High Dissolved Inorganic Carbon Concentrations Research Articles

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.

Compositional variations in algal organic matter during distinct growth phases in karst water

Inland surface water plays an important role in global carbon cycling, which responds to transformation between dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). Studies have shown that algae in karst lakes and reservoirs can convert DIC to organic matter (OM) and form stable carbon sinks via photosynthesis. However, the pathways of conversion of inorganic carbon to organic carbon during algal growth remain unclear and need further investigation. In this study, spectroscopic techniques were applied to investigate the variations in algal organic matter (AOM) composition in the growth metabolism of Chlorella vulgaris and Scenedesmus obliquus under simulated karst water condition. The results showed that algal extracellular organic matter (EOM) contained high DIC concentration during the adaptation phase, which formed the carbon source for algal photosynthesis. In addition, DOC in algae increased after entering the stationary phase, while more OM was released into water. As algal growth proceeded, the amino groups in EOM were consumed to produce more aromatic protein-like material, while more lipid material was produced in intracellular organic matter (IOM). The spectral characterization results could intuitively determine AOM dynamics in different growth stages of algae, which can be used for establishing effective approaches for detecting organic carbon variations and responding to regional carbon cycling in karst water.

Influence of the advection of water masses in the Ballenas Channel on the CO[formula omitted] system in Bahía de los Angeles (Mexico)

The surface waters of the Ballenas Channel (BC) are characterized by thermohaline and biogeochemical conditions that depend on the water masses present. Since these surface waters are transported into Bahía de los Ángeles (BLA), it is relevant to assess their timing, intensity and biogeochemical implications on a seasonal scale. For this purpose, the seasonal and spatial variability of temperature, salinity, dissolved inorganic carbon (DIC) and total alkalinity (TA), were quantified over 19 discrete monthly monitoring campaigns that covered 12 stations in BLA from June 2017 to October 2019. In addition, vertical CTD profiles of thermohaline, apparent oxygen utilization (AOU), and nitrate were obtained for the purposes of identifying the water masses present and determining how they change by season. It was found that the dynamics of DIC, AOU, nitrate, and temperature in BLA respond to the presence of Subtropical Subsurface Water (SSW), evident by the enrichment of the bay with high DIC and nitrate concentrations during winter, but during summer occurs the opposite, with the presence of the Gulf of California Water (GCW). In addition, zonation analysis within BLA indicated three regions consistently found along the year, attributed to different physical and biogeochemical processes. Finally, we also interpreted the data in the context of the interannual variability due to ENSO events by using a relationship between observed temperature–DIC data. A 20-year calculated DIC (DICcalc) time series for an area near BLA indicated that during summer periods under the influence of La Niña events, the DICcal in front to BLA could be 10-12μmol kg −1 higher than El Niño events. These high DIC values, likely promoted by an increased volume of SSW in the BC, is accompanied by a higher nutrients concentration, suggesting that the interannual variability must interact with biological processes within BLA and other adjacent embayment’s in this region.

Mitochondrial phosphoenolpyruvate carboxylase contributes to carbon fixation in the diatom Phaeodactylum tricornutum at low inorganic carbon concentrations.

Photosynthetic carbon fixation is often limited by CO2 availability, which led to the evolution of CO2 concentrating mechanisms (CCMs). Some diatoms possess CCMs that employ biochemical fixation of bicarbonate, similar to C4 plants, but whether biochemical CCMs are commonly found in diatoms is a subject of debate. In the diatom Phaeodactylum tricornutum, phosphoenolpyruvate carboxylase (PEPC) is present in two isoforms, PEPC1 in the plastids and PEPC2 in the mitochondria. We used real-time quantitative polymerase chain reaction, Western blots, and enzymatic assays to examine PEPC expression and PEPC activity, under low and high concentrations of dissolved inorganic carbon (DIC). We generated and analyzed individual knockout cell lines of PEPC1 and PEPC2, as well as a PEPC1/2 double-knockout strain. While we could not detect an altered phenotype in the PEPC1 knockout strains at ambient, low or high DIC concentrations, PEPC2 and the double-knockout strains grown under ambient air or lower DIC availability conditions showed reduced growth and photosynthetic affinity for DIC while behaving similarly to wild-type (WT) cells at high DIC concentrations. These mutants furthermore exhibited significantly lower 13 C/12 C ratios compared to the WT. Our data imply that in P. tricornutum at least parts of the CCM rely on biochemical bicarbonate fixation catalyzed by the mitochondrial PEPC2.

