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1.
A statistical evaluation of the results of HCO3‐ determinations in geothermal waters during the interlaboratory comparison programmes of the International Association of Geochemistry and Cosmochemistry (IAGC) and International Atomic Energy Agency (IAEA) indicated that the analytical uncertainty increases with decreasing concentration of HCO3‐ and was ? 25% for 50 μg ml‐1 and ? 60% for 25 μg ml‐1 of HCO3‐. The analytical method (Method 1) used by chemists and hydrologists works well for waters containing carbonic alkalinity, whereas Method 2 used by geochemists is conceptually incorrect. A stepwise comparison between the theoretical and experimental titration results for a given concentration Na2CO3 (0.0988 mol l‐1) solution was performed to understand the limitations of the titration method for geothermal water analysis. Backward titration from the carbonic acid equivalence point (H2CO3EP) to the original pH after CO2 removal, as had been practised earlier in the geothermal industry, in order to estimate the contribution of silicic and boric alkalinities to the total alkalinity, is incorrect because the amount of standard base (NaOH) added is equivalent to silicic and boric alkalinities plus some OH‐ alkalinity. In a Na2CO3 solution, the added NaOH is equivalent to OH‐ alkalinity only. Backward titration is only needed from the forward titration end point to the H2CO3EP in order to correct the total alkalinity for the excess of standard acid (HCl) added during the forward titration. In the case of a Na2CO3 solution, the H2CO3EP, after removal of CO2 during the forward titration, is at pH = 7, not at pH = 4.5 (3.8) as has been considered in literature. Similarly, the liberation of CO2 during titration occurs well before the point expected theoretically and it is less for shorter titration time. The revised procedure for the determination of carbonic species concentration is presented and illustrated for a water sample from Alchichica Lake, Puebla, Mexico.  相似文献   

2.
Anthropogenic carbon dioxide (CO2) emissions reduce pH of marine waters due to the absorption of atmospheric CO2 and formation of carbonic acid. Estuarine waters are more susceptible to acidification because they are subject to multiple acid sources and are less buffered than marine waters. Consequently, estuarine shell forming species may experience acidification sooner than marine species although the tolerance of estuarine calcifiers to pH changes is poorly understood. We analyzed 23 years of Chesapeake Bay water quality monitoring data and found that daytime average pH significantly decreased across polyhaline waters although pH has not significantly changed across mesohaline waters. In some tributaries that once supported large oyster populations, pH is increasing. Current average conditions within some tributaries however correspond to values that we found in laboratory studies to reduce oyster biocalcification rates or resulted in net shell dissolution. Calcification rates of juvenile eastern oysters, Crassostrea virginica, were measured in laboratory studies in a three-way factorial design with 3 pH levels, two salinities, and two temperatures. Biocalcification declined significantly with a reduction of ∼0.5 pH units and higher temperature and salinity mitigated the decrease in biocalcification.  相似文献   

3.
《Applied Geochemistry》2005,20(10):1941-1964
The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples.Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5–4) or near neutral (pH 6–7); ≈ 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6.The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze.The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= −net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples.A meaningful “net” acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinitymeasured − Hot Aciditymeasured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = −Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured − Aciditycalculated) is recommended with some cautions.  相似文献   

