygen hole" observed in the saturated zone of the cave site. Ion concentration analysis revealed that the groundwater was influenced by the prior accumulation of cinders in the upstream region, leading to sulfate contamination within the foot cave system. However, during the groundwater movement from upstream to downstream, the attenuation rate of pollutants displayed significant variations. Notably, the sulfate content was unusually low within the site cave. Hydrogen and oxygen isotopes provided insights into the differing circulation and movement velocities of groundwater within the local environment. Additionally, sulfate isotopes confirmed the sources of sulfate and the occurrence of bacterial sulfate reduction within the site cave. Consequently, an environmental zoning classification was established based on these analyses. Although the concentration of dissolved ions appears low in the anoxic area, it does not imply a diminished environmental risk. Under reducing conditions, these pollutants can be converted into more aggressive gases, posing a substantial threat to the preservation environment of cave sites. Therefore, sufficient attention should be given to this aspect in order to ensure adequate protection.

Hydrogen isotopic ratio by residual gas analysis during the JET DT campaigns

Abstract The analysis of hydrogen isotope content is crucial for understanding the operation of fusion devices. Hydrogen isotopic analysis in the core and plasma edge is conducted through neutron and spectroscopic diagnostics. In the case of exhaust gas, mass spectrometry is employed using residual gas analyzers (RGAs), along with optical gas analysis (OGA) utilizing an optical Penning gauge. The use of traditional quadrupole mass spectrometers for RGA encounters challenges during discharges with tritium gas due to signal overlap of different hydrogen molecules at the same mass number. This paper introduces a novel technique to address this issue through a cross-related analysis of RGA data with OGA results. Another consideration in mass spectrometry analysis is the instrument’s varying sensitivity concerning the gas mass number. The paper includes gas calibration data results for all the quadrupoles used in the JET gas analysis. Hydrogen isotopic ratios are calculated from RGA detected currents using simple formulas. The results of this procedure are presented for selected DT JET discharges in relation to the JET pulse time, and they are compared with corresponding optical data. Time-averaged hydrogen isotopic ratio values are computed for numerous discharges during the DT and T campaigns.

Hydrochemical appraisal and suitability for irrigation and portable purposes in eastern Himalayan syntaxis of Tibet Plateau

The formation mechanism and quality evaluation of surface water and groundwater have provided valuable information on water management of alpine catchment, such as Tibet Plateau. However, scarce knowledge of surface water and groundwater has been achieved from Eastern Himalayan syntaxis in eastern Tibet due to harsh and complicated natural and geological conditions. This study collected 60 water samples from the Layue alpine catchment within Eastern Himalayan syntaxis, including 35 samples of groundwater and 25 of surface water. A combination of multivariate statistical analysis, ion ratio analysis, geochemical modeling, hydrogen and oxygen isotope analysis, and water quality index (WQI) analysis was employed to explore hydrochemical processes and irrigation and portable suitability. Results indicate that the groundwater types identified include bicarbonate-calcium, sulfate·chlorine-sodium, and mixed bicarbonate-calcium·sodium, while surface water are sulfate·chlorine-sodium, mixed bicarbonate-calcium·sodium, and mixed chlorine-calcium·magnesium types. Groundwater recharge primarily originates from meteoric precipitation, with recharge elevations ranging from 2216 to 3698 m, while surface water receives both precipitation and groundwater recharge in a proportion of 50.51%–87.96%. Silicate weathering and carbonate dissolution predominantly control the hydrochemical compositions. Sodium adsorption ratios (0.75–88.55) and electrical conductivity (85.20–1686.12 μs/cm) indicate water resource are mostly suitable for irrigation. The entropy-weighted water quality index (97% in total <100) denotes the suitability for portable use. These achievements would provide substantial support for the sustainable water management in alpine areas, especially for Tibet Plateau.

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.

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotope Analysis to Characterize Aerobic Biodegradation of 2,3-Dichloroaniline by a Mixed Enrichment Culture.

