δ13CDIC Values Research Articles

Dynamic changes, cycling and downward fate of dissolved carbon and nitrogen photosynthetically-derived from glaciers in upper Indus river basin

Glaciers play key roles in capturing, storing, and transforming global carbon and nitrogen, thereby contributing markedly to their cycles. However, an integrated mechanistic approach is still lacking regarding glacier's primary producers (PP), in terms of stable dissolved inorganic carbon isotope (δ13C-DIC) and its relationship with dissolved carbon and nitrogen transformation d ynamic changes/cycling. Here, we sampled waters from glaciers, streams, tributaries, and the Indus River (IR) mainstream in the Upper IR Basin, Western Himalaya. Dissolved organic matter (DOM) appears to increase, on average, by ∼2.5–23.4% with fluctuations when passing from glaciers to streams-tributaries-IR mainstream (the upper and lower parts, respectively) continuum, implying that DOM originates from glaciers PP and is subsequently degraded. The corresponding fluctuations are observed for fluorescent DOM (FDOM), dissolved organic nitrogen (8.0–106.8%), NO3−-N (−13.5/+16.6%), NH4+-N (−8.8/+13.0%), and NO2−-N (70.7–217.5%). These variations are associated with overall DOM/FDOM transformations, with the production of ending byproducts (e.g. CO2/DIC). The δ13C-DIC values fluctuated from glaciers (−5.3 ± 2.5‰) to streams (−4.4 ± 2.1‰), tributaries (−4.3 ± 1.6‰), and IR mainstream (−4.2 ± 1.3‰). The δ13C-DIC data are consistent with C transformations that involve lighter CO2 emission into the atmosphere, whereas highly depleted DIC/CO2 is the signature of DOM degradation after its fresh production from glaciers PP which originated by photosynthetic activities (e.g. uptake/sink of atmospheric CO2: −8.4‰). Finally, glacier-fed meltwaters would simultaneously contribute to the biogeochemical characteristics of downward margins and specific ecosystems (lake/pond/groundwater/hot springs) via transformation dynamics/cycling of dissolved C and N with high photo/microbial lability. Our results highlight the substantial contribution of western Himalayan glaciers-derived DOM to the global C and N cycles.

Predominant biogenic contribution of dissolved inorganic carbon in karst rivers, Southwest China

Dissolved inorganic carbon (DIC) holds significant importance within river systems, particularly in karst regions. The concentration of DIC is intricately linked to both biological processes, such as the respiration of organic matter, and geological processes, notably the strength of carbonate weathering. This dual influence exerts a profound impact on regional and global carbon cycles. However, the precise biological and geological origins of DIC in karst rivers remain a subject of debate. In this study, we delineate the sources of DIC in a typical karst catchment (Houzhai catchment) through isotopic analysis coupled with water chemistry examination. The results showed that δ13CDIC and Δ14CDIC variations range from −14.0 ‰ to −7.3 ‰ and − 426 ‰ to −31 ‰, respectively, with average values of −10.5 ‰ and − 180 ‰. Results derived from the isotopic mixing model suggest that approximately 83 % of DIC emanates from the soil CO2, while 17 % originates from carbonate sources. This indicates that biological processes exert a greater influence on DIC within the study area compared to geological processes. Seasonal variation, exemplified by higher DOC concentrations and Δ14CDIC values, alongside with lower DIC concentrations and δ13CDIC values during the wet season indicate increased input from biogenic sources, closely related to temperature and moisture conditions. Our study underscores an unbalanced contribution from biogenic and geogenic sources in karst rivers, highlighting potential inaccuracies in past carbon sink flux calculations. The roles of biogenic and geogenic sources in the carbon cycling of karst rivers, as well as their responses to future climate change, warrant a reevaluation.