4.
The present study highlights the first evidence of hydrothermal mineral Thenardite (Na2SO4) from Puga geothermal area, North-western Himalayan belt in Ladakh Geothermal Province, India, which is unequivocal evidence for the presence of high-temperature hydrothermal fluid activity from one of the thickest crust areas of the Earth. The Puga geothermal belt illustrates a fault-bounded hydrothermal system with a clearly defined conductive zone, coinciding with Kiagar Tso fault typically exemplifying a shallow-level medium enthalpic geothermal reservoir. The hydrogeochemistry suggests that thermal and non-thermal waters are of Na-Cl-HCO3 and Ca-Mg-HCO3 type, respectively, with neutral to near alkaline pH. The silica and cation geothermometry reveal sub-surface temperatures around 150 °C and 250 °C, respectively, at shallow depth; however, >250 °C is anticipated at the deepest levels (~3 km). Stable isotope (δD and δ18O) studies explicate depletion of isotopic content for thermal waters over Puga river water and radiogenic isotope (3H) suggests matured thermal waters with ongoing water-rock interactions. The recharge altitude estimation and physiographic studies put forth that geothermal reservoir is recharged with the ice masses located at an altitude of 6458 m above mean sea level (msl) in the west of Puga valley, probably from the highest peak of Polokong La mountain. The two key processes participating in regulation of proportions of the dissolved salts in the thermal waters are silicate weathering and ion-exchange kinetics. The powder X-ray diffraction study reveals a major occurrence of hydrothermal mineral thenardite in the hot spring deposits for the first time along with huge encrustations of trona, borax, calcite and elemental sulfur. The high-temperature fluids encounter thenardite, pyrite, and jarosite-bearing minerals in basement rock causing enrichment of SO42− and Cl− in geothermal waters. The temperature-dependent speciation modelling (50 °C–200 °C) for major ion Na+ reveals the composition of the reservoir fluid (~150 °C): Na+ > NaCO3− > NaSO4− > NaHCO3 > NaF > NaOH. A conceptual evolution model of thermal waters involving the recharge-deep circulation-mixing-discharge of thermal springs is hence put forth in the study using various hydrogeochemical insights.  相似文献   

5.
Epochs of changing atmospheric CO2 and seawater CO2–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO2 and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO2 to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO2 and enhanced biological production and burial of organic C, a small sink of anthropogenic CO2, accompanied by a continuous trend toward increasing autotrophy in coastal waters.  相似文献   

6.
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 (PCO2) 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, PCO2, and the first dissociation constant of carbonic acid (K1) data was consistently higher than that directly measured with a pH electrode. Similarly, calculation of PCO2 of surface waters from pH, DIC, and K1 data gave values up to twice that of atmospheric saturation despite repeated equilibrations with atmospheric PCO2. 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.  相似文献   

7.
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).  相似文献   

8.
Germanium concentrations in geothermal waters in Iceland lie mostly in the range 2–30 ppb. There is an overall positive relation between the germanium content of the water and its temperature. Most of the germanium occurs as Ge(OH)?5in solution but Ge(OH)4 may also be present in significant amounts in saline waters when above 200°C. Evidence indicates that aqueous germanium concentrations are controlled by exchange reactions where it substitutes for silica in silicates and iron in sulphides. It is the rate of dissolution and the relative abundance of the alteration minerals which take up germanium to a variable extent that ultimately fix Ge(OH)4 concentrations in the water. This, together with water pH, fixes total dissolved germanium. It is mostly the primary rock composition that dictates the relative abundance of the alteration minerals. Conductive cooling in upflow zones favours removal of germanium from solution. During the initial stages of boiling of rising hot water dissolution is enhanced but precipitation at later stages.Thermodynamic data of various aqueous germanium species and several minerals are summarized and dissociation constants and solubilities estimated at elevated temperatures using available predictive methods.  相似文献   

9.
Chemical and isotopic compositions of three hot springs and one cold spring in the Kirkgecit geothermal field, located 15 km southwest of Canakkale-Biga in the northwest of Turkey, were monitored five times during 2005 and 2007. The physico-chemical characteristics of the hot springs are average discharge 3–3.5 L/s, surface temperature 45–52°C, pH 8.9–9.3, and electrical conductivity (EC) 620–698 μS/cm. The cold spring has a temperature of 12–13°C, pH 7.5–8.3, and EC 653–675 μS/cm. The hot waters are Na-SO4 type, whereas the cold water is Ca-HCO3 type. Chemical geothermometers suggest that the reservoir temperature is around 80–100°C. The isotopic data (oxygen-18, deuterium and tritium) indicate that the thermal waters are formed by local recharge and deep circulation of meteoric waters.  相似文献   

