Genesis and evolution of high-pCO2 groundwaters of the Mukhen spa (Russian Far East)

We present the chemical and isotope compositions of the water and gas phases of the unique Mukhen cold high-pCO₂ spa. Estimated 5¹⁸O, 5D, and 5¹³C_tic values and data on geology and hydrogeology of the studied area indicate that the source of the groundwaters is meteoric waters, whereas carbon dioxide is of deep genesis and numerous regional faults are gas-feeding channels. Calculations of equilibrium reactions in the water-rock system show that the upper-aquifer waters (HCO₃-Ca-Mg) with low TDS are undersaturated with carbonate minerals, montmorillonites, and aluminosilicates but are oversaturated with kaolinite, whereas the lower-aquifer waters (HCO3-Na) with high TDS are oversaturated with calcite, dolomite, and clay minerals but are undersaturated with main aluminosilicates. We propose a new concept of the formation of these groundwaters, demonstrating that long interaction between rocks and groundwaters in the presence of CO₂ and considerable precipitation of secondary minerals are responsible for the high TDS of the lower-aquifer waters (up to 14 g/L) and their geochemical type (HCO₃-Na) and unusual isotope composition (5¹⁸O = -25.2%c, 5D = -69.0%c).     

Hydrochemistry of groundwater in the Savelugu–Nanton District, Northern Ghana

Calcite (CaCO₃), dolomite [CaMg(CO₃)₂], silicate dissolution, ion-exchange and reverse ion-exchange reactions are the predominant processes influencing groundwater quality in the Savelugu?CNanton District. The main objective of this study is to characterize groundwater and delineate water?Crock interactions responsible for the chemical evolution of groundwater in the District. Eighty-one (81) boreholes were sampled for quality assessment. Results showed that, the pH of the boreholes are slightly acidic to basic ranging from 6.1?C8.3?pH units. Conductivity values are low to high ranging from 147?C23,200???S/cm with, 23.5?% of groundwater within the study area being either brackish (1,500?C5,000???S/cm) or saline (>5,000???S/cm) and therefore, unsuitable for potable purposes. TDS values in groundwater varied widely, ranging from 62?C11,900?mg/L. 61.7?% of groundwater within the study area are fresh (TDS?<?500?mg/L). The chemical constituents generally, have low concentrations and are within the WHO (Guidelines for drinking water quality. Revision of the 1993 Guidelines. Final Task Group Meeting. Geneva, 2004) Guideline values. The relative abundance of cations and anions in the groundwater are in the order: Ca²⁺?>?Na⁺?>?Mg²⁺?>?K⁺ and HCO₃ ^??>?Cl^??>?SO₄ ^2??>?NO₃ ^? respectively. Multivariate statistical analysis showed expected process-based relationship derived mainly from the geochemical and biochemical processes within the aquifer. Hydrochemical facies using piper plot of major ions showed one major hydrochemical water type. The Ca?CMg?CHCO₃ water type. Due to the high cost of drilling of boreholes coupled with the high percentage (×1?%) of people without access to potable water in the Northern Region, it is recommended that the Government of Ghana and other stakeholders within the Water Sector take immediate measures to reduce (to recommended limits for potable uses) the levels of dissolved solids either by installing Reverse Osmosis equipments on such boreholes or employ other relatively known cheaper methods to reduce the dissolved solids to recommended limits. High yielding boreholes with hydrochemical parameters within WHO guideline limits in the Savelugu?CNanton District could also be mechanized to serve a wider area.     

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.     

Removal of nitrates from high-salinity wastewaters from desulphurization process with denitrifying bacteria encapsulated in Lentikats Biocatalyst

Successful elimination of high concentrations of N?CNO _x ^? (up to 250?mg/L) from high salinity wastewaters (up to 35?g/L Cl^??+?17?g/L SO₄ ^2?) originating from desulphurization process within coal power stations was achieved using pure cultures of denitrifying bacteria encapsulated in porous polyvinyl alcohol lenses (so called Lentikats Biocatalyst, LB). Laboratory batch tests revealed inhibitory influence of the raw wastewater on the denitrification activity, which was partially mitigated by the addition of P?CPO₄ ^3?. In following continuous tests, the denitrification activities reached the range 150?C450?mg?N/h/kg LB, i.e., values suitable for industrial scale applications. The higher activities were achieved under a lower salinity, higher N?CNO _x ^? influent concentrations and a prolonged retention time. The effluent N?CNO _x ^? concentrations were below the determination limit of 5?mg/L. After a period of 3?months, a significant decrease of denitrification activity of Lentikats Biocatalyst was observed. Addition of nutrients into the wastewater enabled fast regeneration of the initial activity. The overall results proved the applicability of Lentikats Biocatalysts for the removal of nitrates from high-salinity desulphurization water and other industrial wastewaters of similar character.     

