The Role of CaCO<Subscript>3</Subscript> Reactions in the Contemporary Oceanic CO<Subscript>2</Subscript> Cycle

The present analysis adjusts previous estimates of global ocean CaCO₃ production rates substantially upward, to 133 × 10¹² mol yr^?1 plankton production and 42 × 10¹² mol yr^?1 shelf benthos production. The plankton adjustment is consistent with recent satellite-based estimates; the benthos adjustment includes primarily an upward adjustment of CaCO₃ production on so-called carbonate-poor sedimentary shelves and secondarily pays greater attention to high CaCO₃ mass (calcimass) and turnover of shelf communities on temperate and polar shelves. Estimated CaCO₃ sediment accumulation rates remain about the same as they have been for some years: ~20 × 10¹² mol yr^?1 on shelves and 11 × 10¹² mol yr^?1 in the deep ocean. The differences between production and accumulation of calcareous materials call for dissolution of ~22 × 10¹² mol yr^?1 (~50 %) of shelf benthonic carbonate production and 122 × 10¹² mol yr^?1 (>90 %) of planktonic production. Most CaCO₃ production, whether planktonic or benthonic, is assumed to take place in water depths of <100 m, while most dissolution is assumed to occur below this depth. The molar ratio of CO₂ release to CaCO₃ precipitation (CO₂↑/CaCO₃↓) is <1.0 and varies with depth. This ratio, Ψ, is presently about 0.66 in surface seawater and 0.85 in ocean waters deeper than about 1000 m. The net flux of CO₂ associated with CaCO₃ reactions in the global ocean in late preindustrial time is estimated to be an apparent influx from the atmosphere to the ocean, of +7 × 10¹² mol C yr^?1, at a time scale of 10²–10³ years. The CaCO₃-mediated influx of CO₂ is approximately offset by CO₂ release from organic C oxidation in the water column. Continuing ocean acidification will have effects on CaCO₃ and organic C metabolic responses to the oceanic inorganic C cycle, although those responses remain poorly quantified.     

Understanding the Cyclicity of Chemical Weathering and Associated CO<Subscript>2</Subscript> Consumption in the Brahmaputra River Basin (India): The Role of Major Rivers in Climate Change Mitigation Perspective

Weathering of rocks that regulate the water chemistry of the river has been used to evaluate the CO₂ consumption rate which exerts a strong influence on the global climate. The foremost objective of the present research is to estimate the chemical weathering rate (CWR) of the continental water in the entire stretch of Brahmaputra River from upstream to downstream and their associated CO₂ consumption rate. To establish the link between the rapid chemical weathering and thereby enhance CO₂ drawdown from the atmosphere, the major ion composition of the Brahmaputra River that drains the Himalaya has been obtained. Major ion chemistry of the Brahmaputra River was resolved on samples collected from nine locations in pre-monsoon, monsoon and post-monsoon seasons for two cycles: cycle I (2011–2012) and cycle II (2013–2014). The physico-chemical parameters of water samples were analysed by employing standard methods. The Brahmaputra River was characterized by alkalinity, high concentration of Ca²⁺ and HCO₃ ^? along with significant temporal variation in major ion composition. In general, it was found that water chemistry of the river was mainly controlled by rock weathering with minor contributions from atmospheric and anthropogenic sources. The effective CO₂ pressure (log\({{\text{P}}_{{\text{C}}{{\text{O}}_{\text{2}}}}}\)) for pre-monsoon, monsoon and post-monsoon has been estimated. The question of rates of chemical weathering (carbonate and silicate) was addressed by using TDS and run-off (mm year^?1). It has been found that the extent of CWR is directly dependent on the CO₂ consumption rate which may be further evaluated from the perspective of climate change mitigation The average annual CO₂ consumption rate of the Brahmaputra River due to silicate and carbonate weathering was found to be 0.52 (×10⁶ mol Km^?2 year^?1) and 0.55 (×10⁶ mol Km^?2 year^?1) for cycle I and 0.49 (×10⁶ mol Km^?2 year^?1) and 0.52 (×10⁶ mol Km^?2 year^?1) for cycle II, respectively, which were significantly higher than that of other Himalayan rivers. Estimation of CWR of the Brahmaputra River indicates that carbonate weathering largely dominates the water chemistry of the Brahmaputra River.     