Compound-specific isotope analysis (CSIA) is an established tool to track the in situ transformation of organic chemicals at contaminated sites. In this work, we evaluated the potential of multi-element CSIA to assess biodegradation of 2,3-dichloroaniline (2,3-DCA), which is a major industrial feedstock. Using controlled laboratory experiments, we determined, for the first time, negligible carbon (<0.5‰) and hydrogen (<10‰) isotope fractionation and a significant inverse nitrogen isotope fractionation (>10‰) during aerobic 2,3-DCA biodegradation by a mixed enrichment culture. The tentative identification of a glutamate conjugate of 2,3-DCA as a reaction intermediate indicates that the initial multistep enzymatic reaction may be rate-limiting. The formation of the glutamate adduct would increase the bond energy at the N atom, thus likely explaining the observed inverse N isotope fractionation. The corresponding nitrogen enrichment factor was +6.8 ± 0.6‰. This value was applied to investigate the in situ 2,3-DCA biodegradation at a contaminated site where the carbon and nitrogen isotope signatures from field samples suggested similar aerobic processes by native microorganisms. Under the assumption of the applicability of the Rayleigh model in a pilot wetland treating contaminated groundwater, the extent of biodegradation was estimated to be up to 80-90%. This study proposes multi-element CSIA as a novel application to study 2,3-DCA fate in groundwater and surface water and provides insights into biodegradation pathways.

Hydrogeochemistry of geothermal water in Huangshadong and adjacent areas of Guangdong province: Implications for water-rock interaction

Hydrogeochemical characteristics can reflect important information on the circulation processes of geothermal fluids, reservoir temperatures, etc., which are essential for exploring geothermal field evolution and the rational development of geothermal resources. 23 sets of water samples were collected from Huangshadong and adjacent geothermal fields. Major cations and anions, hydrogen and oxygen isotopes, and 14C activities were analyzed to investigate the hydrogeochemical characteristics of geothermal fluids and their formation mechanisms. Hydrogen and oxygen isotope analysis and major element chemistry indicate that the geothermal waters in the study area are mainly recharged by meteoric water. The chemical facies of the geothermal waters are mainly Na−HCO3 and Ca−HCO3, and most of the geothermal waters have high Na+ contents, which are attributed to the involvement of albite in water-rock interaction and the replacement of Na+ in rocks by Ca2+ or Mg2+ in water. Geothermometry of geothermal waters suggests that the reservoir temperatures are between 140-150 ℃, and the geothermal water circulation depths range from 2.0 to 4.3 km. The residence time of up to 17.3ka for geothermal water likely suggests the earliest precipitation recharge during the Late Pleistocene. Major element chemistry and hydrogen and oxygen isotope systematics indicate essential information on the origins of geothermal waters and water-rock interaction processes and provide a more comprehensive understanding of the geothermal system in Huangshadong and adjacent areas of Guangdong province.

Holocene hydroclimate in highland Costa Rica: new evidence from hydrogen and carbon isotopes in n‐alkanes of terrestrial leaf waxes in a 10 000‐year sediment profile

ABSTRACTWe conducted compound‐specific stable hydrogen (δD) and carbon (δ13C) isotope analysis on n‐alkanes from terrestrial leaf waxes preserved in a 10 000‐year sediment profile from Lago de las Morrenas 1 (9.4925° N, 83.4848° W, 3480 m), a glacial lake on the Chirripó massif of the Cordillera de Talamanca in Costa Rica. Our results demonstrate millennial‐scale variations in hydroclimate across the Holocene, with drier than average conditions in the highlands during the early Holocene, but with gradually increasing precipitation; mesic conditions during the middle Holocene with a gradual drying trend; and highly variable conditions during the late Holocene. This general pattern is punctuated by several centennial‐scale manifestations of global climate events, including dry conditions during the 8200, 5200 and 4200 cal a bp events and the Terminal Classic Drought (1200–850 cal a bp). Our δ13C analyses demonstrate that carbon isotope signals are responding to changes in hydroclimate at the site and reinforce prior interpretations of a stable páramo plant community that established following deglaciation and persisted throughout the Holocene. The shifts in hydroclimate inferred from analyses of n‐alkanes in Lago de las Morrenas 1 sediments show correspondence with charcoal records in multiple lakes, with fires most common during drier intervals.