Simultaneous Determination of Fluorine,Chlorine, Bromine and Iodine in Six Geochemical Reference Materials Using Pyrohydrolysis,Ion Chromatography and Inductively Coupled Plasma‐Mass Spectrometry

Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l^?1 for both F and Cl and 10 ng l^?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg^?1 for F and Cl and 2 μg kg^?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg^?1 for F and Cl, 100 μg kg^?1 for Br and 25 μg kg^?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.     

Arsenic in the Muteh gold mining district, Isfahan, Iran

Following the appearance of symptoms of arsenic toxicity in the inhabitants of villages in the Muteh gold mining region, central Iran, the concentration of this element in various parts of biogeochemical cycle is investigated. For this purpose, rock, groundwater, soil, plant, livestock hair and wool, and human hair samples are collected and analysed. Total arsenic content ranges from 23 to 2,500?mg/kg in rock samples, 7?C1,061???g/l in water, 12?C232?mg/kg in soil, 0.5?C16?mg/kg in plant samples, 4.10?C5.69?mg/kg in livestock hair and wool, and 0.64?C5.82?mg/kg in human hair. Arsenic concentration in various parts of biogeochemical cycle near the gold deposit in a metamorphic complex, and also close to the gold-processing plant, is very high and decreases exponentially with increasing distance from them. Arsenic concentration in water from a well close to the Muteh gold mine is above 1?mg/L. Arsenic in hair samples taken from local inhabitants is above the recommended levels, and the control samples in Shahre-Kord city. Arsenic concentration is higher in male population and correlates positively with age. It is suggested that arsenic resulting from the decomposition of ore mineral such as orpiment (As₂S₃), realgar (As₂S₂) and arsenopyrite (FeAsS) is responsible for polluting natural resources and the human intake via drinking water and the food chain. Gold mining and processing has undoubtedly enhanced the release of arsenic and intensified the observed adverse effects in Muteh area.     

Assessment of mixing between shallow and thermal waters using geochemical and environmental isotope tracers (N Portugal): a review and reinterpretation

Caldas de Moledo thermal (27–46 °C) spring and borehole waters issue in the region of the famous Port Wine vineyards, in the Douro River valley (Northern Portugal). The most abundant lithotypes are lower Cambrian metasedimentary rocks, Variscan granitoids and aplite-pegmatitic veins. The thermal waters are characterised by pH ≈ 9.0, TDS ranging from 200 to 350 mg/L, and belong to the HCO₃–Na facies indicating that the reservoir rock should be mainly granite. Since the local Spa is strongly dependent on water quality, the effects of mixing between local shallow cold groundwaters and deep thermal waters have been properly investigated. In the SO₄ ^2? (mg/L) versus δ¹⁸O (‰ vs. V-SMOW) diagram we can observe that some of the thermal springs show evidences of mixing (higher SO₄ ^2? concentrations) with local meteoric waters infiltrated at lower altitude sites (enriched δ¹⁸O signatures), showing the “altitude effect” in the isotopic composition of the recharge waters. Similar trends can be found in the K⁺, NO₃ ^?, Ca²⁺ and Na⁺ (mg/L) versus δ¹⁸O (‰ vs. V-SMOW) diagrams. It should be stated that SO₄ ^2?, K⁺ and Ca²⁺ are present in the fertilizers and fungicides used in the vineyards in the northern part of the country. Up to now, the thermal waters from boreholes used in the local Spa do not show evidences of mixing with shallow groundwaters contaminated with agrochemicals. The results obtained so far indicate that in the near future, special attention should be put on the possible occurrence of diffuse agricultural contamination (related to the Port Wine vineyards) in the thermal spring waters.     