Dual carbon isotopes (δ13C and Δ14C) were used to reveal the main sources and input fluxes of dissolved inorganic carbon in a karst reservoir in winter

In karst areas, the dissolved inorganic carbon (DIC) concentrations in aquatic systems are typically higher than that in non-karst areas due to intensive carbonate rock weathering. Understanding the sources and input fluxes of DIC in karst reservoirs is crucial for regional carbon cycle studies. This study utilized dual carbon isotopes (δ13CDIC and Δ14CDIC) to estimate the contribution rates and input fluxes of DIC from various sources in Aha Reservoir (AHR), located in southwestern China. Our results indicated that the DIC concentrations (22.33–32.79 mg L−1) and δ13CDIC values (−10.02‰ to −8.55‰) were nearly homogeneous both vertically and laterally in the reservoir (p > 0.05). The Δ14CDIC values (−246.31‰ to −137.86‰) were homogeneous along the vertical profile (p > 0.05), but showed significant horizontal variation (p < 0.05), with values decreasing from −149.57 ± 10.27‰ to −232.85 ± 2.37‰ at the mouths of the inflowing rivers. We found that the inflowing rivers were the primary DIC sources to AHR, contributing 70% of the total input, while groundwater and atmospheric CO2 contributions were relatively minor, at 18% and 12%, respectively. The Jinzhong River (JZR), influenced by industrial and domestic wastewater discharge, contributed the largest DIC input flux at 2.01 t/(km2·mon). In contrast, the Youyu River (YYR), influenced by acidic mine drainage, and the Baiyan River (BYR), influenced by agricultural activities, contributed relatively smaller DIC input fluxes of 1.29 t/(km2·mon) and 1.03 t/(km2·mon), respectively. This study highlights the significant impact of anthropogenic activities on DIC input in AHR, with industrial and domestic wastewater discharges having a greater influence than agricultural activities and acidic mine wastewater inputs. These findings underscore the critical need to manage and mitigate the impacts of human activities on karst reservoir ecosystems.

Metagenomic and isotopic insights into carbon fixation by autotrophic microorganisms in a petroleum hydrocarbon impacted red clay aquifer

Autotrophic microorganisms, the pivotal carbon fixers, exhibit a broad distribution across diverse environments, playing critical roles in the process of carbon sequestration. However, insights into their distribution characteristics in aquifers, particularly in those petroleum-hydrocarbon-contaminated (PHC) aquifers that were known for rich in heterotrophs, have been limited. In the study, groundwater samples were collected from red clay aquifers in the storage tank leakage area of a PHC site, a prevalent aquifer type in southern China and other regions. Metagenomics combined with hydrochemical and inorganic carbon isotope analyses were employed to elucidate the presence of microbial carbon fixation and its driving forces. Results showed that there were hundreds of autotrophic microorganisms participating in distinct carbon fixation processes in the red clay PHC aquifers. Reductive tricarboxylic acid (rTCA) and dicarboxylate/4-hydroxybutyrate (DC/4HB), as well as 3-hydroxypropionate (3HP or/and 3-hydroxypropionate/4-hydroxybutyrate (3HP/4HB)) were the predominant carbon fixation pathways. The abundances of carbon fixation genes and autotrophic microorganisms were significantly and positively correlated with hydrocarbon concentrations and δ13C of dissolved inorganic carbon (δ13C-DIC) values. This finding indicated that the petroleum hydrocarbon significantly promoted the proliferation of carbon fixation microorganisms, leading to a substantial uptake of inorganic carbon. Therefore, we deduce that this process holds considerable potential for carbon sequestration in PHC-contaminated aquifers.

Helium and carbon isotope compositions of thermal fluids in the northeastern Anatolia: Implications for the heat source and volatile flux

In this study, we make a quantitative assessment on the volatile flux of mantle-derived fluids and source of volatiles to explain the geologic controls on the transport of volatiles within thermal fluids of northeastern Anatolia. In line with this objective, we collected 22 samples (gas and water phase) from 16 geothermal fields in NE Turkey covering an area of nearly 100,000 km2 that extends from the eastern termination of North Anatolian Fault towards the Georgian and Armenian borders. The 3He/4He ratios of the samples (R) normalized to the atmospheric 3He/4He ratio (Ra = 1.4 × 10−6) vary from 0.31 to 7.15, and are considerably higher than the crustal value of 0.02Ra. Regarding spatial distribution of helium isotope composition, samples collected from areas of tectonic unrest around the Erzincan and Erzurum pull-apart basins in the southern part are represented by a higher range of 3He/4He ratios (>5 Ra) than those in volcanic areas to the east and northeast of the region. δ13CCO2 values of the gas samples varying from −20.76 to 5.43 ‰ are about 4–5 ‰ lower than δ13CDIC values of the water samples that range from −16.90 to 8.85 ‰, indicating CO2 removal from waters by degassing. CO2/3He ratios of gas samples falling in the range of 3.81 × 109 to 2.83 × 1012 imply that carbon is derived from the mixing between the crustal lithologies and mantle, the latter having a contribution up to 40 %. The maximum flux of mantle-derived fluids is found 88 mm/a at Erzincan (eastern part of the North Anatolian Fault Zone). This value is higher by a factor of about 10 than the western part of the fault zone. Calculations show that degassing from magmatic bodies is the sole mechanism to explain the high helium isotope compositions in the region. Therefore, we suggest that mantle-derived He contents might be due to extensive melting associated with active tectonism. The 3He/Heat ratios of thermal waters in northeastern Turkey were calculated in range of 0.25 to 29.7 × 10−15 cm3(STP)/J, consistent with the data reported for waters along the North Anatolian Fault, indicating a crustal heat source for the geothermal systems in northeastern Turkey.