Uranium (VI) sorption on illite under varying carbonate concentrations: Batch experiments, modeling, and cryogenic time-resolved laser fluorescence spectroscopy study

Dissolved inorganic carbon (DIC) present in groundwaters can affect both the aqueous and surface species of hexavalent uranium (U(VI)) owing to its strong complexation ability with U(VI). However, the effect of DIC on U(VI) sorption on illite, which is a critical component of argillaceous rocks, is still unclear. In this study, we investigated the sorption of U(VI) on conditioned illite du Puy with varying DIC concentrations (up to 250 mM DIC) as a function of pH through batch sorption experiments, surface complexation modeling, and cryogenic time-resolved laser fluorescence spectroscopy (TRLFS). The distribution coefficients of U(VI) decreased with an increase in the DIC concentration. At relatively high DIC concentrations with respect to experimentally investigated range (≥100 mM DIC), no U(VI) sorption was observed. The U(VI) sorption on illite was modeled using the two-site protolysis non-electrostatic surface complexation and cation exchange model. Two ternary surface complexation reactions with carbonate were needed to depict the experimental sorption data in addition to binary and ternary hydroxo surface complexation reactions used to describe the U(VI) sorption to illite without carbonate. Cryogenic TRLFS data revealed that U(VI) did sorb to illite at high DIC concentrations (up to 10 mM DIC). The spectra were unchanged with varying DIC concentrations (2.0, 5.0, and 10 mM DIC) at pH ∼8.5, indicating that the surface speciation of U(VI) remained the same. The decay curves were biexponential, which further indicates that at least two surface species were responsible for the sorption. These results could improve the performance assessment of a deep geological disposal system in a sedimentary host rock.

Disentangling the Effects of Ocean Carbonation and Acidification on Elemental Contents and Macromolecules of the Coccolithophore Emiliania huxleyi.

Elemental contents change with shifts in macromolecular composition of marine phytoplankton. Recent studies focus on the responses of elemental contents of coccolithophores, a major calcifying phytoplankton group, to changing carbonate chemistry, caused by the dissolution of anthropogenically derived CO2 into the surface ocean. However, the effects of changing carbonate chemistry on biomacromolecules, such as protein and carbohydrate of coccolithophores, are less documented. Here, we disentangled the effects of elevated dissolved inorganic carbon (DIC) concentration (900 to 4,930μmolkg−1) and reduced pH value (8.04 to 7.70) on physiological rates, elemental contents, and macromolecules of the coccolithophore Emiliania huxleyi. Compared to present DIC concentration and pH value, combinations of high DIC concentration and low pH value (ocean acidification) significantly increased pigments content, particulate organic carbon (POC), and carbohydrate content and had less impact on growth rate, maximal relative electron transport rate (rETRmax), particulate organic nitrogen (PON), and protein content. In high pH treatments, elevated DIC concentration significantly increased growth rate, pigments content, rETRmax, POC, particulate inorganic carbon (PIC), protein, and carbohydrate contents. In low pH treatments, the extents of the increase in growth rate, pigments and carbohydrate content were reduced. Compared to high pH value, under low DIC concentration, low pH value significantly increased POC and PON contents and showed less impact on protein and carbohydrate contents; however, under high DIC concentration, low pH value significantly reduced POC, PON, protein, and carbohydrate contents. These results showed that reduced pH counteracted the positive effects of elevated DIC concentration on growth rate, rETRmax, POC, PON, carbohydrate, and protein contents. Elevated DIC concentration and reduced pH acted synergistically to increase the contribution of carbohydrate–carbon to POC, and antagonistically to affect the contribution of protein–nitrogen to PON, which further shifted the carbon/nitrogen ratio of E. huxleyi.

