Carbon sequestration and decreased CO2 emission caused by terrestrial aquatic photosynthesis: Insights from diel hydrochemical variations in an epikarst spring and two spring-fed ponds in different seasons

Whether carbonate weathering could produce a stable carbon sink depends primarily on the utilization of dissolved inorganic carbon (DIC) by aquatic phototrophs (the so-called Biological Carbon Pump-BCP effect). On this basis, water temperature (T), pH, electrical conductivity (EC) and dissolved oxygen (DO) were synchronously monitored at 15-min resolution for one and two days respectively in January and October 2013 in Maolan Spring and the spring-fed midstream and downstream ponds in Maolan Nature Reserve, China. A thermodynamic model was used to link the continuous data to allow calculation of CO₂ partial pressures (pCO₂) and calcite saturation indexes (SI_C). A floating static chamber was placed on the water surface successively at all sites to quantify CO₂ exchange flux between atmosphere and water so as to evaluate the BCP effect. Results show that, in both winter and autumn, remarkable diel variations of hydrochemical parameters were present in the midstream pond where DO, pH, and SI_C increased in the day and decreased during the night while EC, $\left[{{\text{HCO}}_3}^{-}\right]$, [Ca²⁺] and pCO₂ showed inverse changes mainly due to the metabolic processes of the flourishing submerged plants, with photosynthesis dominating in the day and respiration dominating at night. However, hydrochemical parameters in the spring and downstream pond show less change since few submerged plants developed there. It was determined that the BCP effect in the midstream pond was 285 ± 193 t C km⁻² a⁻¹ in winter and 892 ± 300 t C km⁻² a⁻¹ in autumn, indicating a potential significant role of terrestrial aquatic photosynthesis in stabilizing the carbonate weathering-related carbon sink.     

Effects of carbon anhydrase on utilization of bicarbonate in microalgae: a case study in Lake Hongfeng

A bidirectional labeling method was established to distinguish the proportions of HCO₃^? and CO₂ utilization pathways of microalgae in Lake Hongfeng. The method was based on microalgae cultured in a medium by adding equal concentrations of NaH¹³CO₃ with different δ¹³C values simultaneously. The inorganic carbon sources were quantified according to the stable carbon isotope composition in the treated microalgae. The effects of extracellular carbonic anhydrase (CAex) on the HCO₃^? and CO₂ utilization pathways were distinguished using acetazolamide, a potent membrane-impermeable carbonic anhydrase inhibitor. The results show utilization of the added HCO₃^? was only 8% of the total carbon sources in karst lake. The proportion of the HCO₃^? utilization pathway was 52% of total inorganic carbon assimilation. Therefore, in the natural water of the karst area, the microalgae used less bicarbonate that preexisted in the aqueous medium than CO₂ derived from the atmosphere. CAex increased the utilization of inorganic carbon from the atmosphere. The microalgae with CAex had greater carbon sequestration capacity in this karst area.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

Does bicarbonate affect the nitrate utilization and photosynthesis of <Emphasis Type="Italic">Orychophragmus violaceus</Emphasis>?

The effect of bicarbonate (HCO₃^?) on the growth and development of plants varies by species. To better understand inorganic carbon and nitrogen assimilation changes of karst-adaptable plants under different HCO₃^? treatments, we conducted experiments on seedlings and in vitro plantlets of Orychophragmus violaceus (Ov). We found that the vital photosynthesis potential (as measured by net photosynthetic rate, actual photochemical efficiency of photosystem-II, photochemical quenching coefficient, and the instantaneous carbon isotope ratio of 3-phosphoglycerate) was consistent under different HCO₃^? treatments of Ov. Bicarbonate’s lack of effect on carbon assimilation of Ov may be related to carbonic anhydrase in Ov converting HCO₃^? to H₂O and CO₂. In this way, Ov could prevent HCO₃^? ion toxicity and high pH from harming its growth and development under HCO₃^? stress. This study also found that high HCO₃^? concentrations could promote nitrogen assimilation and utilization of Ov through changes in related indexes (foliar nitrogen isotope fractionation ratio, stable nitrogen isotope assimilation ratio, foliar stable nitrogen isotope fractionation, nitrate nitrogen utilization efficiency, and nitrate utilization share) under different HCO₃^? treatments. Bicarbonate has different effects on photosynthesis and on inorganic nitrogen assimilation of Ov, which may be connected to photosynthesis providing electrons for nitrate/nitrite reduction through the photosynthetic chain.     