Hidden magma reservoirs: Insights from helium and carbon isotopic compositions in shallow groundwater beneath the Wudalianchi volcanic field, Northeastern China

The lack of strong geothermal manifestations and limited fumarolic activity has sparked widespread debate about the presence of active magma reservoirs beneath the Wudalianchi volcanic field (WVF). Helium (He) in hydrological systems is sensitive and responsive to the mixture of mantle-derived He, making it an excellent tool for deciphering mantle-derived magmatic processes. Through investigating dissolved He and inorganic carbon (DIC) in shallow groundwater of the WVF, we found that He captures mantle characteristics with R/Ra ratios (R equals to 3He/4He ratios, Ra is atmospheric 3He/4He ratio of 1.39 × 10−6) ranging from 0.07 to 2.27 and the highest proportion of mantle-derived He is 30.38 %. In contrast, DIC shows minimal mantle influence, with low concentrations (1.91–7.39 mmol/L) and depleted δ13C-DIC values ranging from −17.9 ‰ to −13.6 ‰. The calculated mantle 4He fluxes in groundwater are 2–3 orders of magnitude higher than that in stable continents and show the signature of volcanic degassing. The high mantle He fluxes and high upward flow rates suggest the efficient release and transfer of mantle-derived He into shallow groundwater through magma degassing. Magma-aging model effectively constraints the period of magmatic activity to within the last 47 ka. These findings, consistent with seismic noise imaging results, support the presence of magma reservoirs in the upper–middle crust. The absence of magmatic carbon signature in groundwater suggests the decoupling of magmatic He and magmatic CO2. Magmatic CO2 may be removed during ascent, possibly being trapped through dissolution or precipitation processes within the low-resistivity bodies identified at ∼2.5 km depth by magnetotelluric imaging. These findings not only contribute to resolving the controversy surrounding the existence of magma reservoirs beneath the WVF but also have broader implications in guiding the exploration and validation of hidden magmatic systems.

Interspecies differences and lake‐specificity in the δ13C and δ18O signatures of charophyte carbonate encrustations

Abstract This study identifies the relationships between the δ13C and δ18O signatures of extant charophyte carbonates (δ13CCARB and δ18OCARB) and the δ13C of dissolved inorganic carbon and δ18O of water (δ13CDIC and δ18OWATER), respectively, and the structure of charophyte beds and the physico‐chemical properties of the ambient water. Inter‐ and intra‐specific differences and lake‐related variability are assessed. Four morphologically different charophyte species (Nitellopsis obtusa, Chara tomentosa, Chara rudis, Chara contraria) were studied in four charophyte‐dominated lakes (Chara‐lakes) in Central Europe. A wide distribution of the species in calcium‐rich freshwater lakes, where they form extensive underwater beds and contribute to the deposition of calcareous sediments, makes the study representative of Chara‐lakes. Charophytes and water above them were sampled monthly (June–September 2008) at permanent study sites. Additionally, three comparative macrophyte‐free pelagic sites were sampled in each lake. For all the charophytes studied, there was a greater variation in the δ13C and δ18O values of the encrustations than of the ambient and pelagic waters. Except for N. obtusa and C. tomentosa, the species differed significantly in the δ13CCARB values. The encrustations were enriched in 13C compared to water DIC. Chara tomentosa encrustations were significantly depleted in 18O compared to N. obtusa and C. contraria. In contrast to Chara species, N. obtusa encrustation was 18O‐enriched compared to surrounding water. The largest isotope differences between carbonate encrustations and surrounding water were found for C. rudis. Considering the δ13CCARB versus δ13CDIC values, only slender species (i.e. N. obtusa and C. contraria) precipitated encrustations close to isotopic equilibrium with water DIC. Based on theoretical δ18OCALCULATED and measured δ18OCARB values, only C. tomentosa precipitated encrustation in equilibrium with the δ18OWATER. Using redundancy analysis, the δ13CCARB values positively correlated with the δ13CDIC and δ18OWATER values and the percent volume of water inhabited by plants. The depth of sites, water mineralisation, alkalinity and fertility were inversely correlated with the δ13CCARB. The redundancy analysis revealed a clear division of samples into species and lakes; lakes were especially distinct. We postulate that the stable C and O isotope compositions of charophyte encrustations are lake‐ rather than species‐specific and that the isotopic signatures of charophyte carbonates are representative of the entire lake epilimnion, not just the vegetated littoral zone. Furthermore, the isotopic signal of bulk sediment can provide environmental information that is as useful as species‐specific isotope values.