10.
Deposition in the New Jersey Pinelands was very acidic (pH=4.17) and contained high levels of SO2 −2 based on bulk deposition measurementsfrom July 1984–July 1986. Streamwater over the same interval in undisturbed watersheds was less acidic (pH =4.52) and had proportionately less SO4 −2. A preliminary alkalinity budget for undisturbed watersheds suggested that SO4 −2 retention within Pinelands watersheds accounted for a large portion of the total alkalinity generated and thereby lessened the impact of acidic deposition on surface waters. The only process capable of explaining the retention of SO4 −2 was microbial sulfate reduction in the extensive wetlands surrounding Pinelands streams which occurred at high rates.  相似文献   

11.
Geothermal resources are very rich in Yunnan, China. However, source of dissolved solutes in geothermal water and chemical evolution processes remain unclear. Geochemical and isotopic studies on geothermal springs and river waters were conducted in different petrological-tectonic units of western Yunnan, China. Geothermal waters contain Ca–HCO3, Na–HCO3, and Na (Ca)–SO4 type, and demonstrate strong rock-related trace elemental distributions. Enhanced water–rock interaction increases the concentration of major and trace elements of geothermal waters. The chemical compositions of geothermal waters in the Rehai geothermal field are very complicated and different because of the magma chamber developed at the shallow depth in this area. In this geothermal field, neutral-alkaline geothermal waters with high Cl, B, Li, Rb Cs, As, Sb, and Tl contents and acid–sulfate waters with high Al, Mn, Fe, and Pb contents are both controlled by magma degassing and water–rock interaction. Geothermal waters from metamorphic, granite, and sedimentary regions (except in the Rehai area) exhibit varying B contents ranging from 3.31 mg/L to 4.49 mg/L, 0.23 mg/L to 1.24 mg/L, and <0.07 mg/L, respectively, and their corresponding δ11B values range from −4.95‰ to −9.45‰, −2.57‰ to −8.85‰, and −4.02‰ to +0.06‰. The B contents of these geothermal waters are mainly controlled by leaching host rocks in the reservoir, and their δ11B values usually decrease and achieve further equilibrium with its surrounding rocks, which can also be proven by the positive δ18O-shift. In addition to fluid–rock reactions, the geothermal waters from Rehai hot springs exhibit higher δ11B values (−3.43‰ to +1.54‰) than those yielded from other areas because mixing with the magmatic fluids from the shallow magma. The highest δ11B of steam–heated waters (pH 3.25) from the Zhenzhu spring in Rehai is caused by the fractionation induced by pH and the phase separation of coexisting steam and fluids. Given the strong water–rock interaction, some geothermal springs in western Yunnan show reservoir temperatures higher than 180 °C, which demonstrate potential for electricity generation and direct-use applications. The most potential geothermal field in western Yunnan is located in the Rehai area because of the heat transfer from the shallow magma chamber.  相似文献   

12.
《Applied Geochemistry》2000,15(6):865-878
Knowledge of the impact of N-fertilizers on the weathering-erosion processes of soils in intensively cultivated regions is of prime importance. Nitrification of NH4− fertilizers produces HNO3 in the basin of the Garonne river, enhancing soil degradation. Their influence on the weathering rates was determined by calculating the consumption rate of atmospheric/soil CO2 by soil weathering and erosion, and its contribution to the total dissolved riverine HCO3−. This contribution was found to be less than 50% which corresponds normally to a complete carbonate dissolution by carbonic acid, suggesting that part of the alkalinity in the river waters is due to carbonate dissolution by an acid other than carbonic acid, probably HNO3.  相似文献   