Assessment of groundwater quality in and around Vedaraniyam,South India

Groundwater from 47 wells were analyzed on the basis of hydrochemical parameters like pH, electric conductivity, total dissolved solids, Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^?, CO₃ ^2?, HCO₃ ^?, NO₃ ^?, PO₄ ^3? and F^? in the Cauvery delta of Vedaraniyam coast. Further, water quality index (WQI), sodium percentage (Na %), sodium absorption ratio, residual sodium carbonate, permeability index and Kelley’s ratio were evaluated to understand the suitability of water for drinking and irrigation purposes. The result shows significant difference in the quality of water along the coastal stretch. The order of dominance of major ions is as follows: Na⁺ ≥ Mg²⁺ ≥ Ca²⁺ ≥ K⁺ and Cl^? ≥ HCO₃ ^? ≥ CO₃ ^2? ≥ PO₄ ^3? ≥ F^?. Na/Cl, Cl/HCO₃ ratio and Revelle index confirmed that 60–70 % of the samples were affected by saline water intrusion. WQI showed that 36 % of the samples were good for drinking and the remaining were poor and unsuitable for drinking purpose. The degradation of groundwater quality was found to be mainly due to over-exploitation, brackish aquaculture practice, fertilizer input from agriculture and also due to domestic sewage.     

Hydrogeochemistry and quality of groundwater of coastal unconfined aquifer in Amol–Ghaemshahr plain,Mazandaran Province,Northern Iran

Groundwater of the unconfined aquifer (1,100 sq. km) of a two-tier coastal aquifer located in the Amol–Ghaemshahr plain, Mazandaran Province, Northern Iran, is classified into fresh and brackish water types. Fresh groundwater (FGW) samples (n = 36) are characterized by Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ and HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, values of the C-ratio (av. = 0.89) and CAI and values of the molar ratios of Ca²⁺/HCO₃ ^?, Ca²⁺/SO₄ ^2?, Mg²⁺/HCO₃ ^? and Mg²⁺/SO₄ ^2? indicate that the ionic load in the FGW is derived essentially from carbonic acid-aided weathering of carbonates and aluminosilicates, saline/sea water trapped in the aquifer sediments (now admixed with the groundwater) and ion exchange reactions. Values of the CAI and Na⁺/Cl^? molar ratio suggest that the part of the Ca²⁺ (±Mg²⁺) content in 23 FGW samples is derived from clay minerals of the aquifer matrix, and part of the Na⁺ content in 20, 12, and 3 FGW samples is derived, respectively, from alkali feldspar weathering, clay minerals of the aquifer matrix and rain water and/or halite. Brackish groundwater (BGW) samples (n = 4) contain Cl^? as the dominant anion and their average total ionic concentration (38.65 meq/L) is 1.79 times higher than that of the FGW samples (21.50 meq/L). BGW pockets were generated by non-conservative mixing of FGW with the upconed saline water from the underlying saline groundwater zone of the semi-confined aquifer along bore wells involved in excessive extraction of groundwater from the unconfined aquifer. Groundwater belongs essentially to “high salinity, low sodium” irrigation water class.     

Geochemical Eccentricity of Ground Water Allied to Weathering of Basalts from the Deccan Volcanic Province,India: Insinuation on CO<Subscript>2</Subscript> Consumption