Revisiting Elevated δ13C Values of Sediment on Modern Carbonate Platforms

AbstractThe measured carbon isotopic compositions of carbonate sediments (δ13Ccarb) on modern platforms are commonly 13C‐enriched compared to predicted values for minerals forming in isotopic equilibrium with the dissolved inorganic carbon (DIC) of modern seawater. This offset undermines the assumption that δ13Ccarb values of analogous facies in the rock record are an accurate archive of information about Earth's global carbon cycle. We present a new data set of the diurnal variation in carbonate chemistry and seawater δ13CDIC values on a modern carbonate platform. These data demonstrate that δ13Ccarb values on modern platforms are broadly representative of seawater, but only after accounting for the recent decrease in the δ13C value of atmospheric CO2 and shallow seawater DIC due to anthropogenic carbon release, a phenomenon commonly referred to as the 13C Suess effect. These findings highlight an important, yet overlooked, aspect of some modern carbonate systems, which must inform their use as ancient analogs.

Unexpected contributions by carbonates and organic matter in a silicate-dominated tropical catchment: An isotope approach

The understanding of global carbon has rarely extended to small-scale tropical river basins. To address these uncertainties, this study aims to investigate the importance of rock weathering and organic matter turnover in the carbon cycle in a terrain dominated by crystalline silicate rocks. The geochemical composition of the dissolved and particulate carbon phases (DIC, DOC and POC) and their stable carbon isotopes were studied in the Deduru Oya River in Sri Lanka. Dissolved inorganic carbon (DIC) was the most dominant carbon phase and its contribution to the total carbon pool varied between 67 and 89 %. Furthermore, the δ13CDIC values in the river varied between −1.1 and −16.5 ‰. The lithological characteristics and molar ratios between Ca2+, Mg2+ and HCO3− indicated rock weathering mainly by CO2 and carbonic acid. The δ13CDIC values for groundwater input were −15.9 ‰, while for carbonate weathering, mainly due to fertiliser input, they reached a value of −12.7 ‰. This input was fed into an isotope mass balance to determine the relative contributions. However, the isotope mass balance was only plausible after correcting for the effects on δ13CDIC caused by degassing and photosynthesis. Our study demonstrated that carbonate weathering and organic matter turnover are essential components of the river carbon cycle even in a silicate dominated catchment. They can represent up to 60 % of the DIC pool. Combined with the higher organic matter turnover and high pCO2 in the river water, it can be suggested that the Deduru Oya River acts as a net source of CO2 in the atmosphere. Our study shows that CO2 degassing and in-stream photosynthesis in tropical river systems need to be considered along with chemical weathering to account for carbon transport and turnover in tropical rivers.

Geochemical tracers associated with methane in aquifers overlying a coal seam gas reservoir