13.
《Applied Geochemistry》1998,13(7):861-884
Concentrations of the rare earth elements (REE), Th and U have been determined in thermal waters emerging from a number of locations in and around the Idaho Batholith. Previous investigators have suggested that the source of heat for the geothermal systems studied is the radioactive decay of K, Th and U which are enriched in the rocks through which the fluids flow. Thus, knowledge of the behavior of REE, Th and U in these systems may contribute to a better understanding of the potential consequences of the interaction of hydrothermal fluids with deeply buried nuclear waste. Such studies may also lead to the possible use of REE as an exploration tool for geothermal resources. The thermal waters investigated may be characterized as near-neutral to slightly alkaline, dilute, NaHCO3-dominated waters with relatively low temperatures of last equilibration with their reservoir rocks (<200°C). REE, Th and U concentrations were measured using Fe(OH)3 coprecipitation, followed by ICP-MS, which yielded detection limits of 0.01–0.003 μg/l for each element, depending on the volume of fluid sample taken. The concentrations of REE, Th and U measured (from <0.1 up to a few μg/l) are 3–5 orders of magnitude less than chondritic, in agreement with concentrations of these elements measured in other similar continental geothermal systems. The REE exhibit light REE-enriched patterns when normalized to chondrite, but when normalized to NASC or local granites, they exhibit flat or slightly heavy REE-enriched trends. These findings indicate that the REE are either taken up in proportion to their relative concentrations in the source rocks, or that the heavy REE are preferentially mobilized. Concentrations of REE and Th are often higher in unfiltered, compared to filtered samples, indicating an important contribution of suspended particulates, whereas U is apparently truly dissolved. In some of the hot springs the REE concentrations exhibit marked temporal variations, which are greater than the variations observed in major element concentrations, alkalinity and temperature. There are also variations in the fluid concentrations of REE, Th and U related to general location within the study area which may be reflective of variations in the concentrations of these elements in the reservoir rocks at depth. Thermal waters in the southern and central parts of the field area all contain ∑REE concentrations exceeding 0.1 μg/l (up to as high as 3 μg/l), Th exceeding 0.2 μg/l and U generally <0.4 μg/l. In contrast, thermal waters from the northern area contain lower ∑REE (<0.6 μg/l) and Th (<0.1 μg/l), but higher U (>3.0 μg/l). Using experimentally measured and theoretically estimated thermodynamic data, the distribution of species for La, Ce and Nd have been calculated and also the solubility of pure, endmember (La, Ce, Nd) phosphate phases of the monazite structure in selected hot spring fluids. These calculations indicate that, at the emergence temperatures, CO2−3 and OH− complexes of the REE are the predominant species in the thermal waters, whereas at the deep-aquifer temperatures, OH complexes predominate. In these thermal waters, monazite solubility is strongly prograde with respect to temperature, with solubility often decreasing several orders of magnitude upon cooling from the deep-aquifer to the emergence temperature. At the surface temperature, calculated monazite solubilities are, within the uncertainty of the thermodynamic data, comparable to the REE concentrations measured in the filtered samples, whereas at the deep-aquifer temperature, monazite solubilities are generally several orders of magnitude higher than the REE concentrations measured in the filtered or unfiltered samples. Therefore, a tentative model is suggested in which the thermal fluids become saturated with respect to a monazite-like phase (or perhaps an amorphous or hydrated phosphate) upon ascent and cooling, followed by subsequent precipitation of that phase. The temporal variations in REE content can then be explained as a result of sampling variable mixtures of particulate matter and fluid and/or variable degrees of attainment of equilibrium between fluid and solid phosphate.  相似文献   