Anaerobic dihydrogen consumption of nutrient-limited aquifer sediment microbial communities examined by stable isotope analysis

ABSTRACT The biogeochemical consequences of dihydrogen (H2) underground storage in porous aquifers are poorly understood. Here, the effects of nutrient limitations on anaerobic H2 oxidation of an aquifer microbial community in sediment microcosms were determined in order to evaluate possible responses to high H2 partial pressures. Hydrogen isotope analyses of H2 yielded isotope depletion in all biotic setups indicating microbial H2 consumption. Carbon isotope analyses of carbon dioxide (CO2) showed isotope enrichment in all H2-supplemented biotic setups indicating H2-dependent consumption of CO2 by methanogens or homoacetogens. Homoacetogenesis was indicated by the detection of acetate and formate. Consumption of CO2 and H2 varied along the differently nutrient-amended setups, as did the onset of methane production. Plotting carbon against hydrogen isotope signatures of CH4 indicated that CH4 was produced hydrogenotrophically and fermentatively. The putative hydrogenotrophic Methanobacterium sp. was the dominant methanogen. Most abundant phylotypes belonged to typical ferric iron reducers, indicating that besides CO2, Fe(III) was an important electron acceptor. In summary, our study provides evidence for the adaptability of subsurface microbial communities under different nutrient-deficient conditions to elevated H2 partial pressures.

Geochemical characteristics of shale gas hydraulic fracturing flowback/produced water in Zheng’an block, northern Guizhou Province, China

Guizhou Province of China is rich in shale gas resources. In recent years, important progress has been made in the exploration and development of shale gas in the Upper Ordovician Wufeng Formation-Lower Silurian Longmaxi Formation in Zheng'an block in northern Guizhou, adjacent to Sichuan Basin. Due to the complex geological conditions and fragile ecological environment in the shale gas distribution area, serious environmental pollution risks may exist in shale gas exploitation. Therefore, this paper conducted element, hydrogen and oxygen isotope analyses for shale gas fracturing flowback/produced water of Well AY7-4 in Zheng'an block. The results showed that the contents of K, Na, Ca, Mg and NH4+ in the flowback/produced water of Well AY7-4 were very high, with an average of 118 mg/L, 7616 mg/L, 266 mg/L, 47 mg/L and 76 mg/L, respectively. The content of Na, Ca and Mg is similar to that of shale gas flowback/produced water in Weiyuan, but lower than that in Changning and Fuling. NH4+ content was similar to that in Changning, but much higher than that in Weiyuan. The average Cl content was 11605 mg/L, which was similar to that in Weiyuan, but lower than that in Changning and Fuling. The average Br content is 48 mg/L, slightly lower than that of Weiyuan, and about half of that of Changning and Fuling. Correspondingly, the Br/Cl value of Well AY7-4 is the lowest, reflecting its relatively low Br content. The average content of Li, B and Sr is 17 mg/L, 10 mg/L and 45 mg/L, respectively, which is similar to that of the Weiyuan, Changning and Fuling shale gas fields. The distribution model of Li and Sr is similar to that of Cl, Br and Na, but the B content and B/Cl value of Well AY7-4 are the lowest. The linear relationship between Br and Cl contents and between δD and δ18O of flowback/produced water of Well AY7-4, freshwater used for hydraulic fracturing and hydraulic fracturing injected fluid indicates that flowback/produced water of Well AY7-4 is mainly the mixed product between low salinity injected fracturing fluid and high salinity brine retained in shale formation. The hydrogen and oxygen isotopic compositions gradually become heavier over time, indicating that the proportion of high salt end formation brine in flowback/produced water is increasing. The contents of Cl, Br, Na and NH4+ in the flowback/produced water of Well AY7-4 are far higher than the allowable discharge value, which is a potential environmental pollution risk and cannot be discharged directly.