Understanding inter-aquifer connectivity or leakage of greenhouse gases and groundwater to aquifers overlying gas reservoirs is important for environmental protection and social licence to operate. Australia's Great Artesian Basin (GAB) is the largest artesian groundwater system in the world with groundwater extracted for agriculture, livestock, mines, energy, private or town water supply. Microbial coal seam gas (CSG) and production water are also extracted from the GAB. Here a range of groundwater tracers is used to investigate the potential for gas and groundwater connectivity between the CSG reservoir and aquifers.The GAB aquifer and alluvium contained a range of methane concentrations (0.001 to 2100 mg/L) that exhibit an increase with depth and δ13C-CH4. Aquifer and alluvium groundwater 87Sr/86Sr were in the range 0.7042 to 0.7082. CSG production waters however had non-radiogenic, distinctive 87Sr/86Sr signatures <0.7036, indicating a lack of significant groundwater leakage. One gassy aquifer bore with 160 mg/L methane conversely has 87Sr/86Sr, δ13C-CH4, δ2H-CH4 and δ13C-DIC values overlapping the CSG waters. In several aquifers δ34S-SO4 and δ18O-SO4 are sourced from windblown surface salts of inland Australian playa lakes in recharge waters. Bacterial sulphate reduction is additionally occurring in a regional aquifer. Cosmogenic isotopes and tritium show recent recharge and mixing with older groundwaters in several shallow aquifers.Groundwater and gas signatures indicate that leakage of groundwater and methane from the CSG reservoir was not occurring in the majority of areas investigated here. Methane was consistent with in situ generation in shallow GAB aquifers by primary microbial CO2 reduction or acetate fermentation. Connectivity of one alluvial bore and the underlying GAB aquifer could not be completely ruled out. Separately, one gassy Springbok GAB aquifer bore is either connected to the underlying CSG gas reservoir, or has in situ secondary microbial CO2 reduction producing methane from interbedded coal within the aquifer. This study is relevant to other basins in Australia and internationally where gas is observed in aquifers that overly conventional, unconventional or coal seam gas reservoirs.

Abiotic processes control carbon dioxide dynamics in temperate karst lakes.

Inland waters are crucial in the carbon cycle, contributing significantly to the global CO2 fluxes. Carbonate lakes may act as both sources and sinks of CO2 depending on the interactions between the amount of dissolved inorganic carbon (DIC) inputs, lake metabolisms, and geochemical processes. It is often difficult to distinguish the dominant mechanisms driving CO2 dynamics and their effects on CO2 emissions. This study was undertaken in three groundwater-fed carbonate-rich lakes in central Spain (Ruidera Lakes), severely polluted with nitrates from agricultural overfertilization. Diel and seasonal (summer and winter) changes in CO2 concentration (CCO2) DIC, and CO2 emissions-(FCO2)-, as well as physical and chemical variables, including primary production and phytoplanktonic chlorophyll-a were measured. In addition, δ13C-DIC, δ13C-CO2 in lake waters, and δ13C of the sedimentary organic matter were measured seasonally to identify the primary CO2 sources and processes. While the lakes were consistently CCO2 supersaturated and FCO2 was released to the atmosphere during both seasons, the highest CCO2 and DIC were in summer (0.36-2.26 µmol L-1). Our results support a strong phosphorus limitation for primary production in these lakes, which impinges on CO2 dynamics. External DIC inputs to the lake waters primarily drive the CCO2 and, therefore, the FCO2. The δ13C-DIC signatures below -12‰ confirmed the primary geogenic influence on DIC. As also suggested by the high values on the calcite saturation index, the Miller-Tans plot revealed that the CO2 source in the lakes was close to the signature provided by the fractionation of δ13C-CO2 from calcite precipitation. Therefore, the main contribution behind the CCO2 values found in these karst lakes should be attributed to the calcite precipitation process, which is temperature-dependent according to the seasonal change observed in δ13C-DIC values. Finally, co-precipitation of phosphate with calcite could partly explain the observed low phytoplankton production in these lakes and the impact on the contribution to increasing greenhouse gas emissions. However, as eutrophication increases and the soluble reactive phosphorus (SRP) content increases, the co-precipitation of phosphate is expected to be progressively inhibited. These thresholds must be assessed to understand how the CO32- ions drive lake co-precipitation dynamics. Carbonate regions extend over 15% of the Earth's surface but seem essential in the CO2 dynamics at a global scale.

