Dissolved Inorganic Carbon Concentrations Research Articles

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 < 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 < 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.

Carbon wet deposition flux and river carbon output in a forest watershed in permafrost region of the Da Xing'an Mountains.

Carbon wet deposition and river carbon output in river basins are important components of global carbon cycle. The assessment of both properties is of great significance for regional carbon budget. However, research on these topics in high-latitude permafrost regions in China is still lacking. We conducted dynamic monitoring of carbon wet deposition and carbon output in the river from May 28th to October 30th, 2022, in Laoyeling watershed, a typical forested watershed in the Da Xing'an Mountains permafrost region. We analyzed the variations of carbon component concentrations and fluxes in precipitation and river water, and estimated the contribution of carbon wet deposition to carbon output in the watershed. The results showed that wet deposition fluxes of dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and total dissolved carbon (TDC) in the Laoyeling watershed were 1354.86, 684.59, and 2039.45 kg·km-2, respectively. The fluxes of DOC, DIC, TDC, particulate organic carbon (POC), particulate inorganic carbon (PIC), and total carbon (TC) in the river were 601.75, 1977.30, 2579.05, 125.13, 21.99, and 2726.17 kg·km-2, respectively. The contribution of TDC wet deposition to the river TDC output was 9941.89 kg, accounting for 17.6% of total output. The DIC concentration in the river showed significant seasonal differences, with increased runoff resulting from precipitation leading to a decrease in DIC concentration in the river and showing a clear dilution effect, while the concentrations of DOC, POC, and PIC increased, mainly due to erosion effect. In conclusion, carbon wet deposition flux in the Laoyeling watershed was mainly determined by precipitation, and its contribution to river carbon output was relatively small compared to other factor. Runoff was the dominant factor affecting river carbon output. The results would provide important insights into carbon cycling and carbon budget balance in permafrost regions under climate change.

Production and fluxes of inorganic carbon and alkalinity in a subarctic subterranean estuary

In this study, we focus on the biogeochemical processes that produce both dissolved inorganic carbon (DIC) and total alkalinity (TA) along a subarctic subterranean estuary (STE) located in the Gulf of St. Lawrence (Magdalen Island, Qc, Canada) in order to evaluate the DIC and TA fluxes as well as the buffering capacity of the exported groundwater to coastal waters. DIC and TA do not behave conservatively during mixing along the groundwater flow path and this implies the occurrence of internal redox reactions that control both their production and consumption. In addition, we show that the origin and composition of the organic carbon within the system alter the carbonate parameters by generating low pH conditions (5.9 - 7.2) and contributing to non-carbonate alkalinity (NCA) that accounts for more than 30% of TA. Whereas iron cycling plays a key role in the production of DIC in the fresh and low-salinity groundwaters, the precipitation of sulfide minerals neutralize the acidity produced by the metabolically produced CO2, in the saline groundwater where sulfate is available. The STE pCO2, computed from the DIC-pHNBS pair ranged from a few ppm to 16000 ppm that results in a CO2 evasion rate of up to 310 mol m−2d−1 to the atmosphere. Based on Darcy flow and the mean concentrations of DIC and carbonate alkalinity (Ac = TA - NCA) in the discharge zone, fluxes derived from submarine groundwater discharge were estimated at 1.43 and 0.70 mol m−2d−1 for DIC and Ac, respectively. Despite a major part of the metabolic CO2 being lost along the groundwater flow path, the SGD-derived DIC flux was still greater than the Ac flux, implying that groundwater discharge reduces the buffering capacity of the receiving coastal waters. This site-specific scale study demonstrates the importance of diagenetic reactions and organic matter remineralization processes on carbonate system parameters in STE. Our results highlight that subarctic STEs could be hot spots of CO2 evasion and a source of acidification to coastal waters that should be considered in carbon budgets.