Hydrochemical characteristics of Lastochka Spa (Primorye, Far East of Russia)

This study presents new data on major, trace and REE element concentration of groundwaters in Lastochka spa located in the northern part of Primorye, Far East of Russia. The studied area is characterized by two types of groundwaters issued from a spring and wells: fresh waters with low mineralization (Total Dissolved Solids is up to 400 mg/l) and high pCO₂ waters with high mineralization (TDS is up to 4700 mg/l). New data and previous δ¹³C_(TIC), oxygen (δ¹⁸O) and hydrogen (δ²H) isotope data indicate that these waters result from meteoric water infiltration in the Sikhote–Alin mountain, circulating at shallow depths in sedimentary rocks. CO₂ in groundwater is of mantle origin.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth’s mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280?°C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F–Cl–Br–I–H₂O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H₂O (D_Cl ^ol/melt = 1.6?±?0.9 × 10^?4) to 0.33 (6) wt% H₂O (D_Cl ^ol/melt = 2.2?±?1.1 × 10^?4). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65–78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F–Cl–Br–I–H₂O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280?°C and 0.3 GPa with (R ²?=?0.99): \(D_{F}^{\text{ol/melt}}\ =\ 3.6\pm 0.4\ \times \ {{10}^{-3}}\ \times \ {{X}_{{{\text{H}}_{\text{2}}}\text{O}}}\left( \text{wt }\!\!\%\!\!\text{ } \right)\ +\ 6\ \pm \ 0.4\times \,{{10}^{-4}}\). The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287–295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65–78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth’s mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.     

Hydrochemistry of urban groundwater in Seoul, South Korea: effects of land-use and pollutant recharge

The ionic and isotopic compositions (δD, δ¹⁸O, and ³H) of urban groundwaters have been monitored in Seoul to examine the water quality in relation to land-use. High tritium contents (6.1–12.0 TU) and the absence of spatial/seasonal change of O–H isotope data indicate that groundwaters are well mixed within aquifers with recently recharged waters of high contamination susceptibility. Statistical analyses show a spatial variation of major ions in relation to land-use type. The major ion concentrations tend to increase with anthropogenic contamination, due to the local pollutants recharge. The TDS concentration appears to be a useful contamination indicator, as it generally increases by the order of forested green zone (average 151 mg/l), agricultural area, residential area, traffic area, and industrialized area (average 585 mg/l). With the increased anthropogenic contamination, the groundwater chemistry changes from a Ca–HCO₃ type toward a Ca–Cl(+NO₃) type. The source and behavior of major ions are discussed and the hydrochemical backgrounds are proposed as the basis of a groundwater management plan.     

Soil temperature and moisture controls on surface fluxes and profile concentrations of greenhouse gases in karst area in central part of Guizhou Province, southwest China

In order to better understand the spatiotemporal variations and interrelationships of greenhouse gases (GHG), monthly surface fluxes and profile concentrations of GHG (CO₂, N₂O and CH₄) in karst areas in the Guizhou Province, southwest China, were measured from June 2006 to May 2007. GHG fluxes showed high variability, with a range of 460.9?C1,281.2?mg?m^?2?h^?1 for CO₂, ?25.4 to 81.5???g?m^?2?h^?1 for N₂O and ?28.7 to ?274.9???g?m^?2?h^?1 for CH₄, but no obvious seasonal change trends of the fluxes existed. Profile concentrations of CO₂, N₂O and CH₄ varied between 0.5 and 31.5?mL?L^?1, 0.273 and 0.734, and 0.1 and 3.5???L?L^?1, respectively. In general, concentrations of CO₂ and N₂O increased with depth, while CH₄ had an inverse trend. However, in October, November and January, the reversal of depth patterns of GHG concentrations took place below 15?cm, close to the soil?Crock interface. The spatiotemporal distribution of CO₂ in soil profile was significantly positively correlated with that of N₂O (p?<?0.05?C0.01) and negatively correlated with that of CH₄ (p?<?0.01). The correlation analysis showed that soil temperature and moisture may be responsible for GHG dynamics in the soils, rather than the exchange of GHG between land and atmosphere.     

Ion Chromatographic Determination of Fluorine and Chlorine in Silicate Rocks Following Alkaline Fusion

