Dissolved Inorganic Carbon In Groundwater Research Articles

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.

Estimation of Groundwater Residence Time Using Radiocarbon and Stable Isotope Ratio in Dissolved Inorganic Carbon and Soil CO2

AbstractEstimation of residence time of groundwater, particularly in regions with inadequate surface waters are very important for formulating sustainable groundwater management policies. We developed a technique for extracting dissolved inorganic carbon (DIC) quantitatively from water for measuring its 14C contents and presented the analytical details here. We also measured stable carbon isotope ratio (δ13C) in soil CO2 and groundwater DIC to correct the groundwater 14C ages. In addition, 14C in soil CO2 were measured for making necessary correction in the initial activity of the recharging water. The corrected 14C contents in the groundwater samples were used to estimate their residence times employing Lumped Parameter Models (LPM), a set of mathematical models to account for the processes that take place during transport from the recharge to the sampling spots. We present a case study focused on the calculation of radiocarbon ages and residence times for a groundwater sample collected from the campus of Physical Research Laboratory in Ahmedabad, Gujarat, India. The study also includes estimations of groundwater residence times using previously measured 14C ages of groundwater samples from Gujarat, India. Various factors controlling the groundwater ages in the LPM and their applicability are discussed.

Combining hydrochemistry and 13C analysis to reveal the sources and contributions of dissolved inorganic carbon in the groundwater of coal mining areas, in East China.

East China is a highly aggregated coal-grain composite area where coal mining and agricultural production activities are both flourishing. At present, the geochemical characteristics of dissolved inorganic carbon (DIC) in groundwater in coal mining areas are still unclear. This study combined hydrochemical and carbon isotope methods to explore the sources and factors influencing DIC in the groundwater of different active areas in coal mining areas. Moreover, the 13C isotope method was used to calculate the contribution rates of various sources to DIC in groundwater. The results showed that the hydrochemical types of groundwater were HCO3-Ca·Na and HCO3-Na. The main water‒rock interactions were silicate and carbonate rock weathering. Agricultural areas were mainly affected by the participation of HNO3 produced by chemical fertilizer in the weathering of carbonate rocks. Soil CO2 and carbonate rock weathering were the major sources of DIC in the groundwater. Groundwater in residential areas was primarily affected by CO2 from the degradation of organic matter from anthropogenic inputs. Sulfate produced by gypsum dissolution, coal gangue accumulation leaching and mine drainage participated in carbonate weathering under acidic conditions, which was an important factor controlling the DIC and isotopic composition of groundwater in coal production areas. The contribution rates of groundwater carbonate weathering to groundwater DIC in agricultural areas and coal production areas ranged from 57.46 to 66.18% and from 54.29 to 62.16%, respectively. In residential areas, the contribution rates of soil CO2 to groundwater DIC ranged from 51.48 to 61.84%. The results will help clarify the sources and circulation of DIC in groundwater under the influence of anthropogenic activities and provide a theoretical reference for water resource management.

An isolated chemolithoautotrophic ecosystem deduced from environmental isotopes: Ayyalon cave (Israel)

The stable isotopes composition of chemolithoautotrophic cave ecosystems is known to differ from epigenic caves. Here we show that in addition, dead carbon (devoid of 14C), is utilized and transferred throughout this ecosystem, rendering it unsuitable for radiocarbon dating. The connectivity of the Ayyalon Cave ecosystem with the surface is studied, along with its sources of energy and carbon, as well as the interconnections between its constituents. We use isotopic evidence to show that its ancient resilient ecosystem is based on an underground food web depending on rich biomass production by chemolithoautotrophic nutrient supplies, detached from surface photosynthesis. Carbon isotopic values indicate that: (1) the microbial biota use bicarbonate from the groundwater (23.34 pMC [% of modern carbon]) rather than the atmospheric CO2 above the water (71.36 pMC); (2) the depleted 14C signal is transferred through the entire ecosystem, indicating that the ecosystem is well-adapted and based on the cave biofilm which is in turn based on groundwater-dissolved inorganic carbon. Incubation of Ayyalon biofilm with 14C-labelled bicarbonate indicates uptake of the radio-labeled bicarbonate by sulfur-oxidizing proteobacteria Beggiatoa, suggesting that these sulfur-oxidizing microorganisms use the water-dissolved inorganic carbon for chemolithoautotrophic carbon fixation. Organic matter in the cave is much lighter in its stable nitrogen and carbon isotopes compared with respective surface values, as expected in chemolithoautotrophic systems. This evidence may be applicative to subsurface voids of ancient Earth environments and extraterrestrial systems.