Dynamics of dissolved inorganic carbon (DIC) and stable C isotope ratios (δ13CDIC) in a tropical watershed with diversified land use in São Paulo State, Brazil

The fluvial transport of dissolved inorganic carbon (DIC) is an important component of the global carbon cycle. Herein, we assessed the dynamics of DIC and the C stable isotopic composition (δ13CDIC) in a watershed with diversified land use in São Paulo State (Brazil), more specifically in the Sorocaba River basin (SRB) and considered the temporal and spatial scales. For this purpose, twelve fluvial samples at each sampling point (e.g., S1, S2, S3, S4 and S5) were collected in the SRB, from June 2009 to May 2010, which represented one complete hydrological cycle that included the extremes of the rainfall and discharge regimes. In addition, the δ13CDIC values were also characterized in the wet and dry season at all sampling points to verify their seasonal variability. The results reflected the seasonal variation in discharges, water temperatures, and electrical conductivities. Most of the DIC was transported in the wet season at all sampling points, where the less negative δ13CDIC values were characterized. The natural sources of DIC are associated with atmospheric/soil CO2 consumption. The anthropogenic impacts on both [DIC] and δ13CDIC are linked to untreated urban sewage that is discharged directly into the Sorocaba River, as well as to aquatic photosynthesis in the Itupararanga Reservoir. From 1970 to 2020, the modeling proposed in this study indicated that the annual flux of DIC (Friver) varied from 9.0 to 78.7 t km−2 a−1, confirming that the El Niño Southern Oscillation (ENSO) controlled Friver in the SRB, with higher and lower Friver values occurring during strong El Niño (EN) and La Niña (LN) years. The average Friver value was 20 t km−2 a−1, which is higher than those obtained in natural several temperate and tropical watersheds due to the influences of urban areas on [DIC] in the SRB.

Response of weathering carbon sink effect to anthropogenic sulfuric acid in different lithological catchments: A case study from Southwest China

Accurately quantifying the carbon sink effect resulting from chemical weathering caused by anthropogenic H2SO4 is imperative to improve the assessment of the global carbon budget. Nevertheless, there is still a lack of precise understanding regarding the impact of anthropogenic H2SO4 on CO2 consumption during chemical weathering. Here, spring water samples were collected monthly from three catchments with distinct bedrock lithologies affected by severe acid precipitation in Southwest China for analyses of hydrogeochemistry and δ13CDIC to quantitatively estimate the effect of anthropogenic H2SO4 on the weathering carbon sink budget. The results show that carbonates contribute 97.4 %, 95.0 % and 88.8 % of the total cationic load using a straightforward method in the Beidiping carbonate catchment, as well as in the Shegengyan and Bianyan silicate catchments, respectively. The [Ca2++Mg2+]/[HCO3−] (0.98–1.19) and [Ca2++Mg2+]/[HCO3−+SO42−] (approximately 1) equivalent ratios, and δ13CDIC values (−16.8 to −8.0 ‰) of the samples suggest that besides H2CO3, H2SO4 is involved in carbonate weathering. The stoichiometry of the chemical compositions of spring water indicates that the presence of H2SO4 enhances carbonate weathering rates by 14.8 %, 8.1 % and 7.5 % while decreasing the CO2 consumption by 8.2 %, 4.3 % and 4.0 % in Beidiping, Shegengyan and Bianyan, respectively. Thus the reduced proportion of karst carbon sink in the carbonate catchment is approximately 2 times that in the silicate catchment, suggesting that carbonate weathering in the karst catchment is more sensitive to acid precipitation. The impact of acid precipitation on rock weathering in the silicate catchment is constrained by the soil buffering effect. Our study highlights the important role of anthropogenic H2SO4 in carbonate weathering, which should be critically evaluated in regional and global carbon cycles in future studies.

Synglacial carbonate records of snowball Earth ocean composition—Evidence from the Nantuo Formation, South China

Abstract The Cryogenian (ca. 717–635 Ma) snowball Earth glaciations ended with the precipitation of “cap” carbonate successions with negative carbon isotope (δ13Ccarb) values, which have been explained by the addition of various 13C-depleted carbon sources in the deglacial process. These arguments assumed that marine dissolved inorganic carbon (DIC) was enriched in 13C in the synglacial ocean. However, this assumption has not yet been tested, because the synglacial ocean chemistry is unknown. In this study, we carried out detailed analyses of the petrology, carbonate carbon (δ13Ccarb) and oxygen (δ18Ocarb) isotopes, organic carbon (δ13Corg) isotopes, major and minor elemental compositions (Ca, Mg, Mn, Fe, Sr), and iron speciation (total Fe, highly reactive Fe, pyrite Fe) of the carbonate layers (also called synglacial carbonate layers) from the Nantuo Formation (ca. 650–635 Ma) on the Yangtze block, South China. Petrographic observations indicated that the synglacial carbonate comprises dolomicrite, mud-crystal powder dolomite, lime dolomite, and dolomitic limestone, supporting an authigenic carbonate origin, and thus, it potentially recorded the ocean chemistry during the Marinoan ice age. The synglacial carbonate is characterized by extreme Mn enrichment, low Fe/Mn ratios, and low δ13Ccarb (−7‰) values. High Mn contents and low Fe/Mn ratios imply marine redox conditions favoring Mn2+ accumulation and Fe2+ oxidation, while low δ13Ccarb values might be attributed to CO2 degassing of submarine volcanoes as well as low primary burial during the glaciation. Since the δ13CDIC value of the synglacial ocean was lower than the δ13Ccarb values of most cap carbonates, we infer the addition of 13C-enriched DIC or removal of 12C during cap carbonate precipitation, such as through carbonate weathering or organic carbon burial. These findings provide new insights into the nature of Cryogenian glaciation, the origin of cap carbonates, and the aftermath of global glaciation.