Diurnal Variations of Hydrochemistry in a Travertine-depositing Stream at Baishuitai, Yunnan, SW China

Diurnal variations of hydrochemistry were monitored at a spring and two pools in a travertine-depositing stream at Baishuitai, Yunnan, SW China. Water temperature, pH and specific conductivity were measured in intervals of 5 and 30 min for periods of 1 to 2 days. From these data the concentrations of Ca²⁺, HCO₃⁻, calcite saturation index, and CO₂ partial pressure were derived. The measurements in the spring of the stream did not show any diurnal variations in the chemical composition of the water. Diurnal variations, however, were observed in the water of the two travertine pools downstream. In one of them, a rise in temperature (thus more CO₂ degassing) during day time and consumption of CO₂ due to photosynthesis of submerged aquatic plants accelerated deposition of calcite, whereas in the other pool, where aquatic plants flourished and grew out of the water (so photosynthesis was taking place in the atmosphere), the authors suggest that temperature-dependent root respiration underwater took place, which dominated until noon. Consequently, due to the release of CO₂ by the root respiration into water, which dominated CO₂ production by degassing induced by temperature increase, the increased dissolution of calcite was observed. This is the first time anywhere at least in China that the effect of root respiration on diurnal hydrochemical variations has been observed. The finding has implications for sampling strategy within travertine-depositing streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, pools and wetlands, where aquatic plants may flourish and grow out of water.     

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle,USA

This study investigated the potential for the uranium mineral carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO₂. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO₄ + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa⁺² > mHCO₃⁻ + 2mCO₃⁻²) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa⁺² < mHCO₃^- + 2mCO₃⁻²) carnotite saturation was not achieved. In systems open to CO_2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO₂ ranging from 10^−3.5 to 10^−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO₂ equal to 10^−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO₂.     

14C in bicarbonate and dissolved organics—a useful tracer?

The tunnel excavation at the Äspö Hard Rock Laboratory opened several fracture zones at various depths in the crystalline bedrock. One of these zones is the `Redox zone', a vertical fracture zone penetrated at 70 m depth. Except for the tunnel intersection, several boreholes were drilled to intersect the zone at various depths (ranging from 5 to 70 m) and distances from the tunnel. The response in groundwater chemistry to the opening of the zone has been monitored in these boreholes during 3 a, starting in 1991 and for the boreholes at 70 m depth the monitoring is still ongoing. The water chemistry during this monitoring can be largely explained by mixing between fresh water and native saline groundwater (4900 ppm Cl⁻). An increase in HCO⁻₃ was recorded, which was interpreted as due to anaerobic respiration. This was supported by ¹⁴C-contents in dissolved organic Carbon and HCO⁻₃, indicating that recent organic C is transported into the zone and oxidised to CO₂. This study exemplifies the use of ¹⁴C-analyses of HCO⁻₃ in order to trace different C sources contributing to the HCO⁻₃ in the groundwater. Three sources were identified: (1) dissolved CO₂, dominantly soil-CO₂ possibly with some contribution of atmospheric CO₂; (2) dissolution of calcite, with low ¹⁴C content, which dominantly occurs in the near-surface recharge area; and (3) oxidation of organic material through anaerobic respiration. Corrections for ¹⁴C and HCO⁻₃ in the native saline water made it possible to determine 2 different fresh water components corresponding to different flow paths. The C isotope data are in accordance with the results from the tracer test and the groundwater flow model, and support that the extensive build up of HCO₃⁻ does not mainly takes place locally within the zone but is transported into the zone by dominantly lateral flow. The results from the monitoring showed that new hydrochemical stability is established, which also comprises the interaction between the organic and inorganic C cycles.     

