Gypsum and halite from the Mid-Atlantic Ridge,DSDP Site 395

Gypsum and halite crystals, together with saponite and phillipsite, were found in a vein in a basalt sill 625 m below the sea floor at DSDP Site 395A, located 190 km west of the crest of the Mid-Atlantic Ridge. The δ³⁴S value of the gypsum (+19.4‰) indicates a seawater source for the sulfate. The δ¹⁸O values of the saponite (+19.9‰) and phillipsite (+18.1‰) indicate either formation from normal seawater at about 55°C or formation from¹⁸O-depleted seawater at a lower temperature.The gypsum (which could be secondary after anhydrite) was formed by reaction between Ca²⁺ released from basalt and SO₄^2? in circulating seawater. The halite could have formed when water was consumed by hydration of basalt under conditions of extremely restricted circulation. A more probable mechanism is that the gypsum was originally precipitated as anhydrite at temperatures above 60°C. As the temperature dropped the anhydrite converted to gypsum. The conversion would consume water, which could cause halite precipitation, and would cause an increase in the volume of solids, which would plug the vein and prevent subsequent dissolution of the halite.     

Water composition and minerals equilibria at the Syri i Kalter spring and in the Bistrica river (South Albania)

Syri i Kalter (“Blue Eye” in english) is the name of the largest spring of Albania, situated in the south of the country, not far from the town of Sarande. The spring is located near the tectonic contact between the Mesozoic-Paleogenic Mali i Gjiere carbonate sequence and the Terziary flysch units of the “Ionian Zone” of Albania. The discharge area is characterized by the presence of Triassic evaporites, mainly constituted by gypsum and anhydrite, associated with clay, limestones, dolomite and halite. The spring consists of several discharge points, yielding as a whole an average water flow of about 11 m³/s.     

Hydrogeochemical evolution of Ordovician limestone groundwater in Yanzhou,North China

Major‐ion compositions of groundwater are employed in this study of the water–rock interactions and hydrogeochemical evolution within a carbonate aquifer system. The groundwater samples were collected from boreholes or underground tunnels in the Ordovician limestone of Yanzhou Coalfield where catastrophic groundwater inflows can be hazardous to mining and impact use of the groundwater as a water supply. The concentration of total dissolved solid (TDS) ranged from 961 to 3555 mg/l and indicates moderately to highly mineralized water. The main water‐type of the middle Ordovician limestone groundwater is Ca‐Mg‐SO₄, with SO₄^2‐ ranging from 537 to 2297 mg/l, and average values of Ca²⁺ and Mg²⁺ of 455.7 and 116.6 mg/l, respectively. The water samples were supersaturated with respect to calcite and dolomite and undersaturated or saturated with respect to gypsum. Along the general flow direction, deduced from increases of TDS and Cl^‐, the main water–rock interactions that caused hydrogeochemical evolution of the groundwater within the aquifer were the dissolution of gypsum, the precipitation of calcite, the dissolution or precipitation of dolomite, and ion exchange. Ion exchange is the major cause for the lower mole concentration of Ca²⁺ than that of SO₄^2‐. The groundwater level of Ordovician aquifer is much higher than that of C‐P coal‐bearing aquifers, so the potential flow direction is upward, and the pyrite in coal is not a possible source of sulfate; additional data on the stable sulfur and oxygen isotopic composition of the sulfate may be helpful to identify its origin. Although ion exchange probably accounts for the higher mole concentration of Na⁺ than that of Cl^‐, the dissolution of aluminosilicate cannot be ruled out. The data evaluation methods and results of this study could be useful in other areas to understand flow paths in aquifers and to provide information needed to identify the origin of groundwater. Copyright © 2012 John Wiley & Sons, Ltd.     

河西走廊花海古湖泊全新世白云石的发现及其环境意义

通过对河西走廊花海古湖泊沉积物的X衍射分析发现,全新世期间有明显的白云石沉积.岩性、沉积过程、石膏以及Fe3+含量的变化表明,花海湖全新世白云石沉积环境以还原环境为主,即还原环境利于白云石的形成,为白云石的成因研究提供了新的证据.白云石作为碳酸盐矿物,可以反映湖水盐度,但并非直接指示了湖水的咸化.随着湖水盐度的进一步增加,在硫酸盐型湖泊中,白云石含量随盐度的增加而相应减少,表明利用白云石分析湖水盐度时需要结合其他矿物进行分析.结合石膏含量的变化,花海湖全新世时期白云石含量的变化可以揭示该区域湖水盐度的变化.在10.478.87 cal ka B.P.早全新世时期,湖水的盐度较高,气候由干向湿转变;8.87 cal ka B.P.时期,有大量石膏沉积,显示了湖水盐度的进一步升高,气候干旱;随后湖水相对淡化,气候湿润;5.50 cal ka B.P.至今,沉积出现间断,气候逐渐干旱.     