Characterization of the benthic biogeochemical dynamics after flood events in the Rhône River prodelta: a data–model approach

Abstract. At the land–sea interface, the benthic carbon cycle is strongly influenced by the export of terrigenous particulate material across the river–ocean continuum. Episodic flood events delivering massive sedimentary materials can occur, but their short-term impact on carbon cycling is poorly understood. In this paper, we use a coupled data–model approach to estimate the temporal variations in sediment–water fluxes, biogeochemical pathways and their reaction rates during these abrupt phenomena. We studied one episodic depositional event in the vicinity of the Rhône River mouth (NW Mediterranean Sea) during the fall–winter of 2021/22. The distributions of dissolved inorganic carbon (DIC), sulfate (SO42-) and methane (CH4) were measured in sediment porewaters collected every 2 weeks before and after the deposition of a 25 cm sediment layer during the main winter flood event. Significant changes in the distribution of DIC, SO42- and CH4 concentrations were observed in the sediment porewaters. The use of an early diagenetic model (FESDIA) to calculate biogeochemical reaction rates and fluxes revealed that this type of flood event can increase the total organic carbon mineralization rate in the sediment by 75 % a few days after deposition. In this period, sulfate reduction is the main process contributing to the increase in total mineralization relative to non-flood deposition. The model predicts a short-term decrease in the DIC flux out of the sediment from 100 to 55 mmolm-2d-1 after the deposition of the new sediment layer with a longer-term increase by 4 %, therefore implying an initial internal storage of DIC in the newly deposited layer and a slow release over relaxation of the system. Furthermore, examination of the stoichiometric ratios of DIC and SO42- as well as model output over this 5-month window shows a decoupling between the two modes of sulfate reduction following the deposition – organoclastic sulfate reduction (OSR) intensified in the newly deposited layer below the sediment surface, whereas anaerobic oxidation of methane (AOM) intensified at depth below the former buried surface. The bifurcation depth of sulfate reduction pathways, i.e., the sulfate–methane transition zone (SMTZ), is shifted deeper by 25 cm in the sediment column following the flood deposition. Our findings highlight the significance of short-term transient biogeochemical processes at the seafloor and provide new insights into the benthic carbon cycle in the coastal ocean.

Assessing biogeochemical controls on porewater dissolved inorganic carbon cycling in the gas hydrate-bearing sediments of the Makran accretionary wedge, Northeastern Arabian Sea off Pakistan

Quantitatively assessing the porewater dissolved inorganic carbon (DIC) cycling in methane-enriched marine sediments is crucial to understanding the contributions of different carbon sources to the global marine carbon pool. In this study, Makran accretionary wedge was divided into Zone 1 (high methane flux area) and Zone 2 (background area). Porewater geochemical compositions (Cl–, SO42–, NH4+, Mg2+, Ca2+, Ba2+, DIC and δ13C-DIC) and a reaction-transport model were used to determine the DIC source and calculate the DIC flux through carbonate precipitation and releasing into overlying seawater in sediments. Zone 1 is characterized by the shallower depth of sulfate-methane transition (SMT), where most of porewater sulfate was consumed by anaerobic oxidation of methane (AOM). In contrast, a relatively low flux of methane diffusion in Zone 2 results in a deeper SMT depth and shallow sulfate is predominantly consumed by organoclastic sulfate reduction (OSR). Based on the porewater geochemical profiles and δ13C mass balance, the proportions of porewater DIC originating from methane were calculated as 51% in Zone 1 and nearly 0% in Zone 2. An increase of porewater DIC concentration leads to authigenic carbonate precipitation. Solid total inorganic carbon (TIC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM) analysis display that carbonate content increases with depth and aragonite appears at or below the depths of SMT. Meanwhile, the flux of DIC released from sediments calculated by the reaction-transport model is 51.3 ~ 90.4 mmol/m2·yr in Zone 1, which is significantly higher than that in Zone 2 (22.4 mmol/m2·yr). This study demonstrates that AOM serves as the dominant biogeochemical process regulating the porewater DIC cycle, which has an important impact on the authigenic carbonate burial and the seawater carbonate chemistry.

Extra O2 evolution reveals an O2-independent alternative electron sink in photosynthesis of marine diatoms.