An organic carbon budget for the Mississippi River turbidity plume and plume contributions to air-sea CO2 fluxes and bottom water hypoxia

We investigated seasonal variability in organic carbon (OC) budgets using a physical-biological model for the Mississippi River turbidity plume. Plume volume was calculated from mixed layer depth and area in each of four salinity subregions based on an extensive set of cruise data and satellite-derived suspended sediment distributions. These physical measurements were coupled with an existing food web model to determine seasonally dependent budgets for labile (reactive on time scales of days to weeks) OC in each salinity subregion. Autochthonous gross primary production (GPP) equaled 1.3×10¹² g C yr⁻¹ and dominated labile OC inputs (88% of the budget) because riverine OC was assumed mostly refractory (nonreactive). For perspective, riverine OC inputs amounted to 3.9×10¹² g C yr⁻¹, such that physical inputs were 3 times greater than biological inputs to the plume. Annually, microbial respiration (R) accounted for 65% of labile OC losses and net metabolism (GPP—R) for the entire plume was, autotrophic, equaling 5.1×10¹¹ g C yr⁻¹. Smaller losses of labile OC occurred via sedimentation (20%), advection (10%), and export to higher trophic levels (5%). In our present model, annual losses of labile OC are 10% higher than inputs, indicating future improvements are required. Application of our model to estimate air-sea carbon dioxide (CO₂) fluxes indicated the plume was a net sink of 2.0×10⁹ mol CO₂ yr⁻¹, of which 90% of the total drawdown was from biotic factors. In all seasons, low salinity waters were a source of CO₂ (pCO₂=560–890 μatm), and intermediate to high salinity waters were a sink of CO₂ (pCO₂=200–370 μatm). Our model was also used to calculate O₂ demand for the development, of regional hypoxia, and our spring and early summer budgets indicated that sedimentation of autochthonous OC from the immediate plume contributed 23% of the O₂ demand necessary for establishment of hypoxia in the region.     

普定岩溶水-碳循环模拟试验场水体双碳同位素特征(δ13C-Δ14C)与碳足迹

河流输送到海洋的溶解无机碳(DIC)和有机碳(OC)受自然和人为双重因素的影响。了解DIC和OC的年龄、来源和转化,有助于掌握全球碳收支和提高现在以及未来自然和人类对河流碳循环影响的估算精度。本研究以普定岩溶水-碳循环试验场泉(地下水)-池(地表水)耦联系统为研究对象,利用双碳同位素(¹³C- ¹⁴C)方法,结合水生植物生长和传统水文地球化学特征,揭示了地下水-地表水系统中DIC和颗粒有机碳(POC)的来源及其转化机制。研究发现:(1)泉-池系统中DIC和POC的Δ¹⁴C具有相同的变化趋势,泉水中Δ¹⁴C值低于池水中Δ¹⁴C值,反映后者可能有“较年轻”的CO₂的加入;(2)池水水化学和碳同位素变化由土地利用类型和池中水生植物共同控制;(3)池水中颗粒有机碳(POC)浓度明显高于泉水,且其Δ¹⁴C值表现出与沉水植物和DIC的一致性(表观年龄均为3 200900 a),说明池水POC主要源于池中水生植物光合作用利用了碳酸盐风化产生的老碳(DIC),使新形成的有机质在表观年龄上“偏老”;(4)池水水体内源有机碳对水体POC的贡献在75%以上,内源有机碳通量(以C计)在250 t·km^-2·a^-1至660 t·km^-2·a^-1之间,相对于其他土地利用类型,草地对应的地表水系统具有最大的内源有机碳占比和通量,指示了沉水植物控制型浅水水体初级生产对有机碳循环的重要作用。综上,我们认为在岩溶区通过土地利用调整来调控水生植物群落对于增加碳汇具有重要潜力。     