14.
The reservoir temperature and conceptual model of the Pasinler geothermal area, which is one of the most important geothermal areas in Eastern Anatolia, are determined by considering its hydrogeochemical and isotope properties. The geothermal waters have a temperature of 51 °C in the geothermal wells and are of Na–Cl–HCO3 type. The isotope contents of geothermal waters indicate that they are of meteoric origin and that they recharge on higher elevations than cold waters. The geothermal waters are of immature water class and their reservoir temperatures are calculated as 122–155 °C, and their cold water mixture rate is calculated as 32%. According to the δ13CVPDB values, the carbon in the geothermal waters originated from the dissolved carbon in the groundwaters and mantle-based CO2 gases. According to the δ34SCDT values, the sources of sulfur in the geothermal waters are volcanic sulfur, oil and coal, and limestones. The sources of the major ions (Na+, Ca2+, Mg2+, Cl?, and HCO3 ?) in the geothermal waters are ion exchange and plagioclase and silicate weathering. It is determined that the volcanic rocks in the area have effects on the water chemistry and elements like Zn, Rb, Sr, and Ba originated from the rhyolite, rhyolitic tuff, and basalts. The rare earth element (REE) content of the geothermal waters is low, and according to the normalized REE diagrams, the light REE are getting depleted and heavy REE are getting enriched. The positive Eu and negative Ce anomalies of waters indicate oxygen-rich environments.  相似文献   

15.
以经岩溶水驯化的小球藻（Chlorella vulgaris）和喜钙念珠藻(Nostoc calcicola Breb.)为实验对象,在封闭体系中用Willbur和 Anderson 方法比较研究两种不同微藻在不同CO2浓度下碳酸酐酶活性变化情况。结果表明:在低于3%CO2浓度的环境中岩溶微藻可通过快速调节自身碳酸酐酶活性来应对CO2升高带来的生境影响,在影响最大的2.5%的环境下小球藻与喜钙念珠藻碳酸酐酶活性分别提高了1.46倍和2.12倍;岩溶微藻应对CO2浓度增大带来的pH下降有着重要的恢复作用,随培养时间增长培养环境中的pH得到恢复;随着CO2浓度的增大,岩溶因子对碳酸酐酶有着重要的影响;培养48 h时Ca2+与喜钙念珠藻碳酸酐酶的相关性最高,而电导率（EC）与小球藻碳酸酐酶相关程度最高。   相似文献   

16.
A statistical evaluation of the results of geochemical analyses of geothermal waters during interlaboratory comparison programmes of the International Association of Geochemistry and Cosmochemistry (IAGC) and International Atomic Energy Agency (IAEA) was performed to estimate the uncertainty of measurement of pH, electrical conductivity, Na+, K+, Ca2+, Mg2+, Li+, Cl?, HCO3?, SO42?, SiO2 and B. The uncertainty of measurement was found to increase exponentially with decrease in value (concentration) for all the parameters except for pH, electrical conductivity and SiO2 and was of the same order of magnitude as the concentrations for values of less than 1 μ ml?1. There was an overall uncertainty of ± 2.5% in the measurement of pH and ± 30% in SiO2. For all the other chemical species the uncertainty data were modelled by exponential curves. The sample IAEA14 was prepared by dissolving commercial reagents (i.e., represents a solution of known composition). Thus, the calculated values are considered to be the conventional true values for each chemical parameter. The difference between the measured mean of the data submitted by participating laboratories and the conventional true value for each parameter (i.e., bias of submitted measurements) for the species Na+, K+, Ca2+, Mg2+, Cl? and SO42? was ‐3.5, ‐1.1, ‐13.3, ‐53.6, ‐12.6 and ‐86.6%, respectively. The observed bias was of the same order of magnitude as statistical fluctuations (1s) for Na+ and K+, but significantly higher for Ca2+, Mg2+, Cl? and SO42?. Two methods, uncertainty interval and GUM (“guide to the expression of uncertainty of measurement”) were used to propagate uncertainty in the pH calculation of geothermal reservoir fluid. The application of the methods is illustrated by considering the IAEA10 and IAEA11 samples analysed in the interlaboratory comparisons as separated geothermal waters at atmospheric pressure.  相似文献   

17.

