Dissolved Inorganic Carbon Concentrations Research Articles

Influence of Rivers, Tides, and Tidal Wetlands on Estuarine Carbonate System Dynamics

AbstractVariations in estuarine carbonate chemistry can have critical impacts on marine calcifying organisms, yet the drivers of this variability are difficult to quantify from observations alone, due to the strong spatiotemporal variability of these systems. Terrestrial runoff and wetland processes vary year to year based on local precipitation, and estuarine processes are often strongly modulated by tides. In this study, a 3D-coupled hydrodynamic-biogeochemical model is used to quantify the controls on the carbonate system of a coastal plain estuary, specifically the York River estuary. Experiments were conducted both with and without tidal wetlands. Results show that on average, wetlands account for 20–30% of total alkalinity (TA) and dissolved inorganic carbon (DIC) fluxes into the estuary, and double-estuarine CO2 outgassing. Strong quasi-monthly variability is driven by the tides and causes fluctuations between net heterotrophy and net autotrophy. On longer time scales, model results show that in wetter years, lower light availability decreases primary production relative to biological respiration (i.e., greater net heterotrophy) resulting in substantial increases in CO2 outgassing. Additionally, in wetter years, advective exports of DIC and TA to the Chesapeake Bay increase by a factor of three to four, resulting in lower concentrations of DIC and TA within the estuary. Quantifying the impacts of these complex drivers is not only essential for a better understanding of coastal carbon and alkalinity cycling, but also leads to an improved assessment of the health and functioning of coastal ecosystems both in the present day and under future climate change.

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.

Disentangling the effects of applying pig slurry or its digestate to winter wheat or a catch crop on dissolved C fluxes

The anaerobic digestion industry, which is still developing, generates biogas from organic waste products. A co-product of this process, digestate, is increasingly produced and can be recycled on agricultural land as an alternative to mineral fertilizers. Biogas digestate is a recent product whose chemical composition differs from that of its source material, and additional data still need to be acquired on its effects on dissolved carbon fluxes. The objectives of this study were to assess (i) the effects of applying biogas digestate on dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) fluxes with different winter crops, (ii) the dynamics of DOC and DIC concentrations during the drainage season, and (iii) the annual dynamics of DOC and DIC fluxes along the soil profile. The study examined effects of applying biogas digestate, pig slurry, or a mineral fertilizer to winter wheat and two catch crops (mustard and a multispecies crop) on DOC and DIC fluxes in the soil. Lysimeters at 40 cm (topsoil) and 90 cm (subsoil) depths were monitored from 2014 to 2023, from November to March (i.e., 9 winter drainage seasons). During the drainage season, the DOC concentration was highest with digestate, and its timing depended on development of the cover crop: from the beginning of the drainage season for mustard and the multispecies crop and around February for wheat. Applying digestate increased the topsoil DOC fluxes (mean of 35.7 ± 13.7 kg.ha−1 with digestate vs. 21.0 ± 6.7 kg.ha−1 with the other treatments), particularly under mustard. Topsoil DIC fluxes were highest with pig slurry due to higher mineralization than that with digestate (mean of 59.1 ± 22.8 kg.ha−1 with pig slurry vs. 46.2 ± 16.3 kg.ha−1 with the other treatments). In the subsoil, DOC fluxes were low (6.2 ± 4.1 kg.ha−1) and DIC fluxes were high (80.0 ± 45.7 kg.ha−1), with no difference among treatments.

Large variations of dissolved carbon occurred in small ponds within an agricultural watershed

Dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) significantly affect the aquatic carbon budget and ecosystem functions. Small ponds are abundant globally and widely distributed especially in agricultural watersheds, however, the variability of DOC and DIC, along with their driving factors, remains poorly understood, which likely hampers the understanding of carbon cycle of inland waters. The presented study was designed to fill the knowledge gap based on a detailed year-long field investigation via examining DOC and DIC concentrations across ponds with differing functionalities (e.g. sewage ponds, irrigation ponds, and natural ponds) of a typical agricultural watershed in eastern China. Our results found a pronounced impact of human activities on pond DOC and DIC, with higher DOC occurring in sewage ponds (10.84 ± 2.83 mg L−1) and irrigation ponds (9.09 ± 2.57 mg L−1) and peak DIC in irrigation ponds (20.36 ± 2.49 mg L−1) compared to that at natural ponds (DOC: 7.54 ± 2.55 mg L−1; DIC: 11.16 ± 3.85 mg L−1) with less human activity. The positive correlations between DOC/DIC and key environmental variables (e.g. nutrients and chlorophyll-a) further demonstrated that human activity can either directly increase the carbon concentrations via pollutant discharge, or indirectly increase DOC concentration via stimulating primary production. Meanwhile, field measurements found precipitation and temperature play roles in determining the carbon variability. Specifically, precipitation increased the DOC of these ponds via enhancing land-based carbon inputs, and decrease the DIC of irrigation ponds via diluting. Temperature can influence the carbon dynamics through increasing primary productivity and metabolism. Our study underscores the roles of human and natural influences in determining the large variations of DOC and DIC in small ponds, which should be considered to better understand the carbon dynamic variability of human-impacted small aquatic systems.

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.

High precision determination of carbon isotope composition and concentration of dissolved inorganic carbon in seawaters

Determination of the isotopic composition and concentration of dissolved inorganic carbon (DIC) in sea water requires not only high measurement accuracy, but also the development of unified approaches to data standardization and material collection. In this work, we studied the effect of sampling methods (“in a container” and “in a vial with acid”, with and without the toxin) on the results of determining the values of δ13C(DIC) and the concentration of DIC in sea water. The analytical protocol was described in detail, based on many years of experience in the selection, measurement and standardization of data obtained for a large number of water samples of the Arctic seas. According to this protocol, the values of δ13C(DIC) and [DIC] can be determined with an error of less than 0.05 ‰ (1σ) and 4.5 rel.% respectively. It has been shown that sampling “in a vial with acid” with their storage for 4 months is accompanied by significant contamination by atmospheric carbon dioxide with an underestimation of δ13C(DIC) values by an average of 0.3–0.8 ‰ and an overestimation of [DIC] values by an average of two times. The absence of the toxin that stops biological activity does not lead to significant shifts in the DIC concentration, but it strongly affects the δ13C(DIC) values, which become underestimated by an average of 1 ‰. Using sampling “in a container”, with toxin addition, and following other recommendations, the samples retain the isotope and concentration parameters of DIC for at least year.

Variability of Dissolved Inorganic Carbon in the Most Extensive Karst Estuarine-Lagoon System of the Southern Gulf of Mexico

AbstractCoastal ecosystems with karstic geology have a unique characteristic where the dissolution of carbonate rocks can increase total alkalinity (TA) and dissolved inorganic carbon (DIC). This results in higher inorganic carbon budgets in coastal areas. One such ecosystem is the Terminos Lagoon, the most extensive tropical estuarine lagoon system in Mexico, located in the karstic aquifer of the Yucatan Peninsula and connected to the southern Gulf of Mexico (sGoM). We measured TA and DIC to evaluate the variability in Terminos Lagoon’s of the carbonate system. We also estimated pH, partial CO2 pressure (pCO2), and aragonite saturation (ΩAr) along two transects from the main lagoon tributaries (Palizada and Candelaria rivers) to the coastal zone during the dry and rainy seasons. During the dry season, TA and DIC concentrations were significantly higher (3092 ± 452 µmol kg-1 TA, 2943 ± 522 µmol kg-1 DIC) than during the rainy season (2533 ± 228 µmol kg−1 TA, 2492 ± 259 DIC µmol kg−1). Our calculations indicate that the rainy season pCO2 (2532 ± 2371 µatm) seems higher than in the dry season (1534 ± 1192 µatm). This leads to a reduction in pH (7.9 ± 0.3 to 7.8 ± 0.3). These significant changes indicate that rain increases the flow of unsaturated river water into the lagoon. The results of this work contribute toward a dissolved inorganic carbon variability baseline in the sGoM and can be helpful to Terminos Lagoon decision-makers.