A simple and accurate method to determine fluorine and chlorine contents in small amounts (∼ 30 mg) in rock has been developed using ion chromatography after extraction by alkaline fusion. Powdered sample was mixed with sodium carbonate and zinc oxide at a mass ratio of 1:3:1, and was fused in an electric furnace at 900 °C for 30-40 minutes. An aqueous solution obtained by dissolving the fused silicate rock was diluted to the appropriate concentration of sodium carbonate (< ∼ 24 mmol l^-1) to minimise the tailing effect on F^- during ion chromatography caused by the large amount of carbonate species originating from the flux. Fluorine and chlorine contents were then determined by a standard additions method. Based on the relative standard deviation of the backgrounds, detection limits of both fluorine and chlorine were ∼ 4 μg g^-1, when 30 mg test portions were fused and diluted by a factor of 1200. We also report new fluorine and chlorine contents in nine GSJ (Geological Survey of Japan) reference materials, including peridotite (JP-1), granite (JG-1a), basalts (JB-1b, 2 and 3), andesites (JA-1 and 2) and rhyolites (JR-1 and 2). Fluorine and chlorine contents in the reference materials in this study were consistent with previously reported values. Reproducibilities were < 10 % for samples with F and Cl concentrations of > 20 μg g-1 and < 20 % with F and Cl < 20 μg g^-1.     

Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

The origin of thermal waters in the northeastern part of the Eger Rift,Czech Republic

An investigation of the thermal waters in the Ústí nad Labem area in the northeastern part of the Eger Rift has been carried out, with the principal objective of determining their origin. Waters from geothermal reservoirs in the aquifers of the Bohemian Cretaceous Basin (BCB) from depths of 240 to 616 m are exploited here. For comparison, thermal waters of the adjacent Teplice Spa area were also incorporated into the study. Results based on water chemistry and isotopes indicate mixing of groundwater from aquifers of the BCB with groundwater derived from underlying crystalline rocks of the Erzgebirge Mts. Unlike thermal waters in Dě?ín, which are of Ca–HCO₃ type, there are two types of thermal waters in Ústí nad Labem, Na–HCO₃–Cl–SO₄ type with high TDS values and Na–Ca–HCO₃–SO₄ type with low TDS values. Carbon isotope data, speciation calculations, and inverse geochemical modeling suggest a significant input of endogenous CO₂ at Ústí nad Labem in the case of high TDS groundwaters. Besides CO₂ input, both silicate dissolution and cation exchange coupled with dissolution of carbonates may explain the origin of high TDS thermal waters equally well. This is a consequence of similar δ¹³C and ¹⁴C values in endogenous CO₂ and carbonates (both sources have ¹⁴C of 0 pmc, endogenous CO₂ δ¹³C around −3‰, carbonates in the range from −5‰ to +3‰ V-PDB). The source of Cl⁻ seems to be relict brine formed in Tertiary lakes, which infiltrated into the deep rift zone and is being flushed out. The difference between high and low TDS groundwaters in Ústí nad Labem is caused by location of the high mineralization groundwater wells in CO₂ emanation centers linked to channel-like conduits. This results in high dissolution rates of minerals and in different δ¹³C(DIC) and ¹⁴C(DIC) fingerprints. A combined δ³⁴S and δ¹⁸O study of dissolved SO₄ indicates multiple SO₄ sources, involving SO₄ from relict brines and oxidation of H₂S. The study clearly demonstrates potential problems encountered at sites with multiple sources of C, where several evolutionary groundwater scenarios are possible.     

Partitioning of fluorine and chlorine between biotite and granitic melt: experimental calibration at 200 MPa H2O

Experiments from 640 to 680?°C, 200 MPa H₂O at?f _O2?≈?NNO, employing a natural?F-rich?vitrophyric rhyolite from Spor Mountain, Utah, assessed the effect of variable Mg′ [100Mg/(Mg?+?Mn?+?Fe)] on the partitioning of fluorine and chlorine between biotite (Bt) and melt. Over this temperature interval, Bt (?±?fluorite, ?±?quartz) is the sole liquidus phase. Partition coefficients for fluorine between biotite and glass (D_F ^Bt/melt) show a strong dependence on the Mg′ of Bt.?D_F ^Bt/melt varies from???1.5 to 7.2 over the range of Mg′ from 21 to 76. A strong linear correlation between?D_F ^Bt/melt?and Mg′ has a slope of 9.4 and extrapolates through the origin (i.e., D_F ^Bt/melt?≈?0 at Mg′?=?0, an annite-siderophyllite solid solution in these experiments). D_Cl ^Bt/melt values (???1 to 6) in the same experiments vary inversely with Mg′. The Al-content of biotite does not vary with the aluminum saturation index (ASI?=?molar Al₂O₃/Σ alkali and alkaline earth oxides) of melt, but two exchange mechanisms involving Al appear to operate in these micas: (1) Al^vi?+?Al^iv?? Si^iv?+?Mg^iv, and Mg^iv?+?2Al^iv? 2Si^iv?+?□^iv. The effects of other components such as Li or other intensive parameters including f _O2 have yet to be evaluated?systematically. At comparable Mg′ of Bt, however, the Spor Mountain rhyolite yields higher D_F ^Bt/melt values than an Li-rich, strongly peraluminous melt previously investigated. The results indicate that the Mg′ of Bt exerts the principal control on halogen partitioning, with ASI and T as second-order variables. The experimental partition coefficients compare well with other experimental results but not with most volcanic rocks. Magmatic Bt from most rhyolites records higher D_F ^Bt/melt due to reequilibration with degassed (H₂O-depleted) magma and perhaps with F₂O_?1 exchange that may accompany oxidation ([Fe³⁺O] [Fe²⁺OH]_?1). This behavior is evident in magmatic biotite from a zoned peraluminous rhyolite complex near Morococala, Bolivia: Bt is sharply zoned with F-rich rims, but Bt(core)-melt inclusion pairs fall on our experimental curve for D_F ^Bt/melt. These experimental data can be used in part to assess the preservation of magmatic volatile contents in plutonic or volcanic silicic rocks. For plutonic rocks, the actual F-content of melt, not a relative activity ratio involving HF species, can be reasonably estimated if the mica has not undergone subsolidus reequilibration. This information is potentially useful for some shallow-level Ca-poor magmas that are thought to be rich in F (e.g., A- and S-type granites) but do not conserve F well as rocks.     