Daytime deposition and nighttime dissolution of calcium carbonate controlled by submerged plants in a karst spring-fed pool: insights from high time-resolution monitoring of physico-chemistry of water

Water temperature, dissolved oxygen (DO), pH, and specific conductivity (spc) were measured in a time interval of 15 min in a karst spring and the spring-fed pool with flourishing submerged plants in Guilin, SW China under dry weather for periods of 2 days. Measurements allowed calculation of calcium and bicarbonate concentrations ([Ca²⁺] and [HCO₃ ⁻]), and thus CO₂ partial pressure ( ) and saturation index of calcite (SIc). Results show that there were not any diurnal variations in the physico-chemical parameters of the water for the spring. However, during daytime periods, pool water decreased to far less than the spring water in a few hours, pH and SIc increased to greater than the spring, and [Ca²⁺] and [HCO₃ ⁻] decreased to less than the spring. During nighttime periods, pool water returned to or even increased to greater than the spring, pH and SIc decreased to less than the spring, and [Ca²⁺] and [HCO₃ ⁻] increased to greater than the spring. The decrease in [Ca²⁺] and [HCO₃ ⁻] to less than the spring during daytime periods implies daytime deposition of calcium carbonate, while the increase in [Ca²⁺] and [HCO₃ ⁻] to greater than the spring during nighttime periods implies nighttime dissolution of calcium carbonate. The direction of the observed changes depended essentially on the illumination, indicating that daytime photosynthetic and nighttime respiratory activities in the pool aquatic plant ecosystem, which were further evidenced by the increase and decrease in DO during daytime and nighttime periods respectively, were the main processes involved. The large variations of the components of the carbonate system imply considerable changes of the capacities of CO₂ and O₂ in water. The finding has implications for water sampling strategy in slow-flowing karst streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, and wetlands, where aquatic plant ecosystem may flourish.     

Carbon isotope fractionation of Thermoanaerobacter kivui in different growth media and at different total inorganic carbon concentration

Chemolithotrophic homoacetogenic bacteria apparently express a characteristic stable carbon isotope fractionation and may contribute significantly to acetate production in anoxic environments. However, fractionation factors (ε) in bacterial cultures have rarely been determined and the effect of substrate availability has not been assessed. We therefore studied the kinetic carbon isotope effect in cultures of Thermoanaerobacter kivui grown at 55 °C. The fractionation factor in HCO₃⁻ buffered medium was ca. 15‰ more negative than that in PO₄³⁻ buffered medium. To test whether the difference was caused by the initial substrate ratio of H₂ and total inorganic carbon (TIC; 0.5 in HCO₃⁻ vs. 4.0 in PO₄³⁻ buffered medium), T. kivui was grown in either [3-(N-morpholino) propanesulfonic acid, MOPS] buffered or PO₄³⁻ buffered media with different HCO₃⁻ concentration. Indeed, the fractionation factor became more negative with increasing HCO₃⁻ concentration and decreasing H₂/TIC ratio. While pH had only a small effect, the fractionation was generally more negative in MOPS buffered than in phosphate buffered media, indicating that the buffer system also affected fractionation. Collectively, the results show that substrate availability and other environmental factors affect the magnitude of isotope fractionation during acetate production by chemolithotrophic homoacetogenesis.     

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.     

CO2 emission from Dianshan Lake in summer, East China

Shallow fresh water bodies in peat areas could be an important contributor to greenhouse gases in the atmosphere.In this study,the partial pressure of CO2 in the surface water of the Dianshan Lake was investigated insitu in August 2011.The average pCO2 in the study area was 2300μatm and fluctuated within the range of 989–5000μatm.pCO2 showed a reverse trend to the variations of pH and DO in the surface water of the Dianshan Lake.The water to air diffusion flux of CO2 of the upstream,middle lake and downstream were respectively 63,33 and 14mmol/m2/d.On average,the diffusion flux of CO2 of the whole lake was 31 mmol/m2/d.Consequently,our results show that during the sampling season,the Dianshan Lake appears to be a great source of CO2.It is also demonstrated that respiration could be the dominant biochemical reaction in the Dianshan Lake in summer.     