Differential Sensitivity of a Symbiont‐Bearing Foraminifer to Seawater Carbonate Chemistry in a Decoupled DIC‐pH Experiment

AbstractLarger benthic foraminifera (LBF) are unicellular eukaryotic calcifying organisms and an important component of tropical and subtropical modern and ancient oceanic ecosystems. They are major calcium carbonate producers and important contributors to primary production due to the photosynthetic activity of their symbiotic algae. Studies investigating the response of LBF to seawater carbonate chemistry changes are therefore essential for understanding the impact of climate changes and ocean acidification (OA) on shallow marine ecosystems. In this study, calcification, respiration, and photosynthesis of the widespread diatom‐bearing LBF Operculina ammonoides were measured in laboratory experiments that included manipulation of carbonate chemistry parameters. pH was altered while keeping dissolved inorganic carbon (DIC) constant, and DIC was altered while keeping pH constant. The results show clear vulnerability of O. ammonoides to low pH and CO32− under constant DIC conditions, and no increased photosynthesis or calcification under high DIC concentrations. Our results call into question previous hypotheses, suggesting that mechanisms such as the degree of cellular control on calcification site pH/DIC and/or enhanced symbiont photosynthesis in response to OA may render the hyaline (perforate and calcitic‐radial) LBF to be less responsive to OA than porcelaneous LBF. In addition, manipulating DIC did not affect calcification when pH was close to present seawater levels in a model encompassing the total population size range. In contrast, larger individuals (>1,200 μm, >1 mg) were sensitive to changes in DIC, a phenomenon we attribute to their physiological requirement to concentrate large quantities of DIC for their calcification process.

Effects of chemical weathering and CO2 outgassing on δ13CDIC signals in a karst watershed

As the important part of carbon cycle research, riverine dissolved inorganic carbon (DIC) has attracted continuous attentions for its close relationship with global climate change. In order to investigate the dominant factors of dissolved inorganic carbon species and its stable carbon isotopic signals in large watershed under base flow condition, 81 river water samples were collected in the Xijiang River during the dry season in 2015. The elemental ratios in river water revealed the hydro-chemistry in Xijiang River were mainly controlled by the carbonate weathering. The characteristics of the most samples were the high DIC concentrations and narrow range of δ13CDIC, which can be interpreted as the result of chemical weathering under open system based on the simulated calculation of soil respiration and mineral dissolution. The relatively lower DIC concentrations and δ13CDIC values have been observed in tributaries draining silicate terrains, this result may be controlled both by the mineral dissolution and CO2 outgassing. Most samples had the over-saturated pCO2 levels compared to the atmosphere, the respiratory quotient (RQ) demonstrated that high pCO2 values were not from the biologic respiration, instead, the groundwater influx with the high soil pCO2 increased pCO2 level in river waters. The CO2 concentration gradient between river water and atmosphere caused a violent CO2 outgassing accompanied isotope fractionation. The outgassing significantly dropped the pCO2 in river water and caused an enrichment of C13 in DIC. Based on the theoretical calculation and previous observation, the negative correlation between the δ13CDIC and pCO2 in river water was caused by the CO2 outgassing. Additionally, the isotope exchange between the DIC and atmosphere CO2 can also partially increase the riverine CO2. This study examined the impacts of soil respiration, minerals dissolution and CO2 outgassing on DIC and δ13CDIC, and found that the riverine δ13CDIC is probably not reflect the mixing of source signals such as soil CO2 and carbonate, instead, it is mainly controlled by the fractionation in minerals dissolution and CO2 outgassing.