Response of dissolved inorganic carbon dynamics to simulated tidal hydrological processes in coastal wetlands

To clarify the impacts of tidal hydrological process shifts caused by sea level rise on the blue carbon cycle, a typical coastal wetland in Jiaozhou Bay was selected for this study. The soils of Suaeda salsa (SS) and Phragmites australis (PA) wetlands were collected to simulate the effects of three types of tidal hydrological processes (Neap tide group, NT; Middle tide group, MT; Spring tide group, ST) on the soil-water dissolved inorganic carbon (DIC) dynamic. The results showed that the concentration of water dissolved inorganic carbon (WDIC) increased rapidly (115% higher) at early stage (days 0–4) under the influence of the tidal hydrological processes. Significant differences were found in WDIC concentration during different tidal hydrological processes (P < 0.05), which were expressed as MT (52.7 ± 13.3 mg L−1) > ST (52.5 ± 12.9 mg L−1) > NT (48.4 ± 10.1 mg L−1). After experiencing the tidal hydrological processes, the soil DIC content showed a net accumulation (55.1 ± 1.29 mg L−1vs. 46.7 ± 1.76 mg L−1, P < 0.001), whereas the soil inorganic carbon (SIC) decreased (2.73 ± 1.64 mg L−1vs. 4.61 ± 1.71 mg L−1), which may be attributed to the dissolution of SIC caused by the uptake of CO2 to form DIC. The accumulation of soil DIC was directly related to the SIC (λ = 1.03, P < 0.01), and indirectly related to soil nutrients (SOC substrate, λ = −0.003) and microbes (microbial biomass, λ = −0.10), and was mainly dominated by abiotic processes (abiotic: 58.1 ± 1.8% to 82.7 ± 2.46% vs. biotic: 17.4 ± 2.46% to 41.9 ± 1.76%). The increase of tidal frequency generally inhibited the accumulation of soil DIC content and promoted the output of WDIC. However, the response of soil DIC in different wetland types to tidal frequency was divergent, which was mainly regulated by the trade-off between soil nutrients and SIC content. Taken together, tidal hydrological processes and their frequency changes reshaped DIC dynamics, promoted the dissolution of SIC and the potential uptake of CO2. These findings enhance the comprehension of the inorganic carbon cycle within coastal wetlands, particularly amidst the backdrop of climate change and the rising sea levels.

Interannual variability of air-sea CO2 exchange in the Northern Yellow Sea and its underlying mechanisms

A three-dimensional (3-D) physical-biogeochemical-carbon cycle coupled model is used to investigate the interannual variability of the air-sea carbon dioxide (CO2) flux (FCO2) in the Northern Yellow Sea (NYS) from 2009 to 2018. The verification of the model indicate that the simulation results for multiple variables exhibit consistency and fit well with the observed data. The study show that although the multi-year average FCO2 in the NYS is close to the source-sink balance, there are obvious interannual differences between different years. In particular, a relatively strong source of atmospheric CO2 (1.0 mmol m–2 d–1) is exhibited in 2014, while a relatively strong sink of atmospheric CO2 (–0.7 mmol m–2 d–1) emerges in 2016. Mechanism analysis indicates that the abnormally high temperature is the main controlling factor for the relatively high CO2 efflux rate in the NYS in 2014, while the abnormally low dissolved inorganic carbon (DIC) concentration is the main factor contributing to the relatively high CO2 influx rate in 2016. Further analysis reveals that the primary reason for the low DIC concentration since the onset of winter in 2016 is the high net decrease rate of DIC in the NYS in 2015, influenced by net community production in the summer and advection processes during the autumn. The abnormally high primary production during the summer of 2015 results in the excessive reduction of DIC concentration through biological processes. In addition, due to the strong northeasterly wind event in November 2015, low-concentration-DIC water from the Yellow Sea (YS) extends into the Bohai Sea (BS). This further leads to higher DIC flux from the NYS into the BS in the upper mixed layer and increases the inflow of low-concentration-DIC water from the Southern Yellow Sea (SYS) into the NYS. These ultimately result in the abnormal reduction of DIC concentration in the upper mixed layer of the NYS during the autumn of 2015. This study enriches our understanding of interannual variability of FCO2 in the NYS, which will not only help to further reveal the variations of FCO2 under human activities and climate change, but also provide useful information for guiding the comprehensive assessment of the carbon budget.