Following the principle of oxygenic photosynthesis, electron transport in the thylakoid membranes (i.e., light reaction) generates ATP and NADPH from light energy, which is subsequently utilized for CO2 fixation in the Calvin-Benson-Bassham cycle (i.e., dark reaction). However, light and dark reactions could discord when an alternative electron flow occurs with a rate comparable to the linear electron flow. Here, we quantitatively monitored O2 and total dissolved inorganic carbon (DIC) during photosynthesis in the pennate diatom Phaeodactylum tricornutum, and found that evolved O2 was larger than the consumption of DIC, which was consistent with 14CO2 measurements in literature. In our measurements, the stoichiometry of O2 evolution to DIC consumption was always around 1.5 during photosynthesis at different DIC concentrations. The same stoichiometry was observed in the cells grown under different CO2 concentrations and nitrogen sources except for the nitrogen-starved cells showing O2 evolution 2.5 times larger than DIC consumption. An inhibitor to nitrogen assimilation did not affect the extra O2 evolution. Further, the same physiological phenomenon was observed in the centric diatom Thalassiosira pseudonana. Based on the present dataset, we propose that the marine diatoms possess the metabolic pathway(s) functioning as the O2-independent electron sink under steady state photosynthesis that reaches nearly half of electron flux of the Calvin-Benson-Bassham cycle.

Influences of hydrodynamics on dissolved inorganic carbon in deep subtropical reservoir: Insights from hydrodynamic model and carbon isotope analysis

Dam construction significantly impacts river hydrodynamics, subsequently influencing carbon biogeochemical processes. However, the influence of hydrodynamic conditions on the migration and transformation of Dissolved Inorganic Carbon (DIC) remains uncertain. To bridge this knowledge gap, we integrated hydrochemistry, isotopic composition (δ13CDIC), and a hydrodynamic model (CE-QUAL-W2) to examine the distinctions, control mechanisms, and environmental effects of DIC biogeochemical processes in a typical large and deep reservoir (Hongjiadu Reservoir) under different hydrodynamic conditions. We evaluated hydrodynamic alterations through the Schmidt stability index and relative water column stability. The analysis disclosed that during weak hydrodynamics periods, the energy necessary for complete mixing the surface and deep water was 34 times higher (3615.32 J/m2 vs.106.86 J/m2), and stability was 13 times greater (312.96 vs. 24.69) compared to periods of strong hydrodynamics. Additionally, the spatiotemporal heterogeneity of DIC concentrations (1.4 % to -9.1 %) and δ13CDIC (-1.7 % to -19.5 %) from the dry to wet seasons reflected disparities in DIC control mechanisms under varied hydrodynamic conditions. Based on model simulations, our calculations indicate that during weak hydrodynamics periods, the enhancement of the biological carbon pump effect resulted in substantial sequestration of DIC, reaching up to 379.6 t-DIC·d−1 in the water. Conversely, during strong hydrodynamics periods, DIC retention capacity decreased by 69.2 t·d−1, resulting in reservoir CO2 emissions of 22.7 × 104 t, which were more than 7 times higher than during weak hydrodynamics periods (3.2 × 104 t). Our findings emphasize the discernible impact of hydrodynamic conditions on reservoir biogeochemical processes related to DIC. Considering the increasing construction of reservoirs globally, understanding and controlling hydrodynamic conditions are crucial for mitigating CO2 emissions and optimizing reservoir management.

Spatiotemporal variability and environmental effects of greenhouse gases, nutrients, and dissolved carbons in an ice-covered reservoir