Analyses of 72 samples from Upper Panjhara basin in the northern part of Deccan Plateau, India, indicate that geochemical incongruity of groundwater is largely a function of mineral composition of the basaltic lithology. Higher proportion of alkaline earth elements to total cations and HCO₃>Cl + SO₄ reflect weathering of primary silicates as chief source of ions. Inputs of Cl, SO₄, and NO₃ are related to rainfall and localized anthropogenic factors. Groundwater from recharge area representing Ca + Mg–HCO₃ type progressively evolves to Ca + Na–HCO₃ and Na–Ca–HCO₃ class along flow direction replicates the role of cation exchange and precipitation processes. While the post-monsoon chemistry is controlled by silicate mineral dissolution + cation exchange reactions, pre-monsoon variability is attributable chiefly to precipitation reactions + anthropogenic factors. Positive correlations between Mg vs HCO₃ and Ca + Mg vs HCO₃ supports selective dissolution of olivine and pyroxene as dominant process in post-monsoon followed by dissolution of plagioclase feldspar and secondary carbonates. The pre-monsoon data however, points toward the dissolution of plagioclase and precipitation of CaCO₃ supported by improved correlation coefficients between Na + Ca vs HCO₃ and negative correlation of Ca vs HCO₃, respectively. It is proposed that the eccentricity in the composition of groundwater from the Panjhara basin is a function of selective dissolution of olivine > pyroxene followed by plagioclase feldspar. The data suggest siallitization (L < R and R _k) as dominant mechanism of chemical weathering of basalts, stimulating monosiallitic (kaolinite) and bisiallitic (montmorillonite) products. The chemical denudation rates for Panjhara basin worked out separately for the ground and surface water component range from 6.98 to 36.65 tons/km²/yr, respectively. The values of the CO₂ consumption rates range between 0.18 × 10⁶ mol//km²/yr (groundwater) and 0.9 × 10⁶ mol/km²/yr (surface water), which indicates that the groundwater forms a considerable fraction of CO₂ consumption, an inference, that is, not taken into contemplation in most of the studies.     

Assessment of soil carbon pool,carbon sequestration and soil CO<Subscript>2</Subscript> flux in unreclaimed and reclaimed coal mine spoils

Surface coal mining inevitably deforests the land, reduces carbon (C) pool and generates different land covers. To re-establish the ecosystem C pool, post-mining lands are often afforested with fast-growing trees. A field study was conducted in the 5-year-old unreclaimed dump and reclaimed coal mine dump to assess the changes in soil CO₂ flux and compared with the reference forest site. Changes in soil organic carbon (SOC) and total nitrogen stocks were estimated in post-mining land. Soil CO₂ flux was measured using close dynamic chamber method, and the influence of environmental variables on soil CO₂ flux was determined. Woody biomass C and SOC stocks of the reference forest site were threefold higher than that of 5-year-old reclaimed site. The mean soil CO₂ flux was highest in 5-year-old reclaimed dump (2.37 μmol CO₂ m^?2 s^?1) and lowest in unreclaimed dump (0.21 μmol CO₂ m^?2 s^?1). Soil CO₂ flux was highly influenced by environmental variables, where soil temperature positively influenced the soil CO₂ flux, while soil moisture, relative humidity and surface CO₂ concentration negatively influenced the soil CO₂ flux. Change in soil CO₂ flux under different land cover depends on plant and soil characteristics and environmental variables. The study concluded that assessment of soil CO₂ flux in post-mining land is important to estimate the potential of afforestation to combat increased emission of soil CO₂ at regional and global scale.     

Carbon Dioxide and Methane Emissions from Mangrove-Associated Waters of the Andaman Islands,Bay of Bengal

We estimated CO₂ and CH₄ emissions from mangrove-associated waters of the Andaman Islands by sampling hourly over 24 h in two tidal mangrove creeks (Wright Myo; Kalighat) and during transects in contiguous shallow inshore waters, immediately following the northeast monsoons (dry season) and during the peak of the southwest monsoons (wet season) of 2005 and 2006. Tidal height correlated positively with dissolved O₂ and negatively with pCO₂, CH₄, total alkalinity (TAlk) and dissolved inorganic carbon (DIC), and pCO₂ and CH₄ were always highly supersaturated (330–1,627 % CO₂; 339–26,930 % CH₄). These data are consistent with a tidal pumping response to hydrostatic pressure change. There were no seasonal trends in dissolved CH₄ but pCO₂ was around twice as high during the 2005 wet season than at other times, in both the tidal surveys and the inshore transects. Fourfold higher turbidity during the wet season is consistent with elevated net benthic and/or water column heterotrophy via enhanced organic matter inputs from adjacent mangrove forest and/or the flushing of CO₂-enriched soil waters, which may explain these CO₂ data. TAlk/DIC relationships in the tidally pumped waters were most consistent with a diagenetic origin of CO₂ primarily via sulphate reduction, with additional inputs via aerobic respiration. A decrease with salinity for pCO₂, CH₄, TAlk and DIC during the inshore transects reflected offshore transport of tidally pumped waters. Estimated mean tidal creek emissions were ～23–173 mmol m^?2 day^?1 CO₂ and ～0.11–0.47 mmol m^?2 day^?1 CH₄. The CO₂ emissions are typical of mangrove-associated waters globally, while the CH₄ emissions fall at the low end of the published range. Scaling to the creek open water area (2,700 km²) gave total annual creek water emissions ～3.6–9.2?×?10¹⁰ mol CO₂ and 3.7–34?×?10⁷ mol CH₄. We estimated emissions from contiguous inshore waters at ～1.5?×?10¹¹ mol CO₂?year^?1 and 2.6?×?10⁸ mol CH₄?year^?1, giving total emissions of ～1.9?×?10¹¹ mol CO₂?year^?1 and ～3.0?×?10⁸ mol CH₄?year^?1 from a total area of mangrove-influenced water of ～3?×?10⁴ km². Evaluating such emissions in a range of mangrove environments is important to resolving the greenhouse gas balance of mangrove ecosystems globally. Future such studies should be integral to wider quantitative process studies of the mangrove carbon balance.     