Hydrogeochemical and Isotopic Characterisation of the Učja Aquifer, NW Slovenia

The groundwater characteristics of the Učja aquifer were investigated using geochemical and isotopic data. The water discharge and physico-chemical properties of the groundwater and the Učja River reflect the climate that is characteristic of the area. The mixed snow/rainfall regime is characteristic for the Učja Valley, with the highest discharges appearing during the spring snowmelt and autumn precipitation, and the lowest discharges in the winter and especially summer months. The temperature of the groundwater and the Učja River is lower in winter and higher in summer. The specific electrical conductivity values indicate a very permeable carbonate aquifer. Higher conductivity values were observed in spring and autumn at all sampling sites, which is related to snowy and rainy periods. The groundwater from the Učja aquifer indicates a uniform type of water (Ca-Mg-HCO3), with Ca2+, Mg2+ and HCO3– the most abundant ions. Differences in Ca2+ and Mg2+ concentrations and in the Mg2+/Ca2+ molar ratio between sampling sites were observed. Those springs with lower Mg2+ and lower Mg2+/Ca2+ molar ratios indicate limestone recharge areas, and those springs with higher Mg2+ and molar ratios indicate interaction with the dolomite hinterland. The pH values confirm alkaline waters characteristic of carbonate aquifers. The hydrogen (δ2H) and oxygen (δ18O) isotope values suggest the main source of water is from precipitation from a complex mixing of maritime and continental air masses. An altitude isotopic effect is observed with minor δ18O and δ2H depletion at higher altitude sampling sites compared to those springs at lower altitudes. The altitude isotopic effect is most prominent in spring. The δ13CDIC values indicate the dissolution of carbonates and the degradation of organic matter.

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.

Microbial coalbed gas and its geological formation process in the Jimsar region of the southern Junggar Basin, NW China

The southern Junggar Basin is abundant in coalbed gas (CBG) resources, with the Jimsar region in the southern part of the basin emerging as a potential CBG development demonstration area. However, further development of the CBG in this region is restricted by the lack of understanding of the genesis and gas reservoir formation mechanisms of the CBG. This study systematically collected CBG samples and associated water samples from the Jimsar region. Stable isotope, hydrogeochemical, and 16S ribosomal ribonucleic acid (rRNA) sequencing studies were carried out. The results demonstrate that the CBG is the primary microbial gas, and CO2 reduction is its formation pathway. Hydrogeochemical analysis shows that the coalbed water receives recharge from meteoric or surface water. The water environment is relatively active (open system). The total dissolved organic carbon (TDOC) in the coalbed water is primarily from coal, and the supply and consumption of the total dissolved nitrogen (TDN) may be relatively balanced. The dissolution of CO2 is the main source of the dissolved inorganic carbon (DIC). Furthermore, the positive δ13CDIC values and high alkalinity indicate microbial methanogenesis. Microbial community structure analysis revealed that the archaea are hydrogenotrophic methanogens in the Jimsar region. The microbial basis for the production of microbial gas is provided by the existence of hydrolytic, acidogenic, and hydrogen-producing acetogenic bacteria as well as methanogenic archaea. Natural gas genetic identification diagrams and detection of methane-oxidizing bacteria (Methylomicrobium) reveal that the CBG may be affected by slight oxidation. In addition, the methanogenic effect is much greater than the methane oxidation. Finally, based on these results and the regional tectonic background, the CBG enrichment and accumulation mode in the Jimsar region was established. This mode can be divided into three geological stages: burial and coalification, surface water recharge and microbial gas generation after uplift and denudation, and CBG accumulation controlled by reverse faults and hydrodynamic sealing. This study enriches the geological theory of CBG accumulation in the Jimsar region and provides guidance for the subsequent exploration and development of the CBG.