Ice cover restructures the distribution of substances in ice and underlying water and poses non-negligible environmental effects. This study aimed to clarify the spatiotemporal variability and environmental effects of methane (CH4), nitrous oxide (N2O), total nitrogen (TN), total phosphorus (TP), dissolved organic carbon (DOC), and dissolved inorganic carbon (DIC) in ice and water columns during different ice-covered periods. We surveyed the ice-growth, ice-stability, and ice-melt periods in an ice-covered reservoir located in Northeast China. The results showed that underlying water (CH4: 1218.9 ± 2678.9 nmol L−1 and N2O: 19.3 ± 7.3 nmol L−1) and ice (CH4: 535.2 ± 2373.1 nmol L−1 and N2O: 9.9 ± 1.5 nmol L−1) were sources of atmospheric greenhouse gases. N2O concentrations were the highest in the bottom water of the reservoir while CH4 accumulated the most below the ice in the riverine zone. These can be attributed to differences in the solubilities and relative molecular masses of the two gases. Higher concentrations of N2O, TN, TP, DOC, and DIC were recorded in the underlying water than those in the ice due to the preferential redistribution of these substances in the aqueous phase during ice formation. Additionally, we distinguished between bubble and no-bubble areas in the riverine zone and found that the higher CH4 concentrations in the underlying water than those in the ice were due to CH4 bubbles. In addition, we reviewed various substances in ice-water systems and found that the substances in ice-water systems can be divided into solute exclusion and particle entrapment, which are attributed to differences between dissolved and particulate states. These findings are important for a comprehensive understanding of substances dynamics during ice-covered periods.

Divergent response of blue carbon components to wetland types and hydrological effects in typical estuarine wetlands of Jiaozhou Bay, China

As ecosystems subject to periodic tides, estuarine wetlands have a significant capacity to sequester carbon over time. Understanding the distribution patterns of soil carbon components and identifying the key factors influencing these patterns are key to gaining insight into the function of “blue carbon” in coastal wetlands. To clarify the response of soil carbon components to wetland types and hydrological effects in estuarine wetlands, the typical estuarine wetlands in Jiaozhou Bay, China were selected as the study area, and the soil organic carbon (SOC), dissolved organic carbon (DOC), microbial biomass carbon (MBC), soil inorganic carbon (SIC) and dissolved inorganic carbon (DIC) under different wetland types and hydrological effects were investigated. The results showed that the SOC, SIC, and MBC contents were significantly influenced by the wetland types. The SOC and MBC contents were as follows: mudflat (GT) > Phragmites australis wetland (PA) > Suaeda salsa wetland (SS). The overall content of SIC was highest in PA, followed by GT and SS. Hydrological effects had significant influence on the soil MBC, DOC and DIC contents. With the increase hydrological effects, the soil MBC content decreased by 38.89%–72.22%, while the DOC and DIC contents increased by 15.13%–19.89% and 13.41%–86.70%, respectively. The results of the correlation analysis and structural equation model indicated that wetland types and hydrological effects directly or indirectly (through changes in soil pH, bulk density, water content, and salinity) drove the changes in soil carbon contents in estuarine wetlands. Altogether, our findings implied that the alterations of wetland types and hydrological effects will affect the blue carbon function of estuarine wetlands. In the future, for accurate assessment of a blue carbon budget for estuarine wetlands, the differences in wetland types and hydrological effects of different areas should be considered.

Calibrating Non‐Thermal Effects on Planktic Foraminiferal Mg/Ca for Application Across the Cenozoic

AbstractForaminiferal Mg/Ca has proven to be a powerful paleothermometer for reconstructing past sea‐surface temperature, which, among other applications, is a critical parameter for boron isotope reconstructions of past surface ocean pH and PCO2. However, recent laboratory culture studies indicate seawater pH and the total dissolved inorganic carbon content (DIC) may both exert a significant additional control on foraminiferal Mg/Ca, likely influencing paleotemperature records as a result of seawater chemistry evolution on geologic timescales. In addition, the seawater Mg/Ca composition (Mg/Casw) has been shown to reduce the sensitivity of foraminiferal Mg/Ca to temperature and possibly its sensitivity to the carbonate system as well. Here we present new Mg/Ca data from laboratory culture experiments with living planktic foraminifera— Globigerinoides ruber (p), Trilobatus sacculifer, and Orbulina universa— grown under a range of different pH and/or seawater DIC conditions and in low Mg/Casw to mimic the chemical composition of the Paleocene ocean. We also conducted targeted [Ca] experiments to help define Mg/Cacalcite–Mg/Casw relationships for each species and conducted new pH experiments with G. bulloides. We find that pH effects on foraminiferal Mg/Ca are reduced or absent at Mg/Casw = 1.5 mol/mol in all three species, and that T. sacculifer is generally insensitive to variable DIC and pH, making it the ideal species for Mg/Ca SST reconstructions back to 20 Ma. We apply our new T. sacculifer calibration to a Middle Miocene Mg/Ca record and provide recommendations for interpreting Mg/Ca records from extinct species.