Disentangling Carbon Concentration Changes Along Pathways of North Atlantic Subtropical Mode Water

AbstractNorth Atlantic subtropical mode water (NASTMW) serves as a major conduit for dissolved carbon to penetrate into the ocean interior by its wintertime outcropping events. Prior research on NASTMW has concentrated on its physical formation and destruction, as well as Lagrangian pathways and timescales of water into and out of NASTMW. In this study, we examine how dissolved inorganic carbon (DIC) concentrations are modified along Lagrangian pathways of NASTMW on subannual timescales. We introduce Lagrangian parcels into a physical‐biogeochemical model and release these parcels annually over two decades. For different pathways into, out of, and within NASTMW, we calculate changes in DIC concentrations along the path (ΔDIC), distinguishing contributions from vertical mixing and biogeochemical processes. The strongest ΔDIC is during subduction of water parcels (+101 μmol L−1 in 1 year), followed by transport out of NASTMW due to increases in density in water parcels (+10 μmol L−1). While the mean ΔDIC for parcels that persist within NASTMW in 1 year is relatively small at +6 μmol L−1, this masks underlying dynamics: individual parcels undergo interspersed DIC depletion and enrichment, spanning several timescales and magnitudes. Most DIC enrichment and depletion regimes span timescales of weeks, related to phytoplankton blooms. However, mixing and biogeochemical processes often oppose one another at short timescales, so the largest net DIC changes occur at timescales of more than 30 days. Our new Lagrangian approach complements bulk Eulerian approaches, which average out this underlying complexity, and is relevant to other biogeochemical studies, for example, on marine carbon dioxide removal.

Sources and Flux of Dissolved Inorganic Carbon in the Hydrothermally Active Corner of a Backarc Basin (Southwestern Okinawa Trough)

AbstractCO2 released from subduction zones plays a vital role in the tectonic carbon cycle. However, the contribution of submarine backarc components to carbon emissions remains poorly understood compared to subaerial arc volcanos. This study utilized a combination of geochemical and hydrodynamic approaches to investigate the sources and flux of dissolved inorganic carbon (DIC) in the deep basin of the southwestern Okinawa Trough. Most deep‐water (depth ≥1,000 m) samples, even those retrieved from sites distant from active venting, exhibited mild geochemical anomalies of elevated 3He/4He ratios and higher DIC content than reference sites. Hydrodynamic observations using bottom‐mounted acoustic instruments in the deep basin revealed strong tidal currents and enhanced turbulent mixing. These findings suggest that active solute dispersal and mixing are responsible for the prevalence of mild geochemical anomalies in the basin. Mixing models indicated that hydrothermal vent fluids are the primary source of excess 3He and DIC above background levels in the deep basin, whereas both CO2 and mineral acid in hydrothermal fluids cause excess acidity. Based on hydrodynamic and geochemical data, a box model estimated a hydrothermal DIC flux of 0.62 ± 1.40 × 1010 mol y−1, equivalent to 40% of CO2 emissions from persistently degassing volcanos in the Ryukyu Arc. Our results suggest that submarine carbon emissions are quantitatively important in subduction systems with subaqueous backarc components.

Lithology constrains the origination of autochthonous carbon in river ecosystems

Dissolved inorganic carbon (DIC) provides a substrate for primary production in the lotic ecosystems, yet carbon's biogeochemical origination in the lotic food webs is still poorly constrained. Here, we assembled a global dataset of isotopic composition (i.e., 13C/12C or δ13C) of DIC and periphyton (algae being the primary producers) in river waters, and carried out a field study in two catchments respectively with carbonate and silicate dominated lithologies on the Tibetan Plateau. A two-endmember mixing model based on the datasets indicated that δ13C and concentrations of DIC in the river waters were largely determined by the catchment-scale chemical weathering of different lithologies. Meanwhile, a significant correlation was obtained between δ13C-DIC and δ13C-periphyton in the datasets, strongly implying that the origination of periphyton carbon was largely regulated by the catchment lithologies. The δ13C-periphyton compositions are also affected by isotopic fractionations during algal primary production, which, in turn, were closely related to the relationships between primary productivity and DIC availability in the rivers. The study advances our understanding of the origination and transfer of carbon biogeochemically bridging the geosphere and biosphere in the lotic ecosystems.

