CO<Subscript>2</Subscript> Air–Sea Exchange due to Calcium Carbonate and Organic Matter Storage,and its Implications for the Global Carbon Cycle

Release of CO₂ from surface ocean water owing to precipitation of CaCO₃ and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO₂ flux to the atmosphere)/(CaCO₃ precipitated). θ depends not only on water temperature and atmospheric CO₂ concentration but also on the CaCO₃ and organic carbon masses formed. In CO₂ generation by CaCO₃ precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO₂ concentration (195–375 ppmv), and increasing CaCO₃ precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO₂ production by carbonate precipitation and it results in lower CO₂ emissions from the surface layer. When atmospheric CO₂ increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO₂ transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO₂. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO₂ flux to the atmosphere is a function of the CaCO₃ and C_org net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO₂ flux near the Last Glacial Maximum is 17 to 7×10¹² mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×10¹² mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO₂ to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO₃ storage and consequent emission of CO₂. These results are in agreement with the conclusions of a number of other investigators. As the CO₂ uptake in mineral weathering is a major flux in the global carbon cycle, the CO₂ weathering pathway that originates in the CO₂ produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 10²–10⁴-year time scales.     

Anomalous carbon isotope fractionation between atmospheric CO2 and dissolved inorganic carbon induced by intense photosynthesis

A stable isotope mass-balance of dissolved inorganic carbon during a blue-green algae bloom in a softwater lake demonstrates that at low partial pressure of carbon dioxide there must be a large net negative carbon isotope fractionation between atmospheric CO₂ and the CO₂ absorbed by lake water at pH = 9.5. The net fractionation of CO₂(g) with respect to HCO⁻₃ was about −13%. compared with about +8%. for water at equilibrium with atmospheric CO₂ at pH ≈ 7. Chemical enhancement of CO₂ invasion at high pH by the reaction CO₂ + OH⁻→ HCO⁻₃ at large apparent film thicknesses may result in carbon isotope fractionation approaching that for a hydroxide solution. This phenomenon, coupled with a decrease in the photosynthetic fractionation, forced the surface water of a softwater lake to achieve increasingly negative δ¹³C values during an algal bloom, which is in the opposite sense to the trend that results from photosynthesis under less extreme conditions. This and other similar systems must operate under non-equilibrium (kinetic) conditions, causing a large kinetic fractionation during CO₂ invasion at pH > 8 and relatively large film thicknesses (i.e., low wind stress).     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Determination of hydrogen ion concentration in softwater lakes using carbon dioxide equilibria

A strategy for determining the hydrogen ion content of fresh waters is proposed that involves total dissolved inorganic carbon (DIC or σCO₂) and CO₂ partial pressure (P_CO2) measurements rather than pH electrode measurements. This recommendation derives from discrepancies between pH and carbon dioxide equilibria measurements made on several softwater lakes at the Experimental Lakes Area, northwestern Ontario. The pH calculated from DIC, P_CO2, and the first dissociation constant of carbonic acid (K₁) data was consistently higher than that directly measured with a pH electrode. Similarly, calculation of P_CO2 of surface waters from pH, DIC, and K₁ data gave values up to twice that of atmospheric saturation despite repeated equilibrations with atmospheric P_CO2. Laboratory experiments demonstrated that the high dissolved organic carbon content of these waters appears to alter the electrode response yielding pH values lower than the true values. Furthermore, the uptake of protons by weak organic acid anions appear to be the cause of the measured difference between total (Gran) and carbonate (DIC — dissolved CO₂) alkalinity. Therefore bicarbonate ion concentration must be calculated from the difference between the total dissolved inorganic carbon content and uncharged dissolved CO₂ content. These procedures should provide more accurate and consistent results in the pH trend in surface waters and hence yield a solid baseline against which the effects of acid precipitation can be assessed.     