Porewater Carbonate Chemistry Dynamics in a Temperate and a Subtropical Seagrass System

Seagrass systems are integral components of both local and global carbon cycles and can substantially modify seawater biogeochemistry, which has ecological ramifications. However, the influence of seagrass on porewater biogeochemistry has not been fully described, and the exact role of this marine macrophyte and associated microbial communities in the modification of porewater chemistry remains equivocal. In the present study, carbonate chemistry in the water column and porewater was investigated over diel timescales in contrasting, tidally influenced seagrass systems in Southern California and Bermuda, including vegetated (Zostera marina) and unvegetated biomes (0–16 cm) in Mission Bay, San Diego, USA and a vegetated system (Thallasia testudinium) in Mangrove Bay, Ferry Reach, Bermuda. In Mission Bay, dissolved inorganic carbon (DIC) and total alkalinity (TA) exhibited strong increasing gradients with sediment depth. Vertical porewater profiles differed between the sites, with almost twice as high concentrations of DIC and TA observed in the vegetated compared to the unvegetated sediments. In Mangrove Bay, both the range and vertical profiles of porewater carbonate parameters such as DIC and TA were much lower and, in contrast to Mission Bay where no distinct temporal signal was observed, biogeochemical parameters followed the semi-diurnal tidal signal in the water column. The observed differences between the study sites most likely reflect a differential influence of biological (biomass, detritus and infauna) and physical processes (e.g., sediment permeability, residence time and mixing) on porewater carbonate chemistry in the different settings.

Dynamics of the Carbonate System Across the Peruvian Oxygen Minimum Zone

The oxygen minimum zone (OMZ) of Peru is recognized as a source of CO2 to the atmosphere due to upwelling that brings water with high concentrations of dissolved inorganic carbon (DIC) to the surface. However, the influence of OMZ dynamics on the carbonate system remains poorly understood given a lack of direct observations. This study examines the influence of a coastal Eastern South Pacific OMZ on carbonate system dynamics based on a multidisciplinary cruise that took place in 2014. During the cruise, onboard DIC and pH measurements were used to estimate pCO2 and to calculate the calcium carbonate saturation state (Ω aragonite and calcite). South of Chimbote (9oS), water stratification decreased and both the oxycline and carbocline moved from 150 m depth to 20-50 m below the surface. The aragonite saturation depth was observed to be close to 50 m. However, values less than 1.2 were detected close to 20 m along with low pH (minimum of 7.5), high pCO2 (maximum 1250 μatm), and high DIC concentrations (maximum 2300 μmol kg-1). These chemical characteristics are shown to be associated with Equatorial Subsurface Water (ESSW). Large spatial variability in surface values was also found. Part of this variability can be attributed to the influence of mesoscale eddies, which can modify the distribution of biogeochemical variables, such as the aragonite saturation horizon, in response to shallower (cyclonic eddies) or deeper (anticyclonic eddies) thermoclines. The analysis of a 21-year (1993-2014) data set of mean sea surface level anomalies (SSHa) derived from altimetry data indicated that a large variance associated with interannual timescales was present near the coast. However, 2014 was characterized by weak Kelvin activity, and physical forcing was more associated with eddy activity. Mesoscale activity modulates the position of the upper boundary of ESSW, which is associated with high DIC and influences the carbocline and aragonite saturation depths. Weighing the relative importance of each individual signal results in a better understanding of the biogeochemical processes present in the area.

Impact of organic and inorganic carbon on the formation of nitrite during the VUV photolysis of nitrate containing water

Nitrite formation during Vacuum UV (VUV) photolysis of nitrate-containing water has been studied in this research. Here the goal was to understand the effect of water matrix, specifically dissolved organic carbon (DOC), dissolved inorganic carbon (DIC) and dissolved oxygen (DO), on the formation of nitrite in nitrate-containing water during treatment with VUV AOP. The results confirmed that the formation of nitrite was considerable during the VUV irradiation, and it increased with increasing the UV fluence. However, the rate of nitrite formation was not linearly correlated with the UV fluence. Also, nitrite formation increased with increasing the DOC in water. Tert-butanol, as OH radical scavenger, was used to elucidate the mechanism behind the impact of DOC. The effect of DIC was only pronounced at very high DIC concentration, which led to lower formation of nitrite. When both DOC and DIC were present in water, DOC had the dominant effect on nitrite formation. DO in water had the impact of reducing the formation of nitrite. All these results can help to understand the mechanisms involved in the transformation of nitrate to nitrite in various water matrices, and guide VUV applications for scientific and industrial proposes.