Hydrochemical characteristics of underground fluid observation wells in Shandong

To explore the hydrochemical characteristics of underground fluid observation wells in the Shandong area, piper diagram and Na-K-Mg triangle diagram methods were used to analyze the hydrochemical types and water-rock chemistry of water samples from 18 underground fluid observation wells in the study area. The results show that the hydrochemical types of underground fluid observation wells in the Shandong area are mainly SO4·Cl-Ca·Mg type, HCO3-Na type, HCO3-Ca·Mg type, and SO4·Cl-Na type. The chemical composition of water is mainly affected by water-rock interaction, rock salt dissolution, ion exchange, and human activities. Hydrogen and oxygen isotope analysis results show that atmospheric precipitation is the main recharge source of fluid wells in this area, and deep water recharge also plays an important role in some observation wells. The research results determine the hydrogeochemical background and well water source of underground fluid wells in the Shandong area and provide the scientific basis for fluid observation environment analysis, seismic monitoring and prediction, and seismic anomaly verification in the area.

Preservation of bone organic fraction is not predictive of the preservation of bone inorganic fraction when assessing stable isotope analysis sample quality control measures

Stable isotope analysis of carbon (C), nitrogen (N), hydrogen (H), and oxygen (O) of archaeological bone has become an increasingly common research method for interpreting human behavior in the past. However, diagenesis of skeletal material can invalidate stable isotope ratios, thereby compromising interpretations. We examine patterns of bone diagenesis using infrared spectroscopy of bone bioapatite samples in relation to indicators of organic preservation quality indicators. We assess crystallinity, an indicator of bioapatite preservation, using the infrared splitting factor (IR-SF) and carbonate content (carbonate to phosphate ratio, C/P) calculated from infrared spectra. We then test the assumption that if the organic fraction of bone is preserved, the mineral fraction will also be unaffected by postmortem chemical alteration. We analyzed 454 bone bioapatite and extracted bone organic sample pairs from modern, historic, and prehistoric humans. Consistent with previous studies, we observed a strong, statistically significant negative linear relationship between IR-SF and C/P (r = −0.855, p < 0.001). Modern bone bioapatite samples unaltered by diagenesis have low IR-SF and high C/P values. There was no significant association between the collagen yield or atomic C:N ratio and IR-SF or C/P values. The range of variation in IR-SF and C/P values for samples with organic yields between 0 and >20 percent spanned the range of modern bone bioapatite unaltered by diagenesis as well as bone bioapatite significantly affected by diagenesis. The lack of predictive patterning between bone inorganic and organic diagenesis suggests that the depositional context and site formation history play critical and independent roles in the organic and mineral fraction of bone. Thus, the preservation of the organic fraction of bone is not predictive of the preservation of the inorganic fraction (e.g., bioapatite).

Impact assessment of the Gajke and Brstje landfills on groundwater status using stable and radioactive isotopes

Waste disposal in landfills represents a severe threat to aquatic environments on the local, regional, and global levels. In Slovenia, there are 69 registered landfills where groundwater is regularly monitored. However, isotope techniques are not regularly employed. Therefore, we employed isotope analysis of hydrogen, carbon, and oxygen in combination with total alkalinity to assess the impact of the selected landfill on groundwater and to evaluate the biogeochemical processes at work. The δ18O, δ2H, δ13CDIC, 3H activity and total alkalinity were determined in October 2020 at 12 sampling points from the surrounding area of the Gajke and Brstje landfills and leachate from the Gajke landfill. The δ18O (-9.24 ± 0.3 ‰) and δ2H (-64.9 ± 2.7 ‰) in groundwater indicate that the main water source consists in direct infiltration of precipitation, with no significant isotopic fractionation. Total alkalinity in the investigated area ranges from 5.45 to 73 mM and δ13CDIC from –14.9 to +6.1 ‰, respectively. Higher values of total alkalinity (up to 73 mM), δ13CDIC (up to +6.1 ‰), δ18O (-7.64 ‰) and 3H (209.8 TU) are detected in the leachate, indicating biogeochemical process related to CO2 reduction or methanogenesis. Methanogenesis could be present at locations GAP-10/13 (Brstje landfill) and G-2 (Gajke landfill) with δ13CDIC values ranging from –8.2 to –7.6 ‰ and with dissolved oxygen values around 0 % and elevated 3H values (from 16 to 18 TU). This study demonstrates the effectiveness of isotopic analysis as a valuable tool for monitoring landfills, revealing shifts in biogeochemical processes within the groundwater there.