Groundwater Discharge as a Source of Dissolved Carbon and Greenhouse Gases in a Subtropical Estuary

Groundwater may be highly enriched in dissolved carbon species, but its role as a source of carbon to coastal waters is still poorly constrained. Exports of deep and shallow groundwater-derived dissolved carbon species from a small subtropical estuary (Korogoro Creek, Australia, latitude ?31.0478°, longitude 153.0649°) were quantified using a radium isotope mass balance model (²³³Ra and ²²⁴Ra, natural groundwater tracers) under two hydrological conditions. In addition, air-water exchange of carbon dioxide and methane in the estuary was estimated. The highest carbon inputs to the estuary were from deep fresh groundwater in the wet season. Most of the dissolved carbon delivered by groundwater and exported from the estuary to the coastal ocean was in the form of dissolved inorganic carbon (DIC; 687 mmol m^?2 estuary day^?1; 20 mmol m^?2 catchment day^?1, respectively), with a large export of alkalinity (23 mmol m^?2 catchment day^?1). Average water to air flux of CO₂ (869 mmol m^?2 day^?1) and CH₄ (26 mmol m^?2 day^?1) were 5- and 43-fold higher, respectively, than the average global evasion in estuaries due to the large input of CO₂- and CH₄-enriched groundwater. The groundwater discharge contribution to carbon exports from the estuary for DIC, dissolved organic carbon (DOC), alkalinity, CO₂, and CH₄ was 22, 41, 3, 75, and 100 %, respectively. The results show that CO₂ and CH₄ evasion rates from small subtropical estuaries surrounded by wetlands can be extremely high and that groundwater discharge had a major role in carbon export and evasion from the estuary and therefore should be accounted for in coastal carbon budgets.     

CO<Subscript>2</Subscript> absorption by alkaline soils and its implication to the global carbon cycle

Motivated by the rapid increase in atmospheric CO₂ due to human activities since the Industrial Revolution, and the climate changes it produced, the world’s concerned scientific community has made a huge effort to investigate the global carbon cycle. However, the results reveal that the global CO₂ budget cannot be balanced, unless a “missing sink” is invoked. Although numerous studies claimed to find the “missing sink”, none of those claims has been widely accepted. This current study showed that alkaline soil on land are absorbing CO₂ at a rate of 0.3–3.0 μmol m⁻² s⁻¹ with an inorganic, non-biological process. The intensity of this CO₂ absorption is determined by the salinity, alkalinity, temperature and water content of the saline/alkaline soils, which are widely distributed on land. Further studies revealed that high salinity or alkalinity positively affected the CO₂ absorbing intensity, while high temperature and water content had a negative effect on the CO₂ absorbing intensity of these soils. This inorganic, non-biological process of CO₂ absorption by alkaline soils might have significant implications to the global carbon budget accounting.     

CO<Subscript>2</Subscript> emissions from a municipal site for final disposal of solid waste in Gualeguaychu,Entre Rios Province,Argentina

This paper estimates CO₂ fluxes in a municipal site for final disposal of solid waste, located in Gualeguaychu, Argentina. Estimations were made using the accumulation chamber methods, which had been calibrated previously in laboratory. CO₂ fluxes ranged from 31 to 331 g m⁻² day⁻¹. Three different populations were identified: background soil gases averaging 46 g m⁻² day⁻¹, intermediate anomalous values averaging 110 g m⁻² day⁻¹ and high anomalous values averaging 270 g m⁻² day⁻¹. Gas samples to a depth of 20 cm were also taken. Gas fractions, XCO₂ < 0.1, XCH₄ < 0.01, XN₂ ~0.71 and XO₂ ~0.21, δ¹³C of CO₂ (−34 to −18‰), as well as age of waste emplacement, suggest that the study site may be at the final stage of aerobic biodegradation. In a first approach, and following the downstream direction of groundwater flow, alkalinity and δ¹³C of dissolved inorganic carbon (−15 to 4‰) were observed to increase when groundwater passed through the disposal site. This suggests that the CO₂ generated by waste biodegradation dissolves or that dissolved organic matter appears as a result of leachate degradation.     