Karst carbon sink mechanism and its contribution to carbon neutralization under land- use management

The chemical weathering process of carbonate rocks consumes a large quantity of CO2. This has great potential as a carbon sink, and it is one of a significant pathway for achieving carbon neutrality. However, the control mechanisms of karst carbon sink fluxes are unclear, and there is a lack of effective and accurate accounting. We took the Puding Shawan karst water‑carbon cycle test site in China, which has identical initial conditions but different land use types, as the research subject. We used controlled experiments over six years to evaluate the mechanisms for the differences in hydrology, water chemistry, concentrations and fluxes of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC). We found that the transition from rock to bare soil to grassland led to increases in the DIC concentration by 0.08–0.62 mmol⋅L−1. The inorganic carbon sink flux (CSF) increased by 3.01–5.26 t⋅C⋅km−2⋅a−1, an increase amplitude of 30–70 %. The flux of dissolved organic carbon (FDOC) increase by 0.28 to 0.52 t⋅C⋅km−2⋅a−1, an increase amplitude of 34–90 %. We also assessed the contribution of land use modifications to regional carbon neutrality, it indicate that positive land use modification can significantly regulate the karst carbon sink, with grassland having the greatest carbon sequestration ability. Moreover, in addition to DOC from soil organic matter degradation, DOC production by chemoautotrophic microorganisms utilizing DIC in groundwater may also be a potential source. Thus, coupled studies of the conversion of DIC to DOC processes in groundwater are an important step in assessing karst carbon sink fluxes.

Changes in the limiting nutrients and dominant phytoplankton communities of three major European rivers: Response to catchment lithologies and human activities

Catchment lithologies and human activities can cause variations in riverine carbon (C), nitrogen (N), and phosphorus (P) loads, and the ratio of these nutrients may affect the primary productivity of rivers and their phytoplankton communities. We conducted a comparative study of biogeochemical variations in three major European rivers—the Rhine, Danube, and Seine—which reveals the impacts of different carbonate outcrops and human impacts (agricultural activities and sewage input) on the changes in the limiting nutrients and phytoplankton community compositions of flowing water systems. N limitation was observed in the Rhine and Danube owing to their low average NO3– loads (4.04–6.45 mg/L). Although the extensive outcrops of carbonate rocks in the Seine catchment result in high average HCO3– concentrations of ∼ 4.68 mmol/L, the elevated inorganic C input did not match the high average NO3– loads (∼19.38 mg/L), driven by intensive agricultural activity and urban sewage input, demonstrating a potential C limitation on productivity. Our results show that the productivity of the Seine River, determined by the chlorophyll-a concentration, was significantly related to the dissolved inorganic carbon (DIC) concentration (coefficient of determination: R2 = 0.68, P < 0.05). Our results demonstrate that changes in DIC content can significantly alter the dominant phytoplankton species in the water column. The high inputs of DIC and aqueous CO2(aq) to the Seine lead to Bacillariophyta proportions that are 3.96–8.81 % and 19.87–22.56 % higher than those of the Rhine and Danube in the wet and dry seasons, respectively. This can be explained by the difference in the efficiency of carbon concentrating mechanisms (CCMs) among phytoplankton species. Therefore, to mitigate river eutrophication and improve the quality of the aquatic environment, we suggest that future water–carbon management in the flowing water systems with abundant nutrients should consider C-limitation alleviation and its potential effect for reducing the abundance of harmful algae.

Aquatic photosynthetic carbon pump driven by periodic temperature variations affects dissolved inorganic carbon and hydrochemical characteristics in a groundwater-fed reservoir

Under the influence of periodic temperature variations, biogeochemical cycling in water bodies is markedly affected by the periodic thermal stratification processes in subtropical reservoirs or lakes. In current studies, there is insufficient research on the influence and mechanism of dissolved inorganic carbon (DIC) distribution in karst carbon-rich groundwater-fed reservoirs under the coupled effects of thermal structure stratification and the biological carbon pump (BCP) effect. To address this issue, the Dalongdong (DLD) reservoir in the subtropical region of southern China was chosen as the site for long-term monitoring and research on relevant physicochemical parameters of water, DIC, and its stable carbon isotope (δ13CDIC), CO2 emission flux, as well as the reservoir's thermal stratification index. The results show that: (1) the DLD reservoir is a typical warm monomictic reservoir, which exhibits regular variations of mixing period-stratification period-mixing period on a yearly scale due to thermal structure changes; (2) DIC was consumed by aquatic photosynthetic organisms in the epilimnion during the stratification period, leading to a decrease in DIC concentration, partial pressure of CO2 (pCO2) and CO2 emission flux, and an increase in stable carbon isotope (δ13CDIC). During the mixing period, the trend was reversed; (3) During the thermal stratification, aquatic photosynthesis and water temperature were the primary factors controlling DIC variations in both the epilimnion and thermocline. Regarding the hypolimnion, calcite dissolution, organic matter decomposition, and water temperature were the dominant controlling factors. These results indicate that although carbon-rich karst groundwater provides a plentiful supply of DIC in the DLD reservoir, its availability is still influenced by variations in the reservoir's thermal structure and the metabolic processes of aquatic photosynthetic organisms. Therefore, to better estimate the regional carbon budget in a reservoir or lake, future studies should especially consider the combined effects of BCP and thermal structure variations on carbon variations.