Spatial variability of groundwater quality and its suitability for drinking and irrigation in the Amik Plain (South Turkey)

In this study, it is determined physicochemical properties of the groundwater and the spatial variability of physicochemical properties of the groundwater in the Amik plain and as well as assess its suitability for drinking and irrigation. A total 92 groundwater samples were collected from drilled well in June 2012. In addition, the 42 of 92 drilled wells were also sampled in September 2012 to evaluate the changes of groundwater properties. According to t test values, the mean Ca²⁺, SO₄ ^2?, Mg²⁺ and TH values in the June period were significantly lower than those of the September period. On the other hand, the mean (CO ₃ ^2?  + HCO₃ ^?) and RSC and MR values in the June period were significantly higher than those of the September period. The order of relative abundance of major cations in the groundwater (in mg L^?1) is in order Na⁺ > Mg²⁺ > Ca²⁺ > K⁺. The order of the anions abundance (mg L^?1) is SO₄ ^2? > Cl^? > HCO₃ ^? > CO₃ ^2? in this research. Log and square-root transformation were carried out for the most of the water properties before the calculation of semivariance. The nugget ratio showed all the variables were strongly spatial dependent except for K⁺ and Mg²⁺ and (CO₃ ^2? + HCO₃ ^?) which showed moderate spatial dependence (ratio ranging from 28 to 49.9 %). Spatial distribution analysis of groundwater quality indicated that The EC, TDS values and Na and Cl^? contents which is important water quality parameters increase from northern towards southern. The total hardness values increase also from northwestern towards southwestern.     

Fluoride-bearing groundwater in Gummanampadu Sub-basin, Guntur District, Andhra Pradesh, India

The functional factors responsible for fluoride (F^?)-bearing groundwater used for drinking as well as for cooking in the area of Gummanampadu Sub-basin, Guntur District, Andhra Pradesh, India are discussed. The study area is a part of an Archean Gneissic Complex, consisting of banded-biotite-hornblende-gneisses, over which the Proterozoic Cumbhum quartzites, shales, phyllites, and dolomitic limestones occur. The chemistry of groundwater is dominated by carbonates (HCO₃ ^? and CO₃ ^2?) at a higher pH. This results in a higher total alkalinity over total hardness, causing an excess alkalinity. Sodium ion is dominated among the cations (Ca²⁺, Mg²⁺, and K⁺). The concentration of F^? (2.1–3.7 mg/L) is higher than that of desirable national limit (1.2 mg/L) prescribed for drinking purpose. A significant positive correlation exists between F^? and pH as well as that between F^? and HCO₃ ^? + CO₃ ^2?. This indicates that the alkaline condition is the prime conducive factor for dissolving F^?-bearing minerals more effectively leading to a higher concentration of F^? in the groundwater. Furthermore, a positive chloro-alkaline index reflects the ion exchange, and an oversaturation with respect to CaCO₃ indicates the evaporation. In addition, a negative relation between the well depth and F^? shows the effect of solubility and/or leaching of salts in different depth levels. These factors regulate the concentration of F^? in the groundwater. On the other hand, a positive correlation of F^? with SO₄ ^2? as well as with K⁺ shows the human land use activities (namely, use of chemical fertilizers, disposal of domestic wastes, etc.), which add F^? to the groundwater. A significant number of the residents of the study area suffer from the health disorders related to fluorosis, which is a consequence of higher concentration of F^? in the drinking water. Thus, this study emphasizes the need for supply of safe drinking water, nutritional diet, rainwater-harvesting structures, and public education to realize “health for all” motto of World Health Organization.     