Provenance of Inorganic Carbon Sinks in Closed Basins

AbstractMuch dissolved inorganic carbon (DIC) may exist in lacustrine carbonates in the terminal lakes of closed basins in arid areas, and inorganic carbon sinks in arid regions are an important hypothesis of global carbon cycle research in recent years. Previous studies have made significant progress in estimating the inorganic carbon content. However, the source of inorganic carbon sinks remains unclear. Here, we choose four typical arid closed basins in North China to investigate the provenance of inorganic carbon sinks. The results show that CO2 absorbed by saline‐alkaline soil is the main source of groundwater DIC in the study area, with a contribution rate of approximately 50%. Forty‐three groundwater radiocarbon ages from arid closed basins indicate that the DIC in groundwater is transported along the direction of water flow and deposited in terminal lakes, forming inorganic carbon sinks. Our study suggests that the total inorganic carbon contents of Zhuye Lake, Yanchi Lake, Huahai Lake, and Qinghai Lake in the Holocene are 0.318 Pg, 0.003 Pg, 0.160 Pg, and 3.289 Pg, respectively. The results demonstrate that inorganic carbon sinks are much larger than lake organic carbon storage, thereby serving as an important carbon cycle factor in arid regions.

Helium-carbon systematics of groundwaters in the Lassen Peak Region

Carbon dioxide emissions from active subaerial volcanoes represent 20–50% of the annual global volcanic CO2 flux (Barry et al., 2014). Passive degassing of carbon from the flanks of volcanoes, and the associated accumulation of dissolved inorganic carbon (DIC) within nearby groundwater, also represents a potentially important, yet poorly constrained flux of carbon to the surface (Werner et al., 2019). Here we investigate sources and sinks of DIC in groundwaters in the Lassen Peak region of California. Specifically, we report and interpret the relative abundance and isotopic composition of helium (3He, 4He) and carbon (12C, 13C, 14C) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected 3He/4He values between 0.19 and 7.44 RA (where RA = air 3He/4He = 1.39 × 10−6), all in excess of the radiogenic production value (~0.05 RA), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (δ13C) vary between −12.6 and − 27.7‰ (vs. VPDB). Measured groundwater DIC/3He values fall in the range of 2.2 × 1010 to 1.1 × 1012. Using helium and carbon isotope data, we explore several conceptual models to estimate surface carbon contributions and to differentiate between DIC derived from soil CO2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use 14C to identify soil-derived DIC (assuming decadal-to-centennial groundwater ages and a soil CO214C activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent δ13C signature between −10.3 and − 59.3‰ (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/3He between 7.0 × 109 and 1.0 × 1012. These apparent δ13C and C/3He values are substantially isotopically lighter than and greater than canonical MORB values, respectively. We suggest that >95% of any external (non-soil-derived) DIC in groundwater must thus be non-mantle in origin (i.e., slab derived or assimilated organic carbon). We further investigate possible sources of external DIC to groundwater using two idealized conceptual approaches: a pure (unfractionated) source mixing model (after Sano and Marty, 1995) and a scenario that invokes fractionation due to calcite precipitation. Because the former model requires carbon contributions from an organic source component with unrealistically low δ13C (~ − 60‰), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial 14C activity. Thus, we cannot rule out the possibility that the true fraction of non-surface-derived DIC in these samples is lower or negligible, despite the pervasive mantle-derived He isotope signatures throughout the region. Following the 14C approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to ~2.2 × 106 kg/yr, which is lower than previous magmatic carbon flux estimates from the Lassen region (Rose and Davisson, 1996). We find that the passive dissolved carbon flux could represent a maximum of ~4–18% of the total Lassen geothermal CO2 degassing flux (estimated to be ~3.5 × 107 kg/yr Rose and Davisson, 1996; Gerlach et al., 2008), which is still more than an order of magnitude smaller than soil gas CO2 flux estimates (7.3–11 × 107 kg/yr) for nearby volcanoes (Sorey et al., 1998; Gerlach et al., 1999; Evans et al., 2002; Werner et al., 2014). We conclude that passive dissolved carbon fluxes should be combined with geothermal fluxes and soil gas fluxes to obtain a complete picture of volcanic carbon emissions globally. Our approach highlights the utility of measuring helium isotopes in concert with the full suite of noble gas abundances, tritium, δ13C and 14C, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.