Triclosan (TCS) is an antimicrobial compound found in many household products used across the world. TCS is not completely removed in wastewater systems, resulting in trace-level concentrations present ubiquitously in surface waters. The direct photodegradation of TCS has been widely studied, with results indicating that TCS breaks down to chlorophenols and dioxins. To date, no studies have specifically investigated the effects of alkalinity on the photolysis of the acidic form of TCS. This study assessed the effect of carbonate/bicarbonate alkalinity, which is ubiquitous in natural waters, on the photolysis rate of TCS. Results indicate that bicarbonate enhances the photodegradation of TCS at pH values well below the pKa of TCS (7.9), with direct photolysis reaction kinetics that are very slow in the absence of buffers, but significant in the presence of bicarbonate (0.711 h?1 at pH 6.55). At pH values well above its pKa, both unbuffered- and buffered-mediated photolysis increased dramatically (1.92 h?1 for direct photolysis and 2.86 h?1 in buffered water) and is attributable to the increased photoreactivity of TCS by its conjugate base. Photolysis of methyl triclosan (MeTCS), a non-acidic analog of TCS, demonstrated the importance of TCS’s acidic functionality as MeTCS did not degrade at any pH. The observed influence of alkalinity on the acidic form of TCS photolysis was attributed to both a decrease in its excited state pKa, coupled with TCS deprotonation through an excited state proton transfer to a base (bicarbonate and to a lesser degree hydrogen phosphate) resulting in the more photo-labile conjugate base form of TCS.

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18.
Saline alkaline lakes that precipitate sodium carbonate evaporites are most common in volcanic terrains in semi‐arid environments. Processes that lead to trona precipitation are poorly understood compared to those in sulphate‐dominated and chloride‐dominated lake brines. Nasikie Engida (Little Magadi) in the southern Kenya Rift shows the initial stages of soda evaporite formation. This small shallow (<2 m deep; 7 km long) lake is recharged by alkaline hot springs and seasonal runoff but unlike neighbouring Lake Magadi is perennial. This study aims to understand modern sedimentary and geochemical processes in Nasikie Engida and to assess the importance of geothermal fluids in evaporite formation. Perennial hot‐spring inflow waters along the northern shoreline evaporate and become saturated with respect to nahcolite and trona, which precipitate in the southern part of the lake, up to 6 km from the hot springs. Nahcolite (NaHCO3) forms bladed crystals that nucleate on the lake floor. Trona (Na2CO3·NaHCO3·2H2O) precipitates from more concentrated brines as rafts and as bottom‐nucleated shrubs of acicular crystals that coalesce laterally to form bedded trona. Many processes modify the fluid composition as it evolves. Silica is removed as gels and by early diagenetic reactions and diatoms. Sulphate is depleted by bacterial reduction. Potassium and chloride, of moderate concentration, remain conservative in the brine. Clastic sedimentation is relatively minor because of the predominant hydrothermal inflow. Nahcolite precipitates when and where pCO2 is high, notably near sublacustrine spring discharge. Results from Nasikie Engida show that hot spring discharge has maintained the lake for at least 2 kyr, and that the evaporite formation is strongly influenced by local discharge of carbon dioxide. Brine evolution and evaporite deposition at Nasikie Engida help to explain conditions under which ancient sodium carbonate evaporites formed, including those in other East African rift basins, the Eocene Green River Formation (western USA), and elsewhere.  相似文献   