Impact of anthropogenic activities on the chemistry and quality of groundwater: a case study from a terrain near Zarand City, Kerman Province, SE Iran

Groundwater of an aquifer located in the vicinity of a large coal washery near Zarand City, Iran consists of two hydrochemically differing facies, which have been informally designated as groundwater (A) and groundwater (B). Groundwater (A) is native, brackish in composition and is characterized by Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and SO₄ ^2? > HCO₃ ^? > Cl^? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, and values of chloro-alkaline indices, C ratio and Na⁺/Cl^? molar ratio indicate that in the groundwater (A), the ionic load of Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ^2? and HCO₃ ^? is derived essentially from weathering of both carbonates and aluminosilicates and direct cation and reverse cation–anion exchange reactions. Groundwater (B) is the polluted variant of the groundwater (A), brackish to saline in composition, and unlike the groundwater (A), consists of HCO₃ ^? as the dominant anion. In comparison with the groundwater (A), the groundwater (B) contains higher concentrations of all ions, and its average ionic load (av. = 59.74 me/L) is 1.43 times higher than that of the groundwater (A) (av. = 41.54 me/L). Additional concentrations of Ca²⁺, Mg²⁺, K⁺, SO₄ ^2?, Cl^? and HCO₃ ^? in the groundwater (B) are provided mainly by downward infiltrating water from the coal washery tailings pond and reverse cation–anion exchange reaction between tailings pond water and exchanger of the aquifer matrix during non-conservative mixing process of groundwater (A) and tailings pond water. Certain additional concentrations of Na⁺, K⁺ and NO₃ ^? in the groundwater (B) are provided by other anthropogenic sources. Quality wise, both groundwaters are marginally suitable for cultivation of salt-tolerant crops only.     

CO<Subscript>2</Subscript> mineralization of natural wollastonite into porous silica and CaCO<Subscript>3</Subscript> powders promoted via membrane electrolysis

CO₂ is a greenhouse gas, whose emissions threaten the existence of human beings. Its inherently safe sequestration can be performed via CO₂ mineralization, which is relatively slow under natural conditions. In this work, an energy-saving membrane electrolysis technique was proposed for accelerating the CO₂ mineralization of wollastonite into SiO₂ and CaCO₃ products. The electrolysis process involved splitting NH₄Cl into HCl and NH₃·H₂O via hydrogen oxidation and water reduction at the anode and cathode of the electrolytic system, respectively. In contrast to the chlor-alkali electrolysis, this method did not involve Cl^? oxidation and the standard potential of the anode was reduced. Additionally, NH₄Cl was used as the electrolyte instead of NaCl; as a result, the generation of NH₃·H₂O instead of NaOH occurred in the catholyte and the cathodic pH dramatically decreased, thus reducing the cathodic potential for hydrogen evolution. The observed changes led to a 73.5% decrease in the energy consumption. Moreover, after the process of CO₂ mineralization was optimized, SiO₂ with a specific surface area of 221.8 m² g^?1 and CaCO₃ with a purity of 99.9% were obtained.     

CO<Subscript>2</Subscript> flux variation and its contribution area in the debris-covered area of Koxkar Glacier,Mt. Tianshan in China