δ13C and 14C activity of groundwater DOC and DIC in the volcanically active and arid Loa Basin of northern Chile

Organic and inorganic carbon reservoirs are investigated in surface and groundwater in the semi to hyper-arid Río Loa Basin in Northern Chile. Part of the study area is within the Andean volcanic arc, and volcanism is responsible for large inputs of 14C-depleted CO2 which hampers groundwater residence time estimations using dissolved inorganic carbon (DIC). To better understand the area’s carbon system, we investigated 14C and δ13C in dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in groundwater and surface water. DOC concentrations are low in all water samples analyzed, 16–53 μM. Fluorescence and δ13C measurements on DOC indicate that dissolved organic matter (DOM) entering groundwater has characteristics of humic compounds derived from terrestrial plants in the recharge area. Fluorescence is lost in groundwater in the lower part of the system due to microbial or abiotic degradation. Changes in 14CDOC and δ13CDOC also indicate that microbial activity contributes to DOC, possibly from geogenic CO2. While the range of 14CDIC is very large, 1.6 to >50 pmC, that of 14CDOC is restricted between 53 and 72 pmC. We estimated C residence times in the volcanic arc, based on corrected 14CDOC, are <3,200 years compared to 14CDIC estimates that range from 2,000 to 15,000 years. While uncertainties in the estimate due to sources and sinks of DOC within the different aquifers exist, the range in age is somewhat restricted, despite the large distances that separate different sampling points and the different types of aquifers sampled. This leads us to conclude that wetter climate conditions in the past increased recharge and storage of the aquifers, and DOC inputs to recharging water was enhanced by more widespread plant growth during those past wet climates.

Biogeochemical Controls on 13CDIC Signatures from Circum-Neutral pH Groundwater in Cu–W–F Skarn Tailings to Acidic Downstream Surface Waters

Regular features of ground and surface waters affected by drainage from mine waste include their acidity and elevated concentrations of dissolved metals, with their attendant negative effects on drinking water quality and aquatic life. One parameter that aids in buffering these waters against acidity and sustains aquatic life is dissolved inorganic carbon (DIC). In this study, the chemical and isotopic (δ13C) composition of primary calcite and DIC (δ13CDIC) in groundwater and surface waters within and downstream, respectively, of abandoned Cu–W–F skarn tailings at Yxsjöberg, Sweden, were used to trace the biogeochemical processes controlling their respective δ13CDIC signatures. In addition, the δ13C signatures of the inorganic (carbonate) fractions of the tailings were used to verify the formation of secondary carbonates within the tailings. Lower average δ13C values of the carbonate fractions (δ13Ccarb = −2.7‰) relative to those of the primary calcite (δ13C = +0.1‰) from the orebodies from which the tailings originated pointed to the precipitation of secondary carbonates. These lower δ13Ccarb signatures were assumed to represent mixed-source C signals involving isotopically light CO2 from the atmosphere, the degradation of organic matter in the upper part of the tailings and HCO3− from calcite dissolution. The groundwater δ13CDIC values (−12.6‰ to −4.4‰) were far lower than the hypothetical range of values (−4.6‰ to +0.7‰) for primary calcite and secondary carbonate dissolution. These signatures were attributed to carbonate (calcite and secondary carbonate) dissolution and the degradation of dissolved organic carbon (DOC) from various organic sources such as peat underneath the tailings and the surrounding forests. Downstream surface water samples collected in May had low δ13CDIC values (−16‰) and high DOC (14 mg C/L) compared to the groundwater samples. These signatures represented the oxidation of the DOC from the wash out of the mires and forests during the snowmelt and spring flood. The DOC and δ13CDIC values of the surface waters from June to September ranged from 6–15 mg·C/L and −25‰ to −8.6‰, respectively. These signatures were interpreted to reflect mixed C sources, including carbonate dehydration by acidity from Fe3+ hydrolysis due to the mixing of groundwater with surface waters and the subsequent diffusive loss of CO2 (g), aquatic photosynthesis, photooxidation, DOC degradation, as well as microbial respiration. Although the 13CDIC signatures of the downstream surface waters seemed to be seasonally controlled and influenced by variable groundwater contributions, the lack of data with respect to DIC concentrations, coupled with multiple potential biogeochemical processes that could influence the DIC pool and 13CDIC values, made it difficult to identify the major regulating process of the 13CDIC signatures. Therefore, other complimentary isotopes and elemental concentrations are recommended in order to decipher the dominant biogeochemical process.