A passive method for sampling water in the soil-plant-atmosphere continuum for stable hydrogen and oxygen isotope analyses.

Hydrogen and oxygen isotopes in water molecules are powerful tools to constrain the dynamics of water cycling within the soil-plant-atmosphere continuum (SPAC). However, the recovery of water from the SPAC requires logistical arrangements and implementation of different time- and cost-consuming techniques in either the field or the laboratory. We developed a passive method to sample water from the three compartments of the SPAC by using a hygroscopic salt of a high water absorbance capacity (CaCl2 ). This method allows either H2 O(V) -H2 O(L) isotope equilibration in the case of infinite water reservoir (atmospheric water vapor (WV)) or quantitative absorption of water from a finite water reservoir (e.g. soil and plants). The water absorbed by CaCl2 was distilled first and subsequently processed for hydrogen and triple oxygen isotope mass spectrometry analyses. The distillation step can be bypassed when employing isotope analytical techniques that are based on equilibration. Our experiments show that anhydrous CaCl2 absorbs WV of 210 ± 6% and 130 ± 6% of its dry weight from an infinite WV reservoir at relative humidity of 60% and 30%, respectively. Chemical and isotope equilibrations between WV and absorbed water were attained within 3 days at room temperature, enabling the back-calculation of the isotope composition of atmospheric WV. Preliminary experiments to extract water from plant and sand (i.e. finite WV reservoir) demonstrate a quasi-complete recovery of water in these matrices without significant isotope fractionation. The reproducibility of our method is better than 1.6‰, 0.32‰, 0.17‰ and 6‰ per meg for δ2 H, δ18 O, δ17 O and 17 O-excess. The CaCl2 -H2 O absorption (passive) method requires very limited logistics in the field facilitating spatial and temporal water vapor/water sampling from atmosphere and soil at low resolution (i.e. average of 3-5 days). Moreover, it allows high sample throughput for the extraction of plant water in the laboratory. The reproducibility of this method is similar to the analytical uncertainty in mass spectrometry analyses.

Miocene surface uplift and orogenic evolution of the southern Andean Plateau (central Puna), northwestern Argentina

We present stable hydrogen-isotope analyses of volcanic glass ([Formula: see text]Dg) and radiometric ages (U-Pb zircon, U-Th calcite, AMS14C) from deformed sedimentary deposits in the vicinity of the intermontane Pocitos Basin in the central Puna of the Andean Plateau at about 24.5°S. Our results demonstrate 2-km surface uplift since the middle to late Miocene and protracted shortening that persists until the present day, while other sectors of the Puna show evidence for tectonically neutral and/or extensional settings. These findings are at odds with previous studies suggesting near-modern elevations (4 km) of the Puna Plateau since the late Eocene and formation of the intermontane Miocene Arizaro-Pocitos Basin associated with gravitational foundering of a dense lithosphere. Geophysical and geochemical data support the removal of continental lithosphere beneath the Puna, but the timing and mechanisms by which this removal occurs have remained controversial. We hypothesize that intermontane basin formation in the central Puna is the result of crustal shortening since about 20 Ma, followed by rapid surface uplift, likely related to lithospheric delamination.

Two-Stage Superimposed Gold Mineralization in the Xiejiagou Gold Deposit, Shandong Province: Insights from Fluid Inclusions, H-O-S Isotopes, and Trace Elements