19.
The goal of this study was to highlight the occurrence of an additional proton-promoted weathering pathway of carbonate rocks in agricultural areas where N-fertilizers are extensively spread, and to estimate its consequences on riverine alkalinity and uptake of CO2 by weathering. We surveyed 25 small streams in the calcareous molassic Gascogne area located in the Garonne river basin (south-western France) that drain cultivated or forested catchments for their major element compositions during different hydrologic periods. Among these catchments, the Hay and the Montoussé, two experimental catchments, were monitored on a weekly basis. Studies in the literature from other small carbonate catchments in Europe were dissected in the same way. In areas of intensive agriculture, the molar ratio (Ca + Mg)/HCO3 in surface waters is significantly higher (0.7 on average) than in areas of low anthropogenic pressure (0.5). This corresponds to a decrease in riverine alkalinity, which can reach 80% during storm events. This relative loss of alkalinity correlates well with the content in surface waters. In cultivated areas, the contribution of atmospheric/soil CO2 to the total riverine alkalinity (CO2 ATM-SOIL/HCO3) is less than 50% (expected value for carbonate basins), and it decreases when the nitrate concentration increases. This loss of alkalinity can be attributed to the substitution of carbonic acid (natural weathering pathway) by protons produced by nitrification of N-fertilizers (anthropogenic weathering pathway) occurring in soils during carbonate dissolution. As a consequence of these processes, the alkalinity over the last 30 years shows a decreasing trend in the Save river (one of the main Garonne river tributaries, draining an agricultural catchment), while the nitrate and calcium plus magnesium contents are increasing.We estimated that the contribution of atmospheric/soil CO2 to riverine alkalinity decreased by about 7-17% on average for all the studied catchments. Using these values, the deficit of CO2 uptake can be estimated as up to 0.22-0.53 and 12-29 Tg1 yr−1 CO2 on a country scale (France) and a global scale, respectively. These losses represent up to 5.7-13.4% and only 1.6-3.8% of the total CO2 flux naturally consumed by carbonate dissolution, for France and on a global scale, respectively. Nevertheless, this loss of alkalinity relative to the Ca + Mg content relates to carbonate weathering by protons from N-fertilizers nitrification, which is a net source of CO2 for the atmosphere. This anthropogenic CO2 source is not negligible since it could reach 6-15% of CO2 uptake by natural silicate weathering and could consequently partly counterbalance this natural CO2 sink.  相似文献   

20.
This study focuses on the hydrochemical characteristics of 47 water samples collected from thermal and cold springs that emerge from the Hammam Righa geothermal field, located in north-central Algeria. The aquifer that feeds these springs is mainly situated in the deeply fractured Jurassic limestone and dolomite of the Zaccar Mount. Measured discharge temperatures of the cold waters range from 16.0 to 26.5 °C and the hot waters from 32.1 to 68.2 °C. All waters exhibited a near-neutral pH of 6.0–7.6. The thermal waters had a high total dissolved solids (TDS) content of up to 2527 mg/l, while the TDS for cold waters was 659.0–852.0 mg/l. Chemical analyses suggest that two main types of water exist: hot waters in the upflow area of the Ca–Na–SO4 type (Hammam Righa) and cold waters in the recharge zone of the Ca–Na–HCO3 type (Zaccar Mount). Reservoir temperatures were estimated using silica geothermometers and fluid/mineral equilibria at 78, 92, and 95 °C for HR4, HR2, and HR1, respectively. Stable isotopic analyses of the δ18O and δD composition of the waters suggest that the thermal waters of Hammam Righa are of meteoric origin. We conclude that meteoric recharge infiltrates through the fractured dolomitic limestones of the Zaccar Mount and is conductively heated at a depth of 2.1–2.2 km. The hot waters then interact at depth with Triassic evaporites located in the hydrothermal conduit (fault), giving rise to the Ca–Na–SO4 water type. As they ascend to the surface, the thermal waters mix with shallower Mg-rich groundwater, resulting in waters that plot in the immature water field in the Na–K–Mg diagram. The mixing trend between cold groundwaters from the recharge zone area (Zaccar Mount) and hot waters in the upflow area (Hammam Righa) is apparent via a chloride-enthalpy diagram that shows a mixing ratio of 22.6 < R < 29.2 %. We summarize these results with a geothermal conceptual model of the Hammam Righa geothermal field.  相似文献   

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