Geochemical Characteristics and Ecological Significance of Carbon Isotopes in Groundwater Under the Influence of Different Land Use Types in Karst Areas

Based on the seasonal characteristics of groundwater hydrochemistry and the carbon isotopes (δ13C) of dissolved inorganic carbon (DIC) in the Hongjiadu Basin, Guizhou Province, this paper discusses the natural processes and anthropogenic factors affecting the characteristics of δ13CDIC in karst groundwaters under different land use types. The results show that the main sources of DIC in groundwater are carbonate weathering and soil CO2. In winter, the δ13CDIC values for groundwater ranged from -14.8‰ to -4.1‰ with an average of -10.1‰ and, in summer, ranged from -14.5‰ to -6.3‰ with an average of -10.2‰. Sulfuric acid from sulfide oxidation in coal-bearing strata and acid rain is involved in carbonate weathering, resulting in the enrichment of groundwater with heavy carbon isotopes. Due to the soil CO2 effect, the δ13CDIC values of woodland groundwater experiencing less disturbance from human activities are lower in summer than in winter. The degradation of organic matter input from residential areas is a significant contributor of DIC to groundwater. The average values of δ13CDIC in winter and summer were -11.9‰ and -11.6‰, respectively, and the seasonal difference was relatively small in residential areas. During different seasons and for different types of land use, human activities could lead to differences in groundwater δ13CDIC values and hydrochemistry. Therefore, δ13CDIC can reflect the impact of human activities on karst aquifers, which has important ecological significance.

Hydro-ecological controls on dissolved carbon dynamics in groundwater and export to streams in a temperate pine forest

Abstract. We studied the export of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) from forested shallow groundwater to first-order streams, based on groundwater and surface water sampling and hydrological data. The selected watershed was particularly convenient for such study, with a very low slope, with pine forest growing on sandy permeable podzol and with hydrology occurring exclusively through drainage of shallow groundwater (no surface runoff). A forest plot was instrumented for continuous eddy covariance measurements of precipitation, evapotranspiration, and net ecosystem exchanges of sensible and latent heat fluxes as well as CO2 fluxes. Shallow groundwater was sampled with three piezometers located in different plots, and surface waters were sampled in six first-order streams; river discharge and drainage were modeled based on four gauging stations. On a monthly basis and on the plot scale, we found a good consistency between precipitation on the one hand and the sum of evapotranspiration, shallow groundwater storage and drainage on the other hand. DOC and DIC stocks in groundwater and exports to first-order streams varied drastically during the hydrological cycle, in relation with water table depth and amplitude. In the groundwater, DOC concentrations were maximal in winter when the water table reached the superficial organic-rich layer of the soil. In contrast, DIC (in majority excess CO2) in groundwater showed maximum concentrations at low water table during late summer, concomitant with heterotrophic conditions of the forest plot. Our data also suggest that a large part of the DOC mobilized at high water table was mineralized to DIC during the following months within the groundwater itself. In first-order streams, DOC and DIC followed an opposed seasonal trend similar to groundwater but with lower concentrations. On an annual basis, leaching of carbon to streams occurred as DIC and DOC in similar proportion, but DOC export occurred in majority during short periods of the highest water table, whereas DIC export was more constant throughout the year. Leaching of forest carbon to first-order streams represented a small portion (approximately 2 %) of the net land CO2 sink at the plot. In addition, approximately 75 % of the DIC exported from groundwater was not found in streams, as it returned very fast to the atmosphere through CO2 degassing.