Alkaline hydrogenotrophic methanogenesis in Methanococcus vannielii at low carbon dioxide concentrations

Capture of carbon dioxide from the atmosphere is challenging and thermodynamically expensive because of its dilute concentration (421 ppm, December 2023). Utilizing the concentrating effect of dissolving atmospheric CO2 in alkaline solution to form dissolved inorganic carbon (DIC), we explored the potential of an alkalotolerant hydrogenotrophic methanogen, Methanococcus vannielii, to capture and convert CO2 at low partial pressures to methane. Kinetic constants for CO2 reduction to CH4 were determined from experiments in serum bottles at low pCO2 at 30˚C. At pH 7, 8, and 9, the apparent KM is 0.4, 1.2, and 1.2 mM DIC and the apparent vmax is 5.6, 7.8, and 2.9 mmol CH4 L−1 OD−1 hr−1, respectively. Using atmosphere-equilibrated DIC concentrations at pH 7, 8, and 9, methane formation rates were 1.1, 2.3, and 2.1 mmol CH4 L−1 OD−1 hr−1, respectively. Our data show that alkaline hydrogenotrophic methanogenesis is an alternative to photosynthetic CO2 fixation for biological capture and conversion of CO2 at atmospheric concentrations at reasonable rates.

Development of an autonomous on-site dissolved inorganic carbon analyzer using conductometric detection

BackgroundThe increase in anthropogenic CO2 concentrations in the Earth's atmosphere since the industrial revolution has resulted in an increased uptake of CO2 by the oceans, leading to ocean acidification. Dissolved Inorganic Carbon (DIC) is one of the key variables to characterize the seawater carbonate system. High quality DIC observations at a high spatial-temporal resolution is required to improve our understanding of the marine carbonate system. To meet the requirements, autonomous DIC analyzers are needed which offer a high sampling frequency, are cost-effective and have a low reagent and power consumption. ResultsWe present the development and validation of a novel analyzer for autonomous measurements of DIC in seawater using conductometric detection. The analyzer employs a gas diffusion sequential injection approach in a “Tube In A Tube” configuration that facilitates diffusion of gaseous CO2 from an acidified sample through a gas permeable membrane into a stream of an alkaline solution. The change in conductivity in the alkaline medium is proportional to the DIC concentration of the sample and is measured using a detection cell constructed of 4 hollow brass electrodes. Physical and chemical optimizations of the analyzer yielded a sampling frequency of 4 samples h−1 using sub mL reagent volumes for each measurement. Temperature and salinity effects on DIC measurements were mathematically corrected to increase accuracy. Analytical precision of ±4.9 μmol kg−1 and ±9.7 μmol kg−1 were achieved from measurements of a DIC reference material in the laboratory and during a field deployment in the southwest Baltic Sea, respectively. SignificanceThis study describes a simple, cost-effective, autonomous, on-site benchtop DIC analyzer capable of measuring DIC in seawater at a high temporal resolution as a step towards an underwater DIC sensor. The analyzer is able to measure a wide range of DIC concentrations in both fresh and marine waters. The achieved accuracy and precision offer an excellent opportunity to employ the analyzer for ocean acidification studies and CO2 leakage detection in the context of Carbon Capture and Storage operations.