Inorganic carbon promotes photosynthesis, growth, and maximum biomass of phytoplankton in eutrophic water bodies

Abstract The traditional perception in limnology has been that phytoplankton biomass in lakes is limited by phosphorus, nitrogen, and light, but not by dissolved inorganic carbon (DIC) because CO2 can be supplied from the atmosphere. We tested the possibility of carbon limitation of photosynthesis, growth, and biomass accumulation of phytoplankton communities across an alkalinity and DIC gradient (0.15–3.26 mM) in nutrient‐rich freshwater. During 47‐day long experiments, we measured phytoplankton biomass, organic carbon, calcium, DIC, pH, and oxygen in indoor, constantly mixed mesocosms with either no removal or a 70% weekly removal of the biomass. Photosynthesis was measured in the morning and in the afternoon at high biomass. Maximum biomass and organic carbon production increased two‐ to four‐fold with DIC, which supported 7% of organic carbon production at low DIC and 53% at high DIC concentration, while atmospheric CO2 uptake supplied the remainder. Weekly biomass removal increased growth rates through improved light conditions leading to enhanced total phytoplankton biomass production at high DIC. Photosynthesis was significantly higher in the morning compared to afternoon due to daily DIC depletion. We conclude that phytoplankton photosynthesis, growth rate, maximum biomass, and organic carbon production can be markedly carbon limited in eutrophic lake waters. Consequently, lakes of high DIC and pH can support a faster primary production by greater DIC use and chemically enhanced atmospheric CO2 uptake.

New insight into the biogeochemical cycling of methane, S and Fe above the Sulfate-Methane Transition Zone in methane hydrate-bearing sediments: A case study in the Dongsha area, South China Sea

Microbially-mediated methane, S and Fe cycling in the sediments can largely reduce the flux of methane from the ocean to the atmosphere. Compared to a large number of records regarding these processes in the sulfate-methane transition zone (SMTZ), detailed information of these processes in the zone above the SMTZ is still required. In this study, a short sediment core DS16 (330 cm) collected from the methane hydrate-bearing Dongsha area, Northern of the South China Sea, was examined by geochemical and microbial methods. Pore water dissolved inorganic carbon (DIC) had an increasing trend with the increasing depth of the sediment, while the value of δ13C-DIC showed a decreasing pattern. The high concentrations of DIC (up to 32.88 mM) and relatively negative δ13C-DIC (down to −30.07‰) indicated the occurrence of anaerobic oxidation of methane (AOM) to some extant above the SMTZ in this region. The variation of concentration profiles of H2S (3.69–12.71 mmol/L) and Fe(III) indicated active S and Fe redox reactions occurred in this zone. Notably, both of the decreasing trends of sulfate and Fe(III) correlated well with those of δ13C-DIC, indicating AOM and organic materials coupled with both sulfate and Fe(III) reduction. Moreover, high-throughput sequencing data showed that a number of archaea (ANME-1) and bacteria (Sulfurovum and Shewanella), which are potential methane-, S- and Fe-metabolic related microorganisms, were detected in these sediments. In addition, the functional genes related to sulfate reduction, sulfur oxidation, and Fe uptake were also detected based on metagenomics analysis. Among them, with the depth increase and Fe(III) concentration decrease, the gene related to Fe3+ uptake mechanism decreased, while the gene related to siderophore uptake mechanism remained constant or even slightly increased. Thus, we propose that bacteria acquired Fe(III) via Fe(III) uptake proteins and siderophore uptake proteins in the Fe-deficient environments for reduction, which then might support the occurrence of Fe-AOM. By integrating these data, we suggest the occurrence of active biogeochemical CH4-S-Fe cycling in the zone above the SMTZ under high methane flux.

Spatial and temporal variations in the geochemistry of shallow groundwater contaminated with nitrate at a residential site.