Stable isotope and aquatic geochemistry of a typical subtropical karst subterranean stream in southwest China

A hydrogeochemical and isotopic study was conducted on the subterranean karst stream, namely the Guancun subterranean stream (GSS). The hydrogeochemical processes of the GSS were controlled through calcite dissolution and precipitation and were driven by the concentration of CO2, which controlled changes in the pH and of PCO2 in the water. The δ18O and δD values of the GSS were within the global meteoric water line and the local meteoric water line, thereby indicating that the water of the GSS comes from precipitation. Certain abnormal δ18O and δD values suggest the effect of evaporation on the GSS given its use in a particular irrigation system, wherein the GSS in transformed into a surface stream and flows for a relatively long time on the surface during the wet season. The δ13CDIC values of the GSS range from −13.5 to −11.3‰ in the dry season and from −13.9 to −9.5‰ in the wet season, thereby indicating that the GSS belongs to a semi-open system. The δ13CDIC values in the GSS were formed by the δ13CDIC values of the soil CO2 and carbonate dissolution at different proportions. According to the simplified mass balance formula, the contributions of carbonate dissolution to the dissolved inorganic carbon (DIC) of the GSS were calculated to be 50.2–58.3% and 48.7–64.7% in the dry and wet seasons, respectively, thereby indicating a less than 50% carbonate dissolution contribution during the formation of DIC in karst groundwater. Moreover, sulfuric acid and nitric acid were observed to participate in karst processes.

Carbonate system biogeochemistry in a subterranean estuary – Waquoit Bay, USA

Quantifying carbon fluxes associated with submarine groundwater discharge (SGD) remains challenging due to the complex biogeochemistry of the carbonate system in the subterranean estuary (STE). Here we conducted time series measurements of total alkalinity (TAlk) and dissolved inorganic carbon (DIC) in a well-studied coastal aquifer (Waquoit Bay, Massachusetts, USA). Groundwater samples were collected monthly from May 2009 to June 2010 across the freshwater-saltwater mixing zone of the Waquoit Bay (WB) STE. The concentrations of both TAlk and DIC in zero-salinity groundwater were variable, but were lower than those in the bay water (S∼28). DIC underwent slightly non-conservative mixing between low and intermediate salinities while there was an apparent additional DIC source at high salinity (>20) in all seasons. TAlk concentrations exhibited even stronger variations, with evidence of both production and consumption in high salinity zones, and consistent TAlk consumption at intermediate salinity in summer and fall (June–December, 2009). The increases in DIC and TAlk at high salinity were attributed to aerobic respiration and denitrification in WB sediments during bay water recharge of the STE. We infer that the loss of TAlk at intermediate salinity reflects H+ production as reduced compounds (e.g. Fe2+) are oxidized within the STE. In terms of impacts on surface water inorganic carbon budgets, the SGD-derived DIC flux was mainly controlled by seasonal changes in SGD while a combination of TAlk concentration variability and SGD drove the TAlk flux. SGD-derived DIC, aqueous CO2, and H+ fluxes to the bay were ∼40–50% higher in summer vs. in winter, a result of enhanced marine groundwater flux and significant TAlk removal (proton addition) during periods of high seawater intrusion. Furthermore, the SGD-derived DIC flux was consistently greater than TAlk flux regardless of season, indicating that SGD serves to reduce the CO2 buffering capacity of surface water. Our results highlight the importance of seasonality and subsurface biogeochemical processes on the subterranean estuary carbonate system and the resulting impact on SGD-derived TAlk, DIC, aqueous CO2, and H+ fluxes to the coastal ocean.