The benthic-pelagic coupling affects the surface water carbonate system above groundwater-charged coastal sediments

Submarine groundwater discharge (SGD) can be a significant source of dissolved nutrients, inorganic and organic carbon, and trace metals in the ocean and therefore can be a driver for the benthic-pelagic coupling. However, the influence of hypoxic or anoxic SGD on the carbonate system of coastal seawater is still poorly understood. In the present study, the production of dissolved inorganic carbon (DIC) and alkalinity (AT) in coastal sediments has been investigated under the impact of oxygen-deficient SGD and was estimated based on the offset between the measured data and the conservative mixing of the end members. Production of ATand DIC was primarily caused by denitrification and sulphate reduction. The ATand DIC concentrations in SGD decreased by approximately 32% and 37% mainly due to mixing with seawater counterbalanced by reoxidation and CO2release into the atmosphere. Total SGD-ATand SGD-DIC fluxes ranged from 0.1 to 0.2mol m-2d-1and from 0.2 to 0.3mol m-2d-1, respectively. These fluxes are probably the reason why the seawater in the Bay of Puck is enriched in ATand DIC compared to the open waters of the Baltic Sea. Additionally, SGD had low pH and was undersaturated with respect to the forms of the aragonite and calcite minerals of CaCO3. The seawater of the Bay of Puck also turned out to be undersaturated in summer (Inner Bay) and fall (Outer Bay). We hypoth​e​size that SGD can potentially contribute to ocean acidification and affect the functioning of the calcifying invertebrates.

Tidal effects on carbon dioxide emission dynamics in intertidal wetland sediments

Understanding the control mechanisms of carbon dioxide (CO2) emissions in intertidal wetland sediments is beneficial for the concern of global carbon biogeochemistry and climate change. Nevertheless, multiple controls on CO2 emissions from intertidal wetland sediments to the atmosphere still need to be clarified. This study investigated the effect of tidal action on CO2 emissions from salt marsh sediments covered by Spartina alterniflora in the Jiaozhou Bay wetland using the static chamber method combined with an infrared CO2 detector. The results showed that the CO2 emission fluxes from the sediment during ebb tides were higher than those during flood tides. The whole wetland sediment acted as a weak source of atmospheric CO2 (average flux: 24.44 ± 16.80 mg C m−2 h−1) compared to terrestrial soils and was affected by the cycle of seawater inundation and exposure. The tidal influence on vertical dissolved inorganic carbon (DIC) transport in the sediment was also quantitated using a two-end member mixing model. The surface sediment layer (5–15 cm) with maximum DIC concentration during ebb tides became the one with minimum DIC concentration during flood tides, indicating the DIC transport from the surface sediment to seawater. Furthermore, aerobic respiration by microorganisms was the primary process of CO2 production in the sediment according to 16 S rDNA sequencing analysis. This study revealed the strong impact of tidal action on CO2 emissions from the wetland sediment and provided insights into the source-sink pattern of CO2 and DIC at the land-ocean interface.

Impacts of Basal Melting of the Totten Ice Shelf and Biological Productivity on Marine Biogeochemical Components in Sabrina Coast, East Antarctica