The concentrations of nitrate (NO3-), major ions, and dissolved inorganic carbon (DIC) and the stable carbon isotopes of DIC (δ13CDIC) in shallow groundwater below a 45 × 60m residential property was investigated over a period of 38months. Our aim was to identify the processes which control the spatial and temporal distribution of NO3- in the shallow groundwater and assess water-rock interactions linked to denitrification. Groundwater sampled quarterly from eight locations showed an average NO3- concentration of 36.8mg/L and a range between 0.1 and 214.9mg/L compared to the US EPA maximum contaminant level of 10mg/L. Heterogeneity in nitrate distribution was from residential application of N-based fertilizers offsite and from onsite application on flower beds and for lawn care. The temporal behavior of nitrate at all eight groundwater locations was markedly different and independent of seasonal hydrologic variations. Nitrate attenuation was spatially controlled by heterogeneous denitrification and rain dilution near roof drains. Groundwater locations with active denitrification were characterized by higher DIC concentrations and lower δ13CDIC from organic carbon mineralization and by higher ionic concentrations from weathering of aquifer minerals. The variation in the relative standard deviations (RSD) of the measured parameters over space (RSD-s) and time (RSD-t) was highest for NO3- associated with variable spatiotemporal input and lowest for pH, pCO2, and δ13CDIC indirectly controlled by denitrification. Denitrification induced mineral weathering products such as DIC, Ca2+, Mg2+, and HCO3- showed medium to high RSD-s and RSD-t. The RSD-s and RSD-t were positively correlated (R2 = 0.85) with the RSD-s showing approximately twofold higher magnitude than RSD-t due to greater variability between monitoring wells locations than variability at each groundwater location over time. Nitrate contamination and denitrification represent important long-term driver of aquifer weathering and changes in groundwater geochemistry below residential communities.

Geochemical controls of the microbially mediated redox cycling of uranium and iron

As oxidation state is often a primary determinant of the mobility of uranium in subsurface environments, a comprehensive understanding of the redox cycling of uranium is essential to predict the fate of this contaminant. The potential of iron to serve as both a reductant and an oxidant of uranium suggests that remediation strategies which primarily rely on the reduction of the uranyl ion (U(VI)) to the poorly soluble uranous ion (U(IV)) to immobilize uranium in the solid phase may be either enhanced or hindered depending on the biogeochemical transformations of iron. To identify the geochemical controls of both uranium and iron redox cycling, batch incubations with the model metal-reducing bacterium Shewanella putrefaciens were conducted with either U(VI), ferrihydrite, or both as terminal electron acceptors, and concentrations of dissolved inorganic carbon (DIC), calcium, and silica were varied to alter aqueous uranyl speciation and secondary mineralization pathways of ferrihydrite. The presence of ferrihydrite increased the pseudo-first order rate constant of initial uranium removal from solution in nearly all conditions compared to uranium-only controls due to a combination of abiotic U(VI) reduction by Fe(II) and solid-phase association of uranium with secondary mineralization products of ferrihydrite. Following an initial period of uranium reduction, U(IV) was oxidized by ferrihydrite which led to a rebound in dissolved uranium. Once ferrihydrite was completely consumed by microbial respiration and secondary mineralization, uranium was again removed from solution via reductive precipitation and association with secondary mineralization products. DIC and calcium enhanced the oxidative dissolution of U(IV) solids but did not affect the redox potential of the U(VI)/U(IV) redox couple despite the formation of aqueous uranyl carbonate and calcium-uranyl carbonate species. Instead, removal of dissolved Fe(II) from solution and the accompanied shift in the redox potential of the Fe(III)/Fe(II) redox couple was responsible for the abrupt shift in iron acting as a reductant of U(VI) to an oxidant of U(IV). The removal of dissolved Fe(II) via siderite precipitation at the highest DIC concentration and in the presence of calcium enhanced the oxidation of U(IV), and the presence of silica limited the conversion of ferrihydrite to magnetite and sustained U(IV) oxidation. A kinetic model was developed which could reproduce incubation time series of uranium and iron speciation provided the thermodynamic favorability of abiotic uranium-iron redox cycling was accounted for. The modeling exercise revealed that the non-uraninite U(IV) solids formed in the incubations have a redox potential approximately 84 mV lower than that of amorphous uraninite, highlighting the need for a thermodynamic characterization of non-uraninite U(IV) solids. The results of this study identify dissolved Fe(II) concentration as the primary geochemical control of the role of iron in uranium redox cycling at moderate to high DIC concentrations and emphasize the importance of considering this parameter when designing site-specific, in situ bioremediation strategies.