The Xiejiagou gold deposit located in the Zhaoyuan-Laizhou gold belt is composed of altered-rock-type gold mineralization and superposed auriferous quartz veins, showing unique two-stage gold mineralization. Oxygen and hydrogen isotopic analyses yielded the following results: δ18OH2O = 0.8‰ to 4.4‰ and δD = −106‰ to −85‰ for altered-rock-type mineralization, and δ18OH2O = 3.6‰ to 5.6‰ and δD = −98‰ to −89‰ for auriferous quartz-veins. Combined studies on Co/Ni, Sb/Bi and As/Ag ratios of pyrites, it can be inferred that the ore-forming fluids were dominated by magmatic water mixed with very little meteoric water. The fractured altered rocks in the ore-hosting fault zones are characterized by mylonitization, cataclastic lithification, and structural lenses, reflecting a compressional (closed) ore-forming system. In contrast, the occurrence of auriferous quartz veins in fissures of altered-rock-type orebodies and the fact that altered-rock-type ores commonly occur as breccias cemented by auriferous quartz veins that reflect an extensional (open) ore-forming system for the vein mineralization. The increase in δ34S values from stage I (5.8‰–7.2‰) to stage II (6.6‰–9.0‰) indicate that the altered-rock-type mineralization was the result of intense water–rock interaction, while the occurrence of immiscible inclusions in auriferous quartz veins demonstrates that fluid immiscibility contributes significantly to gold deposition in the vein-type mineralization. Fluid-inclusion microthermometric data indicate that the fluids for the altered-rock-type mineralization are characterized by moderate-to-high temperature (262–368 °C), and low-to-moderate salinity (4.3–10.8 wt.% NaCl equivalent). In contrast, halite-bearing inclusions are found in auriferous quartz veins, and its fluids are characterized by moderate-to-high temperature (290–376 °C) and moderate-to-high salinity (5.1–41.9 wt.% NaCl equivalent). From early stages (I and II) to the late stage (III), homogenization temperature and high temperature element (W, Sn, and Mo) concentrations in pyrite first decrease and then increase, δ34S values and metallization-related element (Au, Ag, and Bi) concentrations in pyrite first increase and then decrease. Therefore, it can be inferred that the two distinct types of gold mineralization in the Xiejiagou gold deposit may be two separate mineralization events. The presence of magnetite in the auriferous veins suggests an increase in oxidation state during the vein mineralization. Importantly, the Xiejiagou gold deposit preserves two types of mineralization in a single deposit and uniquely records a metallogenic transition from a compressional, reduced environment to an extensional, oxidized environment, as a result of a regional stress field transition that occurred in the Zhaoyuan-Laizhou gold belt at ca. 120 Ma.

Hydrochemical Characteristics and Formation Causes of Ground Karst Water Systems in Gudui Spring Catchment

As one of the famous karst springs in Shanxi Province, the Gudui spring is the only medium-low temperature hot spring, with a long history of development and a rich cultural accumulation. The karst groundwater in the Gudui spring catchment was taken as the research object. Through systematic sample collection and isotope analysis, hydrochemistry (Durov map, ion ratio, Gibbs map, and hydrogen and oxygen isotope) methods were comprehensively used to analyze groundwater hydrochemistry and groundwater system runoff characteristics. The87Sr/86Sr value of karst groundwater in the Gudui spring catchment was 0.709 to 0.717, and the Mg/(Mg+Ca) value was 0.27 to 0.74. By analyzing the Sr isotope composition and Mg/(Mg+Ca) and 1/Sr variation characteristics, it was concluded that the karst groundwater in the Gudui spring catchment was a mixture of deep hot water and shallow cold water. The karst water subsystem of Nanliang spring presented the characteristics of carbonate stratum runoff. The karst water subsystem of Fuling Mountain Gaoxian Haitou spring and the deep circulation subsystem of Houma Basin exhibited the runoff characteristics of carbonate rock and igneous rock strata. The karst water subsystem of Taiershan Jiuyuanshan Gudui spring presented the runoff characteristics of carbonate rock and ancient silicoaluminate strata. The δ18O value in karst groundwater of Guodui spring area ranged from -11.46‰ to -7.81‰, and the average value was -10.08‰. The range of the δD value was -83.7‰ to -60.8‰, and the average value was -73.6‰. This showed that karst groundwater in the spring area was the result of mixing of various types of water. Through comparative analysis of hydrogen and oxygen isotopes of 2014 and 2021 sampling points at the same location, it was concluded that the change in water samples at the Guduiquan resulted from the gradual accumulation of water supplied by Sanquan Reservoir. The change in Sanquan Reservoir was due to the influence of Yellow River diversion. The karst groundwater in the spring area were characterized by large calcium ion, magnesium ion, and sodium ion values; a small potassium ion value; a large sulfate value; and a small chloride value. The hydrochemical types of karst groundwater in Gudui spring catchment could be divided into SO4-Na, SO4-Ca, HCO3-Na, HCO3-Mg, HCO3-Ca, and Cl-Na. The hydrochemical types of karst groundwater showed evident hydrochemical composition zoning from HCO3-Ca·Mg→HCO3·SO4-Ca·Mg→SO4·HCO3-Na·Ca→SO4·Cl-Na·Ca. According to the comprehensive analysis of hydrochemical isotope and hydrogeological conditions, the karst water subsystem of Nanliang spring was primarily recharged by rainfall infiltration in the exposed limestone area and river infiltration, and its karst groundwater was recharged by runoff from south to north to the karst water subsystem of Fuling Mountain Gaoxian Haitou spring and the deep circulation subsystem of Houma Basin. The karst water subsystem of Taier Jiuyuan Mountain Gudui spring received rainfall infiltration supplement and upstream runoff supplement from the exposed limestone area. Its karst groundwater flowed from north to south and received the supply of Sanquan Reservoir from Yellow River water in the natural discharge area of Gudui spring.