Effects of the hydrologic process and geochemistry on dissolved carbon in shallow groundwater surrounding Qinghai Lake

A high concentration of dissolved carbon in groundwater increases drinking water health risks and carbon transport. Understanding the comprehensive impact of hydrologic processes and geochemistry on dissolved carbon in shallow groundwater also is a fundamental prerequisite for estimating the carbon budget of lakes in the Tibetan Plateau. This study investigated the spatial–temporal characteristics of the hydrologic process, geochemistry and dissolved carbon in shallow groundwater by the stable isotope tracer method, Piper diagram and Boomerang envelope model. The driving factors of dissolved carbon in shallow groundwater were explored by correlation analysis and redundancy analysis. The results showed low dissolved inorganic carbon (DIC) concentrations and high dissolved organic carbon (DOC) concentrations during the thawing period and rainy season and high DIC concentrations and low DOC concentrations during the freezing period. The seepage velocity, soil carbon dioxide dissolution and gypsum dissolution were the main factors influencing DIC concentrations during the thawing period. The mineralization and decomposition of DOC and dissolution of carbonate rocks were the main factors influencing DIC concentrations during the freezing period. The concentrations of DOC were mainly controlled by the adsorption of Ca2+ and Mg2+, microbial activity and pollutants produced by human activities. Our results are useful for ecological sustainable development, human health, and research on the carbon transport in groundwater in the Tibetan Plateau.

Escalating Carbon Export from High-Elevation Rivers in a Warming Climate.

High-elevation mountains have experienced disproportionately rapid warming, yet the effect of warming on the lateral export of terrestrial carbon to rivers remains poorly explored and understood in these regions. Here, we present a long-term data set of dissolved inorganic carbon (DIC) and a more detailed, short-term data set of DIC, δ13CDIC, and organic carbon from two major rivers of the Qinghai-Tibetan Plateau, the Jinsha River (JSR) and the Yalong River (YLR). In the higher-elevation JSR with ∼51% continuous permafrost coverage, warming (>3 °C) and increasing precipitation coincided with substantially increased DIC concentrations by 35% and fluxes by 110%. In the lower-elevation YLR with ∼14% continuous permafrost, such increases did not occur despite a comparable extent of warming. Riverine concentrations of dissolved and particulate organic carbon increased with discharge (mobilization) in both rivers. In the JSR, DIC concentrations transitioned from dilution (decreasing concentration with discharge) in earlier, colder years to chemostasis (relatively constant concentration) in later, warmer years. This changing pattern, together with lighter δ13CDIC under high discharge, suggests that permafrost thawing boosts DIC production and export via enhancing soil respiration and weathering. These findings reveal the predominant role of warming in altering carbon lateral export by escalating concentrations and fluxes and modifying export patterns.

Groundwater‐surface water interaction, dissolved organic carbon oxidation and dissolution in carbonate aquifers

AbstractThe high primary porosity and permeability of eogenetic karst aquifers permit water recharged through secondary dissolution features to be temporarily stored in aquifer matrix porosity. The recharged water contains elevated dissolved organic carbon (DOC) concentrations that, when oxidized, enhance limestone dissolution and impact carbon cycling. We evaluate the relationship between DOC oxidation and limestone dissolution using observations at a stream sink‐rise system and reversing spring in the Floridan aquifer, north‐central Florida, USA, where subsurface residence times of recharged water are days and months, respectively. We estimate water chemical compositions during surface water‐groundwater interactions at these two systems with mixing models of surface water and groundwater compositions and compare them with measured DOC, dissolved inorganic carbon (DIC), Ca2+ and dissolved organic nitrogen (DON) concentrations. Differences between measured and modelled concentrations represent net changes that can be attributed to calcite dissolution and redox reactions, including DOC oxidation. DOC losses and Ca2+ gains exhibit significant (p &lt; 0.01) inverse linear correlations at both the reversing spring (slope = −0.9, r2 = 0.99) and the sink‐rise system (slope = −0.4, r2 = 0.72). DOC oxidation in both systems was associated with decreases in the molar C:N ratio (DOC:DON). Significant (p &lt; 0.01) positive linear correlations between increases in Ca2+ and DIC concentrations after correcting for DIC derived from calcite dissolution occurred at both the reversing spring (slope = 1.3, r2 = 0.99) and the sink‐rise system (slope = 1.61, r2 = 0.75). Greater deviations from the expected slope of −1 or +1 at the sink‐rise system than at the reversing spring indicate DOC oxidation contributes less dissolution at the sink‐rise system than at the reversing spring, likely from shorter storage in the subsurface. A portion of the deviation from expected slope values can be explained by the dissolution of Mg‐rich carbonate or dolomite rather than pure calcite dissolution. Despite this, slope values reflect kinetic effects controlling incomplete consumption of carbonic acid during dissolution reactions.