MoDIE: Moderate dissolved inorganic carbon (DI13C) isotope enrichment for improved evaluation of DIC photochemical production in natural waters

Photochemical reactions in natural waters are a sink for dissolved organic carbon (DOC) and a source of dissolved inorganic carbon (DIC). Although considered significant to the carbon budget of the oceans, DIC photoproduction rates remain poorly constrained due to the analytical challenge involved in accurately measuring very low production rates (likely sub-μM h− 1 for blue ocean waters) relative to high background DIC concentrations (~ 2 mM). In an attempt to overcome this analytical limitation, almost all previous DIC photoproduction studies in marine systems have relied on the stripping of background DIC prior to irradiation, with unknown consequences for the integrity of the DOC pool and its photoreactivity, and none have resulted in a satisfactory determination of photoproduced DIC in open ocean waters. Here, we use small additions of NaH13CO3 (< 10% of background DIC concentrations) to achieve moderate DI13C isotope enrichment (MoDIE) of river, estuarine, and seawater samples. We then quantify the shift in δ13C of DIC in irradiated samples via liquid chromatography - isotope ratio mass spectrometry (LC-IRMS) and use these shifts to calculate photoproduced DIC. MoDIE provides a new method to more precisely (± 56 to ± 340 nM DIC) and more rapidly quantify DIC photoproduction compared to previous methods. MoDIE was evaluated by determining initial DIC photoproduction rates, along with associated broadband photochemical efficiency data (ranging from 144 to 280 μmol DIC per mol photons absorbed), in riverine to offshore waters, and produced the earliest time point and most precise measurement of DIC photoproduction in unmodified, low-CDOM, blue water (ag(325) = 0.30 m− 1) reported to date. In addition to measuring small DIC changes from photochemistry, the use of MoDIE could provide a major advance for other ocean carbon cycling studies, including examination of oceanic respiration, carbonate mineral precipitation/dissolution, and assessment of ocean acidification.

Stable carbon isotopic composition of submerged plants living in karst water and its eco-environmental importance

The stable carbon isotopic composition of submerged plants (δ13CP) can be controlled by physiological and environmental factors. Herein, we took advantage of a short, natural karst river with an annual mean bicarbonate (HCO3−) value of 3.8mmolL−1 to study the stable carbon isotopic composition of submerged plants along the river and the influence of environmental conditions on the δ13CP values. The δ13CP values of Ottelia acuminata, Potamogeton wrightii, Vallisneria natans, and Hydrilla verticillata from upstream to downstream show a gradient and ranged from −34.8‰ to −27.8‰, −36.6‰ to −23.7‰, −35.1‰ to −25.3‰, and −38.6‰ to −26.3‰, respectively and even more depleted values for the first two species at the uppermost site. Diurnal variation of water chemistry and concentration of the dissolved inorganic carbon (DIC) and the stable carbon isotopic composition of DIC (δ13CD) indicate that the macrophytes and other primary producers in the river have a very high net photosynthetic rate. The gradient of δ13CP values was consistent with CO2 being a declining source of inorganic carbon for photosynthesis in the downstream transect. The results demonstrate that the high DIC concentration with lower negative δ13C value, particularly in karst water environment has a significant role in controlling the stable carbon isotopic composition of submerged plants living in it.

Identification of groundwater contamination zone around a reclaimed landfill using carbon isotopes.