During the formation and development of glacial meltwater runoff, hydrochemical erosion is abundant, especially the hydrolysis of K/Na feldspar and carbonates, which can consume H⁺ in the water, promote the formation of bicarbonate by dissolving atmospheric CO₂, and affect the regional carbon cycle. From July 21, 2015, to July 18, 2017, the CO₂ concentration and flux were observed by the eddy covariance (EC) method in the relatively flat and open moraine cover area of Koxkar Glacier in western Mt. Tianshan, China. We found that: (1) atmospheric CO₂ fluxes ranged from ??408.95 to 81.58 mmol m^?2 day^?1 (average ? 58.68 mmol m^?2 day^?1), suggesting that the study area is a significant carbon sink, (2) the CO₂ flux footprint contribution areas were primarily within 150 m of the EC station, averaging total contribution rates of 93.30%, 91.39%, and 90.17% of the CO₂ flux in the snow accumulation, snow melting, and glacial melting periods, respectively. Therefore, the contribution areas with significant influences on CO₂ flux observed at EC stations were concentrated, demonstrating that grassland CO₂ flux around the glaciers had little effect at the EC stations, (3) in the predominant wind direction, under stable daytime atmospheric stratification, the measurement of CO₂ flux, as interpreted by the Agroscope Reckenholz Tanikon footprint tool, was 79.09% ± 1.84% in the contribution area. This was slightly more than seen at night, but significantly lower than the average under unstable atmospheric stratification across the three periods of interest (89%). The average distance of the farthest point of the flux footprint under steady state atmospheric conditions was 202.61?±?69.33 m, markedly greater than that under non-steady state conditions (68.55?±?10.34 m). This also indicates that the CO₂ flux observed using EC was affected primarily by hydrochemical erosion reactions in the glacier area, (4) a good negative correlation was found between net glacier exchange (NGE) of CO₂ and air temperature on precipitation-free days. Strong ice and snow ablation could promote hydrochemical reactions of soluble substances in the debris area and accelerated sinking of atmospheric CO₂. Precipitation events might reduce snow and ice melting, driven by reduced regional temperatures. However, a connection between NGE and precipitation, when less than 8.8 mm per day, was not obvious. When precipitation was greater than 8.8 mm per day, NGE decreased with increasing precipitation, (5) graphically, the slope of NGE, related to daily runoff, followed a trend: snow melting period?>?snow accumulation period?>?early glacial ablation period?>?late glacier ablation period?>?dramatic glacier ablation period. The slope was relatively large during snow melting, likely because of CO₂ sinking caused by water–rock interactions. The chemical reaction during elution in the snow layer might also promote atmospheric CO₂ drawdown. At the same time, the damping effect of snow cover and the almost-closed glacier hydrographic channel inhibited the formation of regional runoff, possibly providing sufficient time for the chemical reaction, thus promoting further CO₂ drawdown.     

Freshwater-Saltwater Mixing Effects on Dissolved Carbon and CO<Subscript>2</Subscript> Outgassing of a Coastal River Entering the Northern Gulf of Mexico

The delivery of dissolved carbon from rivers to coastal oceans is an important component of the global carbon budget. From November 2013 to December 2014, we investigated freshwater-saltwater mixing effects on dissolved carbon concentrations and CO₂ outgassing at six locations along an 88-km-long estuarine river entering the Northern Gulf of Mexico with salinity increasing from 0.02 at site 1 to 29.50 at site 6 near the river’s mouth. We found that throughout the sampling period, all six sites exhibited CO₂ supersaturation with respect to the atmospheric CO₂ pressure during most of the sampling trips. The average CO₂ outgassing fluxes at site 1 through site 6 were 162, 177, 165, 218, 126, and 15 mol m^?2 year^?1, respectively, with a mean of 140 mol m^?2 year^?1 for the entire river reach. In the short freshwater river reach before a saltwater barrier, 0.079 × 10⁸ kg carbon was emitted to the atmosphere during the study year. In the freshwater-saltwater mixing zone with wide channels and river lakes, however, a much larger amount of carbon (3.04 × 10⁸ kg) was emitted to the atmosphere during the same period. For the entire study period, the river’s freshwater discharged 0.25 × 10⁹ mol dissolved inorganic carbon (DIC) and 1.77 × 10⁹ mol dissolved organic carbon (DOC) into the mixing zone. DIC concentration increased six times from freshwater (0.24 mM) to saltwater (1.64 mM), while DOC showed an opposing trend, but to a lesser degree (from 1.13 to 0.56 mM). These findings suggest strong effects of freshwater-saltwater mixing on dissolved carbon dynamics, which should be taken into account in carbon processing and budgeting in the world’s estuarine systems.     