Primary diagenetic copper carbonate at the Malbunka copper deposit, Amadeus Basin, Northern Territory, Australia

The Malbunka copper deposit, located about 220km west of Alice Springs, in the Northern Territory of Australia, may be a rare example of primary formation of copper carbonate mineralization. This deposit consists of unusual azurite disks up to 25cm diameter, and lesser amounts of secondary azurite crystals and malachite. Carbon isotope values of the copper carbonate minerals are consistent with formation from groundwater-dissolved inorganic carbon. Oxygen isotope thermometry formation temperature estimates are 5–16°C above ambient temperatures, suggesting the copper carbonates formed at a depth between 0.3 and 1.6km in the Amadeus Basin. Azurite fluid inclusion waters are rich in boron, chlorine, and other elements suggestive of dilute oil basin formation fluids. In addition, presence of euhedral tourmaline with strong chemical zonation suggest that this was a low temperature diagenetic setting. The strong correlation of structures associated with hydraulic fracturing and rich copper carbonate mineralization suggest a strongly compartmentalized overpressure environment. It is proposed that copper carbonates of the Malbunka deposit formed when deep, copper-rich formation fluids were released upward by overpressure-induced failure of basin sediments, permitting mixing with carbonate-rich fluids above. This work bears directly upon exploration for a new type of primary copper deposit, through understanding of the conditions of genesis.

Factors controlling the isotope composition of dissolved inorganic carbon in a karst-dominated wetland catchment, Guizhou Province, Southwest China

Wetlands contain a large proportion of the world’s carbon, of which dissolved inorganic carbon (DIC) is one of the important fractions in wetland carbon cycle. We collected groundwater, river water, and wetland water from the Caohai catchment to investigate the isotope composition of DIC and inorganic carbon cycling. The main sources of groundwater DIC were carbonate dissolution and soil CO2. Groundwater was the main source of riverine DIC, but the δ13CDIC value in river water showed a more positive excursion than groundwater because of phytoplankton photosynthesis and CO2 evasion. Seasonal variations in DIC concentrations and the δ13CDIC indicate the influence of local rainfall events in the high-flow season and the longer residence time of water in the low-flow season. There was marked seasonal variation in the pCO2 and δ13CDIC in wetland water. During the high-flow season, the pCO2 in the emergent plant zone was higher than that of the atmosphere because of respiration of roots and sediments. Because of photosynthesis, the pCO2 in the submerged plant zone was lower than that of the atmosphere. Furthermore, in this zone, the δ13CDIC ranged from −15.13 to −6.68 ‰ (mean value of −10.79 ‰), and may have been influenced by chemically enhanced fractionation and photosynthesis. In the low-flow season, the pCO2 was mostly higher than atmospheric pCO2 because of organic matter decomposition in sediments. Additionally, during this season, the δ13CDIC ranged from −6.23 to −0.06 ‰ (mean value of −2.52 ‰), and may have been influenced by CO2 evasion, CO2 reduction to methane, and phytoplankton photosynthesis.

Field demonstration of CO2 leakage detection in potable aquifers with a pulselike CO2-release test.

This study presents two field pulselike CO2-release tests to demonstrate CO2 leakage detection in a shallow aquifer by monitoring groundwater pH, alkalinity, and dissolved inorganic carbon (DIC) using the periodic groundwater sampling method and a fiber-optic CO2 sensor for real-time in situ monitoring of dissolved CO2 in groundwater. Measurements of groundwater pH, alkalinity, DIC, and dissolved CO2 clearly deviated from their background values, showing responses to CO2 leakage. Dissolved CO2 observed in the tests was highly sensitive in comparison to groundwater pH, DIC, and alkalinity. Comparison of the pulselike CO2-release tests to other field tests suggests that pulselike CO2-release tests can provide reliable assessment of geochemical parameters indicative of CO2 leakage. Measurements by the fiber-optic CO2 sensor, showing obvious leakage signals, demonstrated the potential of real-time in situ monitoring of dissolved CO2 for leakage detection at a geologic carbon sequestration (GCS) site. Results of a two-dimensional reactive transport model reproduced the geochemical measurements and confirmed that the decrease in groundwater pH and the increases in DIC and dissolved CO2 observed in the pulselike CO2-release tests were caused by dissolution of CO2 whereas alkalinity was likely affected by carbonate dissolution.