AbstractTo clarify the impacts of basal melting of the Antarctic ice sheet and biological productivity on biogeochemical processes in Antarctic coastal waters, concentrations of dissolved inorganic carbon (DIC), total alkalinity (TA), inorganic nutrients, chlorophyll a, and stable oxygen isotopic ratios (δ18O) were measured from the offshore slope to the ice front of the Totten Ice Shelf (TIS) during the spring/summer of 2018, 2019, and 2020. Modified Circumpolar Deep Water (mCDW) intruded onto the continental shelf off the TIS and flowed along bathymetric troughs into the TIS cavity, where it formed a buoyant mixture with glacial meltwater from the ice shelf base. Physical oceanographic processes mostly determined the distributions of DIC, TA, and nutrient concentrations. However, photosynthesis and dilution by meltwater from sea ice and the ice shelf base decreased DIC, TA, and nutrient concentrations in surface water near the ice front. These causes also reduced the partial pressure of CO2 (pCO2) in surface water by more than 100 μatm with respect to mCDW in austral summer of 2018 and 2020, and the surface water became a strong CO2 sink for the atmosphere. Phytoplankton photosynthesis changed DIC and TA in a molar ratio of 106:16. Thus, pCO2 decreased mostly as a result of photosynthesis while dilution by glacial and sea ice meltwater had a small effect. The nutrient consumption ratio suggested that photosynthesis was stimulated by iron in the water column, supplied to the surface layer via buoyancy‐driven upwelling and basal ice shelf meltwater in addition to sea ice meltwater.

Changes in Dissolved Inorganic Carbon Across Yangtze River Regulated by Dam and River‐Lake Exchange

AbstractThe boom in dam construction and continuous river‐lake exchange has had a profound impact on the transmission and transformation of riverine dissolved inorganic carbon (DIC). An in‐depth understanding of the change mechanisms of DIC concentrations and sources driven by dam operation and lake recharge is crucial for regulating greenhouse gas emissions and evaluating the impact of DIC on the global carbon cycle. This study investigated dam‐ and lakes‐driven DIC via the concentration and δ13C of DIC, combined with anions, cations, δD and δ18O in the main stream of the Yangtze River. DIC showed a decreasing trend from upper reach (2,262.31 ± 113.69 μmol kg−1) to lower reach (1,771.61 ± 89.36 μmol kg−1). Carbonate dissolution proportion (from 36.45% to 28.44%) and atmospheric CO2 proportion (from 37.51% to 22.94%) of DIC decreased from upper reach to lower reach, whereas soil CO2 proportion of DIC (from 26.01% to 48.63%) increased. The control of dam operation on DIC biogeochemical process was revealed from different time scales. From the perspective of short‐term seasonal changes (from 2020 to 2021), the mineralization of organic matter in the dry season strengthened CO2 degassing and calcite precipitation, reducing the DIC and increasing the proportion of soil CO2. Meanwhile, longer periods of runoff retention provided sufficient time for water–rock reactions in the wet season and increased the DIC and carbonate dissolution source in the reservoir area. On a long‐term scale (from 2009 to 2021), a decrease in pH driven by sediment mineralization contributed to an annual increase in DIC in the reservoir. The flow of lakes mixed into the mainstream was revealed by the enrichment of δ18O, and river‐communicating recharge decreased the DIC and carbonate dissolution source. We show that dam operation and lake inflow change DIC concentrations and sources and therefore need to be considered in the transmission and transformation processes of DIC in the river‐ocean continuum.

Preparation and quality control of in‐house reference materials for marine dissolved inorganic carbon and total alkalinity measurements

AbstractAccurate measurements of seawater carbonate chemistry are crucial for marine carbon cycle research. Certified reference materials (CRMs) are typically analyzed alongside samples to correct measurements for calibration drift. However, the COVID‐19 pandemic led to a limited access to CRMs. In response to this shortage, we prepared and monitored in‐house reference materials (IHRMs) for total alkalinity (TA) and dissolved inorganic carbon (DIC), over 12 and 15 months, respectively. Overall, TA was stable, but a slight increase in DIC of about 2 μmol kg−1 occurred over 15 months. The increase could potentially be attributed to bacterial growth, despite mercuric chloride fixation and repeated UV exposure. It is noted that this small increase was most likely within our instrument and measurements uncertainties. Our repeated measurements also identified a few bottles that had TA or DIC concentrations 4–5 μmol kg−1 higher than the rest, indicating issues during cleaning, fixation, or storage of individual bottles. This study emphasizes the importance of careful and continuous monitoring if self‐prepared IHRMs are used. Given that the amount of work required is very high, IHRM preparation is only recommended when CRMs are not available.