Using hydrochemistry and environmental isotopes in the assessment of groundwater quality in the Euphrates alluvial aquifer,Syria

Hydrochemical and environmental isotope methods were used to characterize the groundwater quality in ten wells belonging to the Euphrates alluvial aquifer in Syria, with the aim to assess the origin and dynamic of groundwater salinization in this system. The Euphrates River (ER) water along its entire course in Syria is rather fresh (TDS < 0.5 g/L), and thus, it is suitable for drinking and irrigation purposes. Groundwater salinity progressively increases from north to south, changing from almost freshwater (TDS < 0.6 g/L), with a Ca–Mg and HCO₃ type near the Syrian–Turkish border to brackish water (1 < TDS < 3 g/L), with a Ca–Mg or Na–Ca–Mg and SO₄–HCO₃ type in the vicinity of Al-Raqqa, and hence it can safely be used for irrigation. Downstream Deir-Ezzor the groundwater quality becomes fairly saline to very saline (3 < TDS < 29 g/L), with a Na–Cl type, and therefore it has an absolute hazard (SAR > 5) for irrigation uses. This pattern of chemical evolution, which is also clearly reflected in the variations of groundwater ionic ratios, completely agrees with the thermodynamic simulation results obtained by an experimental evaporation essay of a water sample taken from the ER near Deir-Ezzor. Stable isotopes permit the distinction between three main evaporation processes: under high, intermediate and low humidity conditions. Radioisotopes (³H and ¹⁴C) indicate the recent age and renewability of groundwater in this aquifer and confirm that its origin is entirely belonged to the ER water, either by direct bilateral interconnection or by vertical infiltration of the irrigation water totally taken from the ER. Relationships between major ions and δ¹⁸O values of the groundwater allow to differentiate between two main enrichment processes: either evaporation only or evaporation plus dissolution, that can explain altogether the development of groundwater salinity in such a dry area.     

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.     

Balancing the Oceanic Calcium Carbonate Cycle: Consequences of Variable Water Column ��

The paired chemical reactions, Ca²⁺ + 2HCO₃ ^? ? CaCO₃ + CO₂ + H₂O, overestimate the ratio of CO₂ flux to CaCO₃ flux during the precipitation or dissolution of CaCO₃ in seawater. This ratio, which has been termed ??, is about 0.6 in surface seawater at 25°C and at equilibrium with contemporary atmospheric CO₂ and increases towards 1.0 as seawater cools and pCO₂ increases. These conclusions are based on field observations, laboratory experiments, and equilibrium calculations for the seawater carbonate system. Yet global geochemical modeling indicates that small departures of ?? from 1.0 would cause dramatic, rapid, and unrealistic change in atmospheric CO₂. ?? can be meaningfully calculated for a water sample whether or not it is in equilibrium with the atmosphere. The analysis presented here demonstrates that the atmospheric CO₂ balance can be maintained constant with respect to seawater CaCO₃ reactions if one considers the difference between CaCO₃ precipitation and burial and differing values for ?? (both <1.0) in regions of precipitation and dissolution within the ocean.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.     

Hydrogeochemical characterization and evolution of a regional karst aquifer in the Cuatrociénegas area,Mexico

The Cuatrociénegas area is useful for the investigation of the effect of groundwater extraction in the Chihuahuan freshwater xeric ecoregion. It has been investigated at this time using a selection of geochemical indicators (major, minor and trace elements) and δ³⁴S data, to characterize the origin of groundwater, the main geochemical processes and the mineral/groundwater interactions controlling the baseline geochemistry. The area is composed of limestones of Mesozoic age, with a composite thickness of about 500 m, overlaid by basin fill (poorly consolidated young sediments). Substantial water extraction and modification of natural discharges from the area along the last century have produced a detrimental impact on ecosystem structure and function. Water–rock interactions, mixing and evaporative processes dominate the baseline groundwater quality. Natural recharge is HCO₃–Ca type in equilibrium with calcite, low salinity (TDS?<?500 mg/L), Cl^? lower than 11 mg/L and average Li⁺ concentration of 0.005 mg/L. Along the groundwater flow systems, δ³⁴S evidence and mass transfer calculations indicate that Cretaceous gypsum dissolution and dedolomitization reactions adjust water composition to the SO₄–Ca type. The increase of water–rock interaction is reflected by Cl^? values increase (average 68 mg/L), TDS up to about 1500 mg/L and an average Li⁺ concentration of 0.063 mg/L. Calculations with chemical geothermometers indicate that temperature at depth could be at maximum of 15–20 °C higher than field-measured temperature for pozas. After groundwater is discharged to the surface, chemical evolution continues; water evaporation, CO₂ degassing and precipitation of minerals such as gypsum, calcite and kaolinite represent the final processes and reactions controlling water chemical composition.     