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.     

18.5kaB. P.以来东北四海龙湾玛珥湖全岩有机碳同位素记录及其古气候环境意义

结合含水量、TOC含量和TOC/TN比值变化曲线,18·5kaB·P·以来的四海龙湾玛珥湖沉积物全岩有机碳同位素组成（^δ13C_TOC）记录可划分为3个阶段:1)末次冰期晚期（18·5～14·7kaB·P·）,^δ13C_TOC值偏正,变化范围为-29·50‰～-26·18‰,平均值约为-28·10‰;2)末次冰消期（14·7～11·7kaB·P·）,^δ13C_TOC值显著偏负,变化范围为-33·92‰～-28·40‰,平均值约为-31·75‰,在^δ13C_TOC值变化曲线上表现为一个低谷,但在类似YoungerDryas的冷干事件期间（12·7～11·7kaB·P·）,^δ13C_TOC值再次显著偏正,最高可达-28·4‰;3)全新世以来（11·7kaB·P.至今）,^δ13C_TOC值变化幅度不大（-30·85‰～-27·37‰）,基本上都在平均值-29·1‰左右。研究表明,大气CO₂浓度变化是影响18·5kaB·P·以来四海龙湾玛珥湖^δ13C_TOC值变化的主导因素。     

Geochemistry of the mineral waters and gases of the Mukhen deposit,Far East

This work reports new hydrochemical data on the two types of cold high p CO₂ groundwaters from the Mukhen deposit (Khabarovsk district). The first type is classed with HCO₃-Ca-Mg waters with a relatively low TDS (up to 1.7 g/l) and high concentrations of Fe²⁺, Mn²⁺, Ba²⁺, and SiO₂. The second type is of HCO₃-Na composition with high TDS (up to 14 g/l) and elevated Li⁺, B, Sr²⁺, Br^?, and I^?. New oxygen (δ¹⁸O) and hydrogen (δD) isotopic data on the waters and carbon (δ¹³C) isotopic data on the gas phase, together with a detailed geological and hydrogeological analysis of the study area, allowed us to decipher the origin of both the mineral waters. Based on the tritium content (³H) in the ground and surface waters of the area, the duration of the mineral water circulation was estimated. It was established that the both types of groundwaters were formed during interaction of meteoric water with bedrock under active influence of CO₂, however HCO₃-Na groundwaters have longer residence time than HCO₃-Ca-Mg groundwaters.     

Irreversible water–rock mass transfer accompanying the generation of the neutral,Mg–HCO3 and high-pH,Ca–OH spring waters of the Genova province,Italy

In a recent survey of the spring waters of the Genova province, many neutral Mg–HCO₃ waters and some high-pH, Ca–OH waters were found in association with serpentinites. All the springs are of meteoric origin as indicated by the stable isotopes of water and dissolved N₂ and Ar. Interaction of these meteoric waters with serpentinites determines a progressive evolution in the chemistry of the aqueous phase from an immature Mg-rich, SO₄–Cl facies of low salinity to an intermediate Mg–HCO₃ facies (pH 7.0–8.5, P_CO210^−3.5–10^−2.5 bar, Eh 150–250 mV), and to a mature Ca–OH facies (pH 10–12, P_CO2 10^−9.4−10^−10.6 bar, Eh-390 to-516 mV). The irreversible water–rock mass transfer leading to these chemical changes in the aqueous phase was simulated through reaction path modeling, assuming bulk dissolution of a local serpentinite, and the precipitation of gibbsite, goethite, calcite, hydromagnesite, kaolinite, a montmorillonite solid mixture, a saponite solid mixture, sepiolite, and serpentine. The simulation was carried out in two steps, under open-system and closed-system conditions with respect to CO₂, respectively. The calculated concentrations agree with analytical data, indicating that the computed water-rock mass transfer is a realistic simulation of the natural process. Moreover, the simulation elucidates the role of calcite precipitation during closed-system serpentinite dissolution in depleting the aqueous solution of C species, allowing the concurrent increment in Ca and the acquisition of a Ca–OH composition. Calcium–OH waters, due to their high pH, tend to absorb CO₂, precipitating calcite. Therefore, these waters might be used to sequester anthropogenic CO₂, locally preventing environmental impact to the atmosphere.     