Chemical and isotopic analyses of groundwater from piezometers localized around a reclaimed landfill were performed in order to identify the boundaries of groundwater contamination zone. Spatial distribution of dissolved inorganic carbon (DIC) concentration and stable carbon isotopes in the groundwater was used to distinguish the piezometers localized within the contaminated aquifer. Background groundwater was characterized by low DIC concentration (from 1.8 to 5.0 mmol/L) and negative values of δ13CDIC (from -20.6‰ to -12.4‰). Higher DIC concentrations (from 6.0 to 12.5 mmol/L) and higher values of δ13CDIC (from -10.9 to +3.6‰) were determined in groundwater contaminated by landfill leachate. The study confirmed that δ13CDIC value in the groundwater was a useful tracer in determining the extent of the contamination zone around the landfill. In general, upgradient from the landfill, carbon isotopic composition of groundwater depended on natural sources of carbon and δ13CDIC values were negative. Downgradient from the landfill, where groundwater was contaminated by the landfill leachate, δ13CDIC values were higher, sometimes even positive.

Enhanced autotrophic growth of Nannochloris sp. with trona buffer for sustainable carbon recycle

In this study, a potential applicability of a modified Shuisheng-4 culture medium with trona buffer for CO2(g) capture and the resultant CO2-rich solution was investigated for the autotrophic growth of Nannochloris sp. Trona is an inexpensive naturally-occurring mineral with high solubility in water. Trona solution after absorbing CO2(g) controlled at pH ~7 ~ 8 contains high dissolved inorganic carbon (DIC) concentration in water applicable to both open and closed systems and the pH is suitable for the growth. High DIC concentration was also found to enhance the autotrophic growth rate when the Na+ concentration is ~ < 0.12 M. However, the tolerance of a marine green alga, Nannochloris sp., to Na+ ion was found to twice as much as that of a freshwater green alga, Chlorella vulgaris. Therefore, it is anticipated that trona buffer solution has potential for better CO2 utilization for the mutual benefit of microalgae-derived biofuels production and carbon recycle.

Controls on the sources and cycling of dissolved inorganic carbon in the Changjiang and Huanghe River estuaries, China: 14C and 13C studies

AbstractThe Changjiang (Yangtze River) and Huanghe (Yellow River) are the two largest rivers in China, and they transport large amounts of terrestrial carbon to the coastal waters of the East China Sea and the Bohai Sea. The sources and cycling of riverine carbon in these two large river estuaries, however, have not been well studied. In this article, we present the results of dual isotope (Δ14C and δ13C) measurements of dissolved inorganic carbon (DIC) collected in the low reaches of the Changjiang and Huanghe and their estuaries during two cruises in 2014. Our results indicate that both the Changjiang and Huanghe carry very high concentrations of DIC ranging from 1384 μmol kg−1 to 1732 μmol kg−1 and 2711 μmol kg−1 to 4120 μmol kg−1, respectively, and DIC levels varied with flow rates during high and low discharge periods. The cycling of DIC exhibited conservative behavior in both the Changjiang and Huanghe estuaries, suggesting DIC levels were controlled mainly by physical mixing processes.Δ14C‐DIC values indicate that the Changjiang and Huanghe transport aged DIC (1060–1380 yr old). Both Δ14C‐DIC and δ13C‐DIC values also showed conservative mixing in the two estuaries. Using a dual carbon isotopic model, we calculated that atmospheric CO2 consumed mainly by silicate weathering was a major source, contributing 65.2 ± 9.0% and 73.4 ± 3.0% of DIC in the Changjiang and Huanghe, and 96.9–97.7% (by air‐sea exchange) of DIC in the coastal waters of the East China Sea (ECS) and Bohai Sea, respectively. Our results indicate that carbonate dissolution was an important (12.3–17.4%) but not major process controlling the high DIC levels in both rivers, as suggested previously. Compared with the large Amazon River, respiration of riverine organic matter (OM) played a less important role, contributing only 15.4–17.2% of DIC in the two Asian rivers. Flux calculations indicate that the Changjiang and Huanghe discharged 1.46 × 1013 g and 6.28 × 1011 g DIC into the ECS and Bohai Sea in 2014, which were 9 and 17 times higher than the DOC fluxes in the two rivers. These large fluxes of riverine DIC, especially of aged DIC, could have significant impacts on primary production and carbon cycling in the ECS and Bohai Sea.