Air–water CO<Subscript>2</Subscript> flux in an algae bloom year for Lake Hongfeng,Southwest China: implications for the carbon cycle of global inland waters

The carbon cycle of global inland waters is quantitatively comparable to other components in the global carbon budget. Among inland waters, a significant part is man-made lakes formed by damming rivers. Man-made lakes are undergoing a rapid increase in number and size. Human impacts and frequent algae blooms lead to it necessary to make a better constraint on their carbon cycles. Here, we make a primary estimation on the air–water CO₂ transfer flux through an algae bloom year for a subtropical man-made lake—Hongfeng Lake, Southwest China. To do this a new type of glass bottles was designed for content and isotopic analysis of DIC and other environmental parameters. At the early stage of algae bloom, CO₂ was transferred from the atmosphere to the lake with a net flux of 1.770 g·C·m^?2. Later, the partial pressure (pCO₂) of the aqueous CO₂ increased rapidly and the lake outgassed to the atmosphere with a net flux of 95.727 g·C·m^?2. In the remaining days, the lake again took up CO₂ from the atmosphere with a net flux of 14.804 g·C·m^?2. As a whole, Lake Hongfeng released 4527 t C to the atmosphere, accounting for one-third of the atmosphere/soil CO₂ sequestered by chemical weathering in the whole drainage. With an empirical mode decomposition method, we found air temperature plays a major role in controlling water temperature, aqueous pCO₂ and hence CO₂ flux. This work indicates a necessity to make detailed and comprehensive carbon budgets in man-made lakes.     

Carbon isotopic fractionation during a mesocosm bloom experiment dominated by Emiliania huxleyi: Effects of CO2 concentration and primary production

We investigated the effect of CO₂ and primary production on the carbon isotopic fractionation of alkenones and particulate organic matter (POC) during a natural phytoplankton bloom dominated by the coccolithophore Emiliania huxleyi. In nine semi-closed mesocosms (∼11 m³ each), three different CO₂ partial pressures (pCO₂) in triplicate represented glacial (∼180 ppmv CO₂), present (∼380 ppmv CO₂), and year 2100 (∼710 ppmv CO₂) CO₂ conditions. The largest shift in alkenone isotopic composition (4-5‰) occurred during the exponential growth phase, regardless of the CO₂ concentration in the respective treatment. Despite the difference of ∼500 ppmv, the influence of pCO₂ on isotopic fractionation was marginal (1-2‰). During the stationary phase, E. huxleyi continued to produce alkenones, accumulating cellular concentrations almost four times higher than those of exponentially dividing cells. Our isotope data indicate that, while alkenone production was maintained, the interaction of carbon source and cellular uptake dynamics by E. huxleyi reached a steady state. During stationary phase, we further observed a remarkable increase in the difference between δ¹³C of bulk organic matter and of alkenones spanning 7-12‰. We suggest that this phenomenon is caused mainly by a combination of extracellular release of ¹³C-enriched polysaccharides and subsequent particle aggregation induced by the production of transparent exopolymer particles (TEP).     

Net Ecosystem Metabolism and Nonconservative Fluxes of Organic Matter in a Tropical Mangrove Estuary, Piauí River (NE of Brazil)

Net ecosystem metabolism (NEM) was measured in the Piauí River estuary, NE Brazil. A mass balance of C, N, and P was used to infer its sources and sinks. Dissolved inorganic carbon (DIC) concentrations and fluxes were measured over a year along this mangrove dominated estuary. DIC concentrations were high in all estuarine sections, particularly at the fluvial end member at the beginning of the rainy season. Carbon dioxide concentrations in the entire estuary were supersaturated throughout the year and highest in the upper estuarine compartment and freshwater, particularly at the rainy season, due to washout effects of carbonaceous soils and different organic anthropogenic effluents. The estuary served as a source of DIC to the atmosphere with an estimated flux of 13 mol CO₂ m^?2 year^?1. Input from the river was 46 mol CO₂ m^?2 year^?1. The metabolism of the system was heterotrophic, but short periods of autotrophy occurred in the lower more marine portions of the estuary. The pelagic system was more or less balanced between auto- and heterotrophy, whereas the benthic and intertidal mangrove region was heterotrophic. Estimated annual NEM yielded a total DIC production in the order of 18 mol CO₂ m^?2 year^?1. The anthropogenic inputs of particulate C, N, and P, dissolved inorganic P (DIP), and DIC were significant. The fluvial loading of particulate organic carbon and dissolved inorganic nitrogen (DIN) was largely retained in two flow regulation and hydroelectric reservoirs, promoting a reduction of C:N and C:P particulate ratios in the estuary. The net nonconservative fluxes obtained by a mass balance approach revealed that the estuary acts as a source of DIP, DIN, and DIC, the latter one being almost equivalent to the losses to the atmosphere. Mangrove forests and tidal mudflats were responsible for most of NEM rates and are the main sites of organic decomposition to sustain net heterotrophy. The main sources for this organic matter are the fluvial and anthropogenic inputs. The mangrove areas are the highest estuarine sources of DIP, DIC, and DIN.     