Major ion geochemistry of shallow groundwater in the Qinghai Lake catchment, NE Qinghai-Tibet Plateau

Conventional hydrochemical techniques and statistical analyses were applied to better understand the solute geochemistry and the hydrochemical process of shallow groundwater in the Qinghai Lake catchment. Shallow groundwater in the Qinghai Lake catchment is slightly alkaline, and is characterized by a high ion concentrations and low water temperature. The total dissolved solids (TDS) in most of the samples are <1,000?mg/L, i.e. fresh water and depend mainly on the concentration of SO₄ ^2?, Cl^? and Na⁺. Groundwater table is influenced directly by the residents?? groundwater consumption. Most of the groundwaters in the Qinghai Lake catchment belong to the Ca²⁺(Na⁺) ?CHCO₃ ^? type, while the Qinghai Lake, part of the Buha (BHR) and the Lake Side (LS) samples belong to the Na⁺?CCl^? type. The groundwater is oversaturated with respect to aragonite, calcite and dolomite, but not to magnesite and gypsum. Solutes are mainly derived from strong evaporite dissolution in Daotang, BHR and LS samples and from strong carbonate weathering in Hargai and Shaliu samples. Carbonate weathering is stronger than evaporite dissolution with weak silicate weathering in the Qinghai Lake catchment. Carbonate weathering, ion exchange reaction and precipitation are the major hydrogeochemical processes responsible for the solutes in the groundwater in the Qinghai Lake catchment. Most of the shallow groundwaters are suitable for drinking. More attention should be paid to the potential pollution of nitrate, chloride and sulfide in shallow groundwater in the future.     

Geochemical Characteristics and Expansion Properties of a Highly Potassic Perlitic Rhyolite from Lopburi, Thailand

Miocene volcanic rocks from northeast of Lopburi, Thailand, include a suite of highly potassic (<6.3% K₂O) perlitic rhyolites that are similar chemically to rhyolites from Sardinia (which are also perlitic) and Vulcano. Electron microprobe analysis using a defocussed beam has shown that glass compositions contain up to 12.9% K₂O (0.9% Na₂O), and within the same samples spherulites are enriched in Na₂O (<6.2%) and depleted in K₂O (2.1%). The perlitic rhyolites contain up to 4% water of meteoric origin; from Fourier transform infra‐red spectroscopy data, expansion on heating involves a reduction in both hydroxyl and molecular water contents. When expanded using a laboratory test furnace, specific gravities as low as 26 kg/m³ have been achieved for a 0.15–0.3‐mm feed size fraction (reference perlite ores from Milos and Sardinia gave 47 and 33 kg/m³, respectively), and 10 kg/m³ for a 0.5–1‐mm fraction separated after expansion. Expansion involves the loss of fluorine from the perlite, presumably as HF; unexpanded perlite contains 90–550 mg/kg F, which is reduced on expansion by 4–65%. Water‐soluble fluorine after expansion is increased by a factor of 10 up to 3.3 mg/kg. Expansion also increases the availability of K to plants by a factor of up to 6, with a maximum available K content of 1245 mg K/kg perlite. This contrasts markedly with the chemically inert character of other, commercial, perlites, suggesting that the distinctive K‐enrichment of the perlitic rhyolite has given a raw material capable of generating products with nutritional functionality for plant growers.     