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH₃ to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. The objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al³⁺ (2.8 or 5 mM), HCO₃⁻ (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO₂(CO₃)₂⁻² and UO₂(CO₃)₃⁻⁴) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO₂(OH)₃⁻ and UO₂(OH)₄⁻²) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO₂CO₃], cejkaite [Na₄(UO2)(CO₃)₃] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO₂)(SiO₄)·1.5H₂O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.     

Authigenic mineralogy, depositional environments and evolution of fault-bounded lakes of the Yunnan Plateau, south-western China

The Dianchi, Erhai and Fuxian lakes lie in faulted basins in a subtropical humid region of the Yunnan Plateau, China. Three groups of authigenic minerals have been recognized in their recent sediments - carbonate minerals, Fe-bearing minerals and silica minerals. The main authigenic minerals are goethite, calcite, aragonite, siderite and quartzine. Goethite is chemically precipitated from a colloidal suspension. Calcite is a widespread chemical precipitate that is present in deep parts of the lakes and in shallow areas associated with aquatic macrophytes. Aragonite is mainly biochemical in origin, and commonly associated with shallow benthos. Siderite forms in reducing environments, associated with pore waters with a high P_CO2 that resulted from microbial degradation of organic matter. It forms mainly in deep-water environments. Quartzine, which occurs mainly in delta front and prodeltaic sites, forms from diatom dissolution and dissolved silica introduced by streams. Six authigenic mineral associations are recognized, each of which can be related to depositional setting within the lake and the stage of lake development. The same associations can also be recognized in a 480-m-long core recovered from Dianchi Lake. Strong reducing environments and migrating pore fluids with high P_CO2 have led to the early diagenetic alteration of some of the initial authigenic minerals. Using the mineral associations from the modern lakes, the Pliocene to Recent history of Dianchi Lake has been interpreted, and is in general agreement with palaeoenvironmental reconstructions based upon palaeontological and other evidence.     

Rapid Alkalization in Lake Inawashiro, Fukushima, Japan: Implications for Future Changes in the Carbonate System of Terrestrial Waters

The global carbon cycle, one of the important biogeochemical cycles controlling the surface environment of the Earth, has been greatly affected by human activity. Anthropogenic nutrient loading from urban sewage and agricultural runoff has caused eutrophication of aquatic systems. The impact of this eutrophication and consequent photosynthetic activity on CO₂ exchange between freshwater systems and the atmosphere is unclear. In this study, we focused on how nutrient loading to lakes affects their carbonate system. Here, we report results of surveys of lakes in Japan at different stages of eutrophication. Alkalization due to photosynthetic activity and decreases in PCO₂ had occurred in eutrophic lakes (e.g., Lake Kasumigaura), whereas in an acidotrophic lake (Lake Inawashiro) that was impacted by volcanic hot springs, nutrient loading was changing the pH and carbon cycling. When the influence of volcanic activity was stronger in the past in Lake Inawashiro, precipitation of volcanic-derived iron and aluminum had removed nutrients by co-precipitation. During the last three decades, volcanic activity has weakened and the lake water has become alkalized. We inferred that this rapid alkalization did not result just from the reduction in acid inputs but was also strongly affected by increased photosynthetic activity during this period. Human activities affect many lakes in the world. These lakes may play an important part in the global carbon cycle through their influence on CO₂ exchange between freshwater and the atmosphere. Biogeochemical changes and processes in these systems have important implications for future changes in aquatic carbonate systems on land.