A model of the diagenetic evolution of coaly sedimentary organic matter

Elemental composition was used to calculate the amounts of compounds produced during the diagenetic evolution of a coal series from the Mahakam delta (Kalimantan, Indonesia). These calculations were based on the following hypotheses: organic nitrogen does not take part in reactions and remains unchanged in the residual organic matter, the only compounds produced are water, carbon dioxide and hydrocarbons.This approach shows that carbon loss during diagenesis is mainly as CO₂, and hydrogen loss is mainly as H₂O. Hydrocarbon production is negligible, in accordance with absence of bacterial methane accumulations in the Mahakam delta.The δ¹³C of coals in the sequence becomes about 2 per mil more positive over the diagenetic depth range of coal evolution. Accounting for the coal δ¹³C change in terms of CO₂ loss requires that the CO₂ given off have δ¹³C of about ?40%.. Such negative CO₂ has not been observed in natural systems, except when CH₄ is undergoing oxidation. Several plausible causes for this effect are discussed.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

Isotopic and Chemical Constraints on the Biogeochemistry of Dissolved Inorganic Carbon and Chemical Weathering in the Karst Watershed of Krka River (Slovenia)

The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ¹³C_DIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO₃ ^?, Ca²⁺ and Mg²⁺ originating from carbonate dissolution. The Mg²⁺/Ca²⁺ and Mg²⁺/HCO₃ ^? molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO₂ concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO₂ downstream. The δ¹³C values in river water range from ?15.6 to ?9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO₂, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO₂ has minor influence on the inorganic carbon pool in the Krka River.     

Co-precipitation of Sr2+ and Ba2+ with aragonite by membrane diffusion of CO2 between 10 and 50 °C

Aragonite is precipitated by a new CO₂-diffusion technique from a Ca²⁺–Mg²⁺–Cl⁻ solution between 10 and 50 °C. Crystallisation of aragonite instead of calcite occurs by maintaining a [Mg²⁺]/[Ca²⁺] ratio of 2 in the fluid. The dissolved inorganic carbon (DIC) is received by diffusion of CO₂ through a polyethylene membrane (diffusion coefficient: D_CO2=10^−6.4 cm² s⁻¹ at 19 °C). It is suggested that significant amounts of DIC may be transferred by diffusion of CO₂ in natural systems if the CO₂ gradient is high. The CO₂-diffusion technique is used as a kind of simple mixed flow reactor for the co-precipitation of barium and strontium with aragonite. The distribution coefficients of Ba²⁺ and Sr²⁺ decrease from 10 to 50 °C according to D_Ba,a*=2.42−0.03595T (°C) and D_Sr,a*=1.32−0.005091T (°C). At 25 °C, the distribution coefficients are D_Ba,a*=1.5±0.1 and D_Sr,a*=1.19±0.03. The effect of temperature on D_Ba,a* is about one order of magnitude higher versus that on D_Sr,a*. Thus, Ba²⁺ may be a potential paleotemperature indicator if the composition of the solution is known.     

Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis

Pore water profiles of total-CO₂, pH, PO^3?₄, NO^?₃ plus NO^?₂, SO^2?₄, S^2?, Fe²⁺ and Mn²⁺ have been obtained in cores from pelagic sediments of the eastern equatorial Atlantic under waters of moderate to high productivity. These profiles reveal that oxidants are consumed in order of decreasing energy production per mole of organic carbon oxidized (O₂ > manganese oxides ~ nitrate > iron oxides > sulfate). Total CO₂ concentrations reflect organic regeneration and calcite dissolution. Phosphate profiles are consistent with organic regeneration and with the effects of release and uptake during inorganic reactions. Nitrate profiles reflect organic regeneration and nitrate reduction, while dissolved iron and manganese profiles suggest reduction of the solid oxide phases, upward fluxes of dissolved metals and subsequent entrapment in the sediment column. Sulfate values are constant and sulfide is absent, reflecting the absence of strongly anoxic conditions.     