Potentially harmful metals,and health risk evaluation in groundwater of Mardan,Pakistan: Application of geostatistical approach and geographic information system

This study investigates the values of pH, total dissolved solids (TDS), elevation, oxidative reduction potential (ORP), temperature, and depth, while the concentrations of Br, and potentially harmful metals (PHMs) such as Cr, Ni, Cd, Mn, Cu, Pb, Co, Zn, and Fe in the groundwater samples. Moreover, geographic information system (GIS), XLSTAT, and IBM SPSS Statistics 20 software were used for spatial distribution modeling, principal component analysis (PCA), cluster analysis (CA), and Quantile-Quantile (Q-Q) plotting to determine groundwater pollution sources, similarity index, and normal distribution reference line for the selected parameters. The mean values of pH, TDS, elevation, ORP, temperature, depth, and Br were 7.2, 322 mg/L, 364 m, 188 mV, 29.6 °C, 70 m, 0.20 mg/L, and PHMs like Cr, Ni, Cd, Mn, Cu, Pb, Co, Zn, and Fe were 0.38, 0.26, 0.08, 0.27, 0.36, 0.22, 0.04, 0.43 and 0.86 mg/L, respectively. PHMs including Cr (89%), Cd (43%), Mn (23%), Pb (79%), Co (20%), and Fe (91%) exceeded the guideline values set by the world health organization (WHO). The significant R² values of PCA for selected parameters were also determined (0.62, 0.67, 0.78, 0.73, 0.60, 0.87, ?0.50, 0.69, 0.70, 0.74, ?0.50, 0.70, 0.67, 0.79, 0.59, and ?0.55, respectively). PCA revealed three geochemical processes such as geogenic, anthropogenic, and reducing conditions. The mineral phases of Cd(OH)_2, Fe(OH)_3, FeOOH, Mn₃O_4, Fe₂O_3, MnOOH, Pb(OH)_2, Mn(OH)_2, MnO_2, and Zn(OH)₂ (?3.7, 3.75, 9.7, ?5.8, 8.9, ?3.6, 2.2, ?4.6, ?7.7, ?0.9, and 0.003, respectively) showed super-saturation and under-saturation conditions. Health risk assessment (HRA) values for PHMs were also calculated and the values of hazard quotient (HQ), and hazard indices (HI) for the entire study area were increased in the following order: Cd>Ni>Cu>Pb>Mn>Zn>Cr. Relatively higher HQ and HI values of Ni, Cd, Pb, and Cu were greater than one showing unsuitability of groundwater for domestic, agriculture, and drinking purposes. The long-term ingestion of groundwater could also cause severe health concerns such as kidney, brain dysfunction, liver, stomach problems, and even cancer.     

Nitric oxide emissions from soils: a case study with temperate soils from Saxony, Germany

Nitrogen oxides (NO _x ) are involved in acid rain and ozone formation, as well as destruction. NO _x are climate-relevant trace gases in the atmosphere. Atmospheric NO _x originate from anthropogenic emissions (mainly combustion processes). NO from natural processes derives from thunderstorms and soil microbial processes. They may play a crucial role in soil?Catmosphere feedback processes. This study aims to investigate NO _x -emissions from soils under different land use, geographical and meteorological conditions. NO _x -emissions were quantified in both field and laboratory experiments with a closed static chamber. Disturbed soil samples have been used for laboratory experiments. A climate chamber was used to regulate soil temperature of the samples. Field experiments showed that NO-soil emissions strongly depend on soil temperature. NO-emissions from a soil under meadow showed significant daily variations, unlike soil below spruce forest. Peak emission values were 18???g NO?CN?m^?2?h^?1 above meadow and 1.3???g NO?CN?m^?2?h^?1 under forest canopy. In addition, NO-emissions of meadow and forest soil were studied in a climate chamber, enhanced by an additional experiment with agricultural soil. These experiments revealed strong exponential correlations of NO-emissions and soil temperature. Maximum values reached above 400???g NO?CN?m^?2?h^?1 from agricultural soils at soil temperatures above 50°C. This study shows that soil NO-emissions strongly depend on temperature, vegetation type and geographical position. Consequently, NO-emissions may have a positive feedback effect on climate change.