The curved 14C vs. δ13C relationship in dissolved inorganic carbon: A useful tool for groundwater age- and geochemical interpretations

Determination of the 14C content of dissolved inorganic carbon (DIC) is useful for dating of groundwater. However, in addition to radioactive decay, the 14C content in DIC (14CDIC) can be affected by many geochemical and physical processes and numerous models have been proposed to refine radiocarbon ages of DIC in groundwater systems. Changes in the δ13C content of DIC (δ13CDIC) often can be used to deduce the processes that affect the carbon isotopic composition of DIC and the 14C value during the chemical evolution of groundwater. This paper shows that a curved relationship of 14CDIC vs. δ13CDIC will be observed for groundwater systems if (1) the change in δ13C value in DIC is caused by a first-order or pseudo-first-order process, e.g. isotopic exchange between DIC and solid carbonate, (2) the reaction/process progresses with the ageing of the groundwater, i.e. with decay of 14C in DIC, and (3) the magnitude of the rate of change in δ13C of DIC is comparable with that of 14C decay. In this paper, we use a lumped parameter method to derive a model based on the curved relationship between 14CDIC and δ13CDIC. The derived model, if used for isotopic exchange between DIC and solid carbonate, is identical to that derived by Gonfiantini and Zuppi (2003). The curved relationship of 14CDIC vs. δ13CDIC can be applied to interpret the age of the DIC in groundwater. Results of age calculations using the method discussed in this paper are compared with those obtained by using other methods that calculate the age of DIC based on adjusted initial radiocarbon values for individual samples. This paper shows that in addition to groundwater age interpretation, the lumped parameter method presented here also provides a useful tool for geochemical interpretations, e.g. estimation of apparent rates of geochemical reactions and revealing the complexity of the geochemical environment.

Contrasting carbon export dynamics of human impacted and pristine tropical catchments in response to a short‐lived discharge event

AbstractUtilising newly available instrumentation, the carbon balance in two small tropical catchments was measured during two discharge events at high temporal resolution. Catchments share similar climatic conditions, but differ in land use with one draining a pristine rainforest catchment, the other a fully cleared and cultivated catchment. The necessity of high resolution sampling in small catchments was illustrated in each catchment, where significant chemical changes occurred in the space of a few hours or less. Dissolved and particulate carbon transport dominated carbon export from the rainforest catchment during high flow, but was surpassed by degassing of CO2 less than 4 h after the discharge peak. In contrast, particulate organic carbon dominated export from the cleared catchment, in all flow conditions with CO2 evasion accounting for 5–23% of total carbon flux. Stable isotopes of dissolved inorganic carbon (DIC) in the ephemeral rainforest catchment decreased quickly from ~1.5 ‰ to ~ −16 ‰ in 5 h from the flood beginning. A two‐point mixing model revealed that in the initial pulse, over 90% of the DIC was of rainwater origin, decreasing to below 30% in low flow. In the cultivated catchment, δ13CDIC values varied significantly less (−11.0 to −12.2 ‰) but revealed a complex interaction between surface runoff and groundwater sources, with groundwater DIC becoming proportionally more important in high flow, due to activation of macropores downstream. This work adds to an increasing body of work that recognises the importance of rapid, short‐lived hydrological events in low‐order catchments to global carbon dynamics. Copyright © 2013 John Wiley &amp; Sons, Ltd.