Spatial variability of hydrochemistry and environmental controls in karst aquifers of the southern Iberian Peninsula: Implications for climate change impact assessment

Carbonate aquifers are crucial water and carbon reservoirs globally, particularly in semi-arid climates. However, these systems are susceptible to the impacts of climate change, given their sensitivity to specific environmental factors. This study presents the hydrochemical (water temperature, pH, electrical conductivity, and major ions) and isotopic (δ13C) composition of 39 karst springs in the southern Iberian Peninsula, along with the parameterization of environmental factors (temperature, precipitation, recharge altitude, and vegetation cover quantified by the Normalized Differential Vegetation Index, NDVI) in their recharge areas. The spatial analysis revealed that the climatic and environmental factors follow a longitudinal pattern producing a notable west-east environmental gradient in the study area. Through a statistical analysis based on Principal Component Analysis (PCA), it was found that environmental factors control the spatial variability of groundwater hydrochemistry in these karstic aquifers. The δ13CDIC values in groundwater, ranging from −1.84 to −12.46 ‰, show a prevalence of C4 plants mainly in the more arid study sectors and indicate an origin of dissolved inorganic carbon (DIC) mainly in biological processes in the recharge area. In addition, a relationship between NDVI values, equilibrium partial pressure of CO2 (pCO2), and groundwater bicarbonate content was observed. Springs further west of the study area exhibited higher bicarbonate content (about 400 ppm), which was associated with higher pCO2 levels (about 10,000 and 15,000 ppm) and higher NDVI values (between 0.5 and 0.7). In contrast, aquifers located further to the east had lower bicarbonate levels (<200 ppm), with an average pCO2 of about 2000 ppm and the lowest NDVI values (<0.3). Furthermore, the spatial variability and the relationship between environmental factors and groundwater hydrochemistry allow for the assessment of potential climate change impacts in carbonate systems with a comparison between aquifers in wetter regions and those in semi-arid conditions.

Lipidomic diversity and proxy implications of archaea from cold seep sediments of the South China Sea

Cold seeps on the continental margins are characterized by intense microbial activities that consume a large portion of methane by anaerobic methanotrophic archaea (ANME) through anaerobic oxidation of methane (AOM). Although ANMEs are known to contain unique ether lipids that may have an important function in marine carbon cycling, their full lipidomic profiles and functional distribution in particular cold-seep settings are still poorly characterized. Here, we combined the 16S rRNA gene sequencing and lipidomic approaches to analyze archaeal communities and their lipids in cold seep sediments with distinct methane supplies from the South China Sea. The archaeal community was dominated by ANME-1 in the moderate seepage area with strong methane emission. Low seepage area presented higher archaeal diversity covering Lokiarchaeia, Bathyarchaeia, and Thermoplasmata. A total of 55 core lipids (CLs) and intact polar lipids (IPLs) of archaea were identified, which included glycerol dialkyl glycerol tetraethers (GDGTs), hydroxy-GDGTs (OH-GDGTs), archaeol (AR), hydroxyarchaeol (OH-AR), and dihydroxyarchaeol (2OH-AR). Diverse polar headgroups constituted the archaeal IPLs. High concentrations of dissolved inorganic carbon (DIC) with depleted δ13CDIC and high methane index (MI) values based on both CLs (MICL) and IPLs (MIIPL) indicate that ANMEs were active in the moderate seepage area. The ANME-2 and ANME-3 clades were characterized by enhanced glycosidic and phosphoric diether lipids production, indicating their potential role in coupling carbon and phosphurus cycling in cold seep ecosystems. ANME-1, though representing a smaller proportion of total archaea than ANME-2 and ANME-3 in the low seepage area, showed a positive correlation with MIIPL, indicating a different mechanism contributing to the IPL-GDGT pool. This also suggests that MIIPL could be a sensitive index to trace AOM activities performed by ANME-1. Overall, our study expands the understanding of the archaeal lipid composition in the cold seep and improves the application of MI using intact polar lipids that potentially link to extent ANME activities.

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.