Methane and CO2 production in the wetland Lake Podpeč (Slovenia)

PurposeThis study deals with the identification of CH4 and CO2 sources in the high-carbonate wetland Lake Podpeč in the Ljubljana Marshes, Slovenia.Materials and methodsLake Podpeč is situated on the periphery of the Ljubljana Marshes in central Slovenia. A combination of chemical analysis and natural abundance analysis of stable carbon and hydrogen isotopes of CH4, along with analysis of dissolved inorganic carbon (DIC), was employed in an incubation experiment.Results and discussionThe isotopic composition of dissolved inorganic carbon (δ13CDIC) suggests three main processes occurring during incubation: oxic degradation of organic matter (OM), anoxic OM degradation, and methanogenesis. During oxic degradation of OM, the δ13CDIC values slightly decrease from − 13.2 to − 14.5‰. However, after 50 days, the δ13CDIC values started to increase, reaching − 12.2‰ by the end of the experiment. 13C enrichment coincided with the formation of CH4, which began to increase simultaneously. The CH4 produced had an average δ13CCH4 value of − 67 ± 1‰ and δ2HCH4 value of − 389 ± 3‰, suggesting that CH4 is formed through acetate fermentation. The contribution of calcite dissolution to DIC increased during the degradation of OM by 53%. However, during methanogenesis, there was no significant change in the concentrations of Ca, and the estimated contribution to DIC was only 3%.ConclusionsThis study enhances our understanding of methane production in wetland Lake Podpeč and its relevance in the context of other high-carbonate lakes. The findings offer insights into the complex interactions between OM degradation, methane production pathways, and carbonate dissolution, which has implications for the global carbon cycle and greenhouse gas emissions.

Migration of Eastern North American monarch butterflies via the South-east and the Atlantic: evidence from stable isotopes, thin layer chromatography, DNA and phenotype

Abstract Monarch butterflies, Danaus plexippus (L.), from eastern North America are well known for their incredible autumn migration to Mexico; however, not all monarchs follow this route. There is evidence of monarchs overwintering and reproducing in Florida, arriving to insular and continental Caribbean, and roosting by the thousands in the Yucatán, Mexico. This work aims to present evidence that these monarchs are part of two current migratory routes, that we consider as the south-eastern and the Atlantic routes, routes that were probably more prominent in the past. Monarchs were collected for 12 months in south Florida, for 4 years in Cuba in November and once in March, in the Yucatán and Guatemala at different times, and once in northern Venezuela. We used two independent techniques, stable hydrogen isotope (δ2H) analyses of the wings and/or thin layer chromatography (TLC), to trace the monarch’s natal grounds. We analysed the DNA of monarchs collected in St. Marks in the Florida Panhandle, Cuba and Guatemala, and compared those data against previously-analysed DNA data from monarchs in the Americas to characterize their genetic structure and to assess the possible movement and presence of North American monarchs and/or their alleles outside the USA. Our results support the existence of south-eastern and Atlantic migratory routes. TLC, isotope and DNA analyses showed the arrival of likely North American monarchs in Cuba, Yucatán, Guatemala, Venezuela and other areas of the Americas. North American monarchs found in these areas have different natal grounds, phenotypic traits and DNA signature than Mexican migrants. Monarchs from the south-eastern route mostly originated in the south-east USA and fed on local Asclepias spp., such as Asclepias viridis, Asclepias humistrata, Asclepias perennis and Asclepias asperula. Butterflies from this migratory route move east, enter the Florida Peninsula, pass to Cuba, fly to the Yucatán and then to Guatemala where they appear to overwinter in the high mountains of Guatemala where Abies guatemalensis occurs. Monarchs that are part of the Atlantic route move east of the Appalachians, enter the Florida Peninsula, and from there pass to the insular and continental Caribbean. The main host plants for the Atlantic monarchs are A. perennis and A. humistrata; in contrast, Mexican monarchs mainly feed on Asclepias syriaca. Some monarchs from these two proposed migratory routes, south-eastern and Atlantic, will stay in the places where they travelled and others will return via Florida and Mexico. We propose a scenario for how the different migratory routes evolved.