Geochemistry and quality of groundwater of Gummanampadu sub-basin, Guntur District, Andhra Pradesh, India

Groundwater survey has been carried out in the area of Gummanampadu sub-basin located in Guntur District, Andhra Pradesh, India for assessing the factors that are responsible for changing of groundwater chemistry and consequent deterioration of groundwater quality, where the groundwater is a prime source for drinking and irrigation due to non-availability of surface water in time. The area is underlain by the Archaean Gneissic Complex, over which the Proterozoic Cumbhum rocks occur. The results of the plotting of Ca²⁺ + Mg²⁺ versus HCO₃ ^? + CO₃ ^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄ ^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃ ^? + CO₃ ^2?, Na⁺ versus Ca²⁺ and Na⁺: Cl^? versus EC indicate that the rock–water interaction under alkaline condition is the main mechanism in activating mineral dissociation and dissolution, causing the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, CO₃ ^2?, SO₄ ^2? and F^? ions into the groundwater. The ionic relations also suggest that the higher concentrations of Na⁺ and Cl^? ions are the results of ion exchange and evaporation. The influences of anthropogenic sources are the other cause for increasing of Mg²⁺, Na⁺, Cl^?, SO₄ ^2? and NO₃ ^? ions. Further, the excess alkaline condition in water accelerates more effective dissolution of F^?-bearing minerals. Moreover, the chemical data plotted in the Piper’s, Gibbs’s and Langelier–Ludwig’s diagrams, computed for the chloro-alkaline and saturation indices, and analyzed in the principal component analysis, support the above hypothesis. The groundwater quality is, thus, characterized by Na⁺ > Ca²⁺ > Mg²⁺ > K⁺: HCO₃ ^? + CO₃ ^2? > Cl^? > SO₄ ^2? > NO₃ ^? > F^? facies. On the other hand, majority of groundwater samples are not suitable for drinking with reference to the concentrations of TDS, TH, Mg²⁺ and F^?, while those are not good for irrigation with respect to USSL’s and Wilcox’s diagrams, residual sodium carbonate, and magnesium hazard, but they are safe for irrigation with respect to permeability index. Thus, the study recommends suitable management measures to improve health conditions as well as to increase agricultural output.     

CO<Subscript>2</Subscript>-assisted removal of nutrients from municipal wastewater by microalgae <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> and <Emphasis Type="Italic">Scenedesmus obliquus</Emphasis>

Axenic culture of microalgae Chlorella vulgaris ATCC^® 13482 and Scenedesmus obliquus FACHB 417 was used for phycoremediation of primary municipal wastewater. The main aim of this study was to measure the effects of normal air and CO₂-augmented air on the removal efficacy of nutrients (ammonia N and phosphate P) from municipal wastewater by the two microalgae. Batch experiments were carried out in cylindrical glass bottles of 1 L working volume at 25 °C and cool fluorescent light of 6500 lux maintaining 14/10 h of light/dark cycle with normal air supplied at 0.2 L min^?1 per liter of the liquid for both algal strains for the experimental period. In the next set of experiments, the treatment process was enhanced by using 1, 2 and 5% CO₂/air (vol./vol.) supply into microalgal cultures. The enrichment of inlet air with CO₂ was found to be beneficial. The maximum removal of 76.3 and 76% COD, 94.2 and 92.6% ammonia, and 94.8 and 93.1% phosphate after a period of 10 days was reported for C. vulgaris and S. obliquus, respectively, with 5% CO₂/air supply. Comparing the two microalgae, maximum removal rates of ammonia and phosphate by C. vulgaris were 4.12 and 1.75 mg L^?1 day^?1, respectively, at 5% CO₂/air supply. From kinetic study data, it was found that the specific rates of phosphate utilization (q _phsophate) by C. vulgaris and S. obliquus at 5% CO₂/air supply were 1.98 and 2.11 day^?1, respectively. Scale-up estimation of a reactor removing phosphate (the criteria pollutant) from 50 MLD wastewater influent was also done.