Tufa and travertines of southern Italy: deep‐seated,fault‐related CO2 as the key control in precipitation

Continental carbonates of Quaternary age in southern Italy commonly exhibit the facies of calcareous tufa, often reported as related to shallow aquifers fed by meteoric waters and to organic processes. A close spatial relationship exists between the mappable tufa deposits and major Quaternary extensional faults. With respect to the Ca‐Mg‐HCO₃ composition of limestone aquifers’ springs, tufa‐depositing springs exhibit higher salinity and alkalinity, are slightly warmer, have lower pH and are enriched in SO₄ and CO₂. Their δ¹³C values are systematically positive and compatible with a deep‐seated carbon source. A clear input of soil‐derived organic carbon is indicated only for small, non‐mappable tufas deposited by perched springs. The dataset indicates that the large tufa deposits owe their origin to a supplementary source of CO₂ advected by degassing through active faults, as a necessary prerequisite for inducing a rise of total dissolved salts and alkalinity. Meteoric waters that have come from a shallow aquifer are able to precipitate only limited amount of carbonates.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

The geochemistry of dissolved inorganic carbon in a surficial groundwater aquifer in North Inlet, South Carolina, and the carbon fluxes to the coastal ocean

We report measurements of pH, total dissolved inorganic carbon (DIC), total or titration alkalinity (TAlk), Ca²⁺, Mg²⁺, sulfate, and sulfide data at the seawater-freshwater interface in a shallow groundwater aquifer in North Inlet, South Carolina. These measurements and a diagenetic modeling analysis indicate that the groundwaters at North Inlet are mixtures of seawater and freshwater end-members and are seriously modified by carbon dioxide inputs from organic carbon degradation via SO₄²⁻ reduction across the entire salinity range and fermentation and CaCO₃ dissolution in the low-salinity region. DIC and TAlk are several times higher than the theoretical dilution line, whereas Ca²⁺ is slightly higher and SO₄²⁻ is somewhat lower than the dilution line. Partial pressure of CO₂ in the groundwater is extremely high (0.05 to 0.12 atm). These deviations are consistent with theoretical predictions from known diagenetic reactions. Estimated groundwater DIC fluxes to the South Atlantic Bight from either the surficial aquifer (via salt marshes) or the Upper Floridan Aquifer (direct input) are significant when compared to riverine flux in this area.     

Quantification of photosynthetic inorganic carbon utilisation via a bidirectional stable carbon isotope tracer

The amount of bicarbonate utilised by plants is usually ignored because of limited measurement methods. Accordingly, this study quantified the photosynthetic assimilation of inorganic carbon (CO₂ and HCO₃ ^?) by plants. The net photosynthetic CO₂ assimilation (P _N), the photosynthetic assimilation of CO₂ and bicarbonate (P _N’), the proportion of increased leaf area (f _LA) and the stable carbon isotope composition (δ¹³C) of Orychophragmus violaceus (Ov) and Brassica juncea (Bj) under three bicarbonate levels (5, 10 and 15 mm NaHCO₃) were examined to determine the relationship among P _N, P _N’ and f _LA. P _N’, not P _N, changed synchronously with f _LA. Moreover, the proportions of exogenous bicarbonate and total bicarbonate (including exogenous bicarbonate and dissolved CO₂-generated bicarbonate) utilised by Ov were 2.27 % and 5.28 % at 5 mm bicarbonate, 7.06 % and 13.28 % at 10 mm bicarbonate, and 8.55 % and 17.31 % at 15 mm bicarbonate, respectively. Meanwhile, the proportions of exogenous bicarbonate and total bicarbonate utilised by Bj were 1.77 % and 3.28 % at 5 mm bicarbonate, 2.11 % and 3.10 % at 10 mm bicarbonate, and 2.36 % and 3.09 % at 15 mm bicarbonate, respectively. Therefore, the dissolved CO₂-generated bicarbonate and exogenous bicarbonate are important sources of inorganic carbon for plants.