A model of photosynthetic CO2 assimilation in C3 leaves accounting for respiration and energy recycling by the plastidial oxidative pentose phosphate pathway.

Recently, we reported estimates of anaplerotic carbon flux through the oxidative pentose phosphate pathway (OPPP) in chloroplasts into the Calvin-Benson cycle. These estimates were based on intramolecular hydrogen isotope analysis of sunflower leaf starch. However, the isotope method is believed to underestimate the actual flux at low atmospheric CO2 concentration (Ca ). Since the OPPP releases CO2 and reduces NADP+ , it can be expected to affect leaf gas exchange under both rubisco- and RuBP-regeneration-limited conditions. Therefore, we expanded Farquhar-von Caemmerer-Berry models to account for OPPP metabolism. Based on model parameterisation with values from the literature, we estimated OPPP-related effects on leaf carbon and energy metabolism in the sunflowers analysed previously. We found that flux through the plastidial OPPP increases both above and below Ca ≈ 450 ppm (the condition the plants were acclimated to). This is qualitatively consistent with our previous isotope-based estimates, yet gas-exchange-based estimates are larger at low Ca . We discuss our results in relation to regulatory properties of the plastidial and cytosolic OPPP, the proposed variability of CO2 mesophyll conductance, and the contribution of day respiration to the A/Ci curve drop at high Ca . Furthermore, we critically examine the models and parameterisation and derive recommendations for follow-up studies.

The Isotopic Composition of Rainfall on a Subtropical Mountainous Island

Abstract Tropical islands are simultaneously some of the most biodiverse and vulnerable places on Earth. Water resources help maintain the delicate balance on which the ecosystems and the population of tropical islands rely. Hydrogen and oxygen isotope analyses are a powerful tool in the study of the water cycle on tropical islands, although the scarcity of long-term and high-frequency data makes interpretation challenging. Here, a new dataset is presented based on weekly collection of rainfall H and O isotopic composition on the island of O‘ahu, Hawai‘i, beginning from July 2019 and still ongoing. The data show considerable differences in isotopic ratios produced by different weather systems, with Kona lows and upper-level lows having the lowest δ2H and δ18O values, and trade-wind showers the highest. The data also show significant spatial variability, with some sites being characterized by higher isotope ratios than others. The amount effect is not observed consistently at all sites. Deuterium excess shows a marked seasonal cycle, which is attributed to the different origin and history of the air masses that are responsible for rainfall in the winter and summer months. The local meteoric water line and a comparison of this dataset with a long-term historical record illustrate strong interannual variability and the need to establish a long-term precipitation isotope monitoring network for Hawai‘i. Significance Statement The isotopic composition of water is often used in the study of island water resources, but the scarcity of high-frequency datasets makes the interpretation of data difficult. The purpose of this study is to investigate the isotopic composition of rainfall on a mountainous island in the subtropics. Based on weekly data collection on O‘ahu, Hawai‘i, the results improve our understanding of the isotopic composition of rainfall due to different weather systems, like trade-wind showers or cold fronts, as well as its spatial and temporal variability. These results could inform the interpretation of data from other mountainous islands in similar climate zones.