Isotopes of Carbon in a Karst Aquifer of the Cumberland Plateau of Kentucky, USA

In this study, the concentration and isotopic composition of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) are measured in the karst groundwater of the Otter Creek watershed of the Cumberland Plateau of Kentucky, USA. Comparisons among these data and with the geochemistry of carbonate and gypsum equilibrium reactions reveal that DOC concentration is inversely related to discharge, multiple reaction pathways provide DIC with isotopic enrichment that may be directly related to mineral saturation, and oxidation of reduced sulfur is possible for dissolution. DOC is derived from C3 vegetation with an average δ13CDOC of ‒27‰. DIC in groundwater is derived from both pedogenic CO2 and HCO3- from dissolved carbonate. At input sites to the karst aquifers DIC concentrations are expectedly low, less than 1 mmol/L, in waters that are undersaturated with respect to calcite. At the output of these karst aquifers DIC concentrations reach 3 mmol/L in waters that are at or above calcite saturation. Values of δ13CDIC range between ‒6.3 and ‒12.4‰ with CO2 degassing and calcite precipitation at some sites obfuscating a simple relationship between δ13CDIC, discharge, and mineral saturation. In addition, concentrations of DIC in sulfur seeps within the watershed range between 2–7 mmol/L with δ13CDIC values in some samples skewed more toward the anticipated value of carbonate bedrock than would be expected from reactions with carbonic acid alone. This suggests that the oxidation of reduced sulfur from shallow oilfield brines liberates bedrock DIC through reactions with sulfuric acid.Keywords: dissolved organic carbon, dissolved inorganic carbon, sulfur redox, ion geochemistry, saturation index. Keywords: dissolved organic carbon, dissolved inorganic carbon, sulfur redox, ion geochemistry, saturation index. DOI: 10.3986/ac.v42i2-3.668

Constraining carbon sources and growth rates of freshwater microbialites in Pavilion Lake using 14C analysis

This study determined the natural abundance isotopic compositions ((13)C, (14)C) of the primary carbon pools and microbial communities associated with modern freshwater microbialites located in Pavilion Lake, British Columbia, Canada. The Delta(14)C of dissolved inorganic carbon (DIC) was constant throughout the water column and consistent with a primarily atmospheric source. Observed depletions in DIC (14)C values compared with atmospheric CO(2) indicated effects due either to DIC residence time and/or inputs of (14)C-depleted groundwater. Mass balance comparisons of local and regional groundwater indicate that groundwater DIC could contribute a maximum of 9-13% of the DIC. (14)C analysis of microbial phospholipid fatty acids from microbialite communities had Delta(14)C values comparable with lake water DIC, demonstrating that lake water DIC was their primary carbon source. Microbialite carbonate was also primarily derived from DIC. However, some depletion in microbialite carbonate (14)C relative to lake water DIC occurred, due either to residence time or mixing with a (14)C-depleted carbon source. A detrital branch covered with microbialite growth was used to estimate a microbialite growth rate of 0.05 mm year(-1) for the past 1000 years, faster than previous estimates for this system. These results demonstrate that the microbialites are actively growing and that the primary carbon source for both microbial communities and recent carbonate is DIC originating from the atmosphere. While these data cannot conclusively differentiate between abiotic and biotic formation mechanisms, the evidence for minor inputs of groundwater-derived DIC is consistent with the previously hypothesized biological origin of the Pavilion Lake microbialites.

Hydrogeochemistry and dissolved inorganic carbon isotopic composition on karst groundwater in Maolan, southwest China

The forest ecosystem in the Maolan karst forest, southwest China is the only concentrated, intact, and relatively stable karst forest ecosystem which has survived in the area at the same latitude in the world, and is a valuable karst forest plant resource as well. Groundwater samples from Maolan karst forest were collected from wells and springs during summer; and concentrations of major ions and dissolved inorganic carbon (DIC) isotopic compositions were measured. The pH values range from 7.2 to 8.3 results from the dissolution of carbonate, HCO3− is the dominant species of DIC in groundwater. Calcium and HCO3−, followed by Mg2+ and SO42− dominate the chemical composition of major ions in the groundwaters. Groundwater samples have δ13C values in the range from −8.1‰ to −16.6‰, which are lower than that of the other karst city groundwaters in the southwest China. Combining δ13CDIC ratios with measurements of HCO3− and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Carboniferous carbonate aquifers, where processes can be both degradation of organic matters in the soil and the carbonate dissolution.