The geochemistry of El Misti volcano,Peru fumaroles

El Misti is a 5822 m strato volcano in southern Peru. The mineralogy of the fumaroles is essentially sulfur, anhydrite, gypsum and ralstonite which are precipitated by acid vapors at 100°C–125°C. There are 2 to 6 parts per thousand chloride concentrations and several parts per million sodium, potassium, magnesium, calcium, iron and zinc concentrations in the condensed vapors. Elemental ratios indicate near complete leaching of the wall rock by the vapors. Arsenic and selenium are contaminants of the sulfur but are absent from the other minerals. Both the gypsum and anhydrite contain strontium and lead and show no tendency to fractionate these metals. The anhydrite alone contains significant thallium and bismuth. Bromine, strontium, thallium and lead are present in the ralstonite. The average δ D and δ O¹⁸ ratios from the fumarolic condensates are ?31.4 ‰ and +4.8 ‰ respectively. A marine contaminated heavy water source at depth is indicated as the parent water for the vapors.     

Hydrogeochemistry and quality of groundwater in a part of Damodar Valley,Eastern India: an integrated geochemical and statistical approach

The influence of geochemical processes and quality of groundwater in a rural tract of Damodar Valley region were investigated. The study has distinguished the groundwater as fresh, soft to moderately hard and mainly CaHCO₃ type. The paired samples student’s t test shows the significant seasonal variations of pH, HCO₃^?, and Fe. Amphoteric exchange has lessened HCO₃^? concentration in post-monsoon which subsequently has caused to drop pH. Quite the reverse, the monsoon precipitation has triggered the additional release of Fe from iron-bearing sediments. The contaminant Cl^? is from the domestic wastewater as is evidenced by field observations. The inter-variable relations, cation and anion mechanisms, and mineral saturation indices reveal that the dissolutions of silicate and carbonate minerals are the primary sources of major ions in groundwater. The chloro-alkaline indices showed the role of ion exchange too in water chemistry. The R-mode factor analysis also successfully identified two dominant processes regulating water chemistry—geogenic sources (Ca²⁺, Mg²⁺, Na⁺, and HCO₃^?) and anthropogenic inputs (mainly Cl^?). The groundwater is found unsuitable for drinking at 82 and 93% of wells in pre- and post-monsoon seasons, respectively mainly due to elevated Fe content. The water from more than 90% of wells is appropriate for irrigation uses. The study recommends the proper treatment of contaminated water for consumption and measures to protect the groundwater from the waste water infiltration.     

Groundwater mineralisation processes in Mediterranean semi‐arid systems (Cap‐Bon,North east of Tunisia): hydrogeological and geochemical approaches

The groundwater of the Korba plain represents major water resources in Tunisia. The Plio‐Quaternary unconfined aquifer of the Cap‐Bon (north‐east Tunisia) is subject to the intensive agricultural activities and high groundwater pumping rates due to the increasing of the groundwater extraction. The degradation of the groundwater quality is characterized by the salinization phenomena. Groundwater were sampled and analysed for physic‐chemical parameters: Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^‐, SO₄^2‐, HCO₃^‐, NO₃^‐, pH, electrical conductivity (EC), and the temperature (T°). The hydrochemical analysis is coupled with the calculation of the saturation indexes (SI gypsum, SI halite, SI calcite and SI dolomite), ionic derivation and with the ion correlations compared to chloride concentrations: Na⁺/ Cl^‐, Ca²⁺/ Cl^‐ and Mg²⁺/ Cl^‐ ratios. Seawater fractions in the groundwater were calculated using the chloride concentration. Those processes can be used as indicators of seawater intrusion progression. EC methods were also conducted to obtain new informations on the spatial scales and dynamics of the fresh water–seawater interface of coastal groundwater exchange. The mixing zone between freshwater and saltwater was clearly observed from the EC profile in the investigated area where a strong increase in EC with depth was observed, corresponding to the freshwater and saltwater interface. Results of hydrochemical study revealed the presence of direct cation exchange linked to seawater intrusion and dissolution processes associated with cations exchange. These results, together with EC investigation, indicated that the groundwater is affected by seawater intrusion and is still major actor as a source of salinization of the groundwater in Korba coastal plain. Further isotopic and hydrological investigations will be necessary to identify and more understood the underlying mechanisms. Copyright © 2012 John Wiley & Sons, Ltd.     

Hydrological and isotopic characterization of river water,groundwater, and groundwater recharge in the Heihe River basin,northwestern China

We used hydrochemistry and environmental isotope data (δ¹⁸O, δD, tritium, and ¹⁴C) to investigate the characteristics of river water, groundwater, and groundwater recharge in China's Heihe River basin. The river water and groundwater could be characterized as Ca²⁺? Mg²⁺? HCO₃^?? SO₄^2? and Na⁺? Mg²⁺? SO₄^2?? Cl^? types, respectively. Hydrogeochemical modelling using PHREEQC software revealed that the main hydrogeochemical processes are dissolution (except for gypsum and anhydrite) along groundwater flow paths from the upper to middle Heihe reaches. Towards the lower reaches, dolomite and calcite tend to precipitate. The isotopic data for most of the river water and groundwater lie on the global meteoric water line (GMWL) or between the GMWL and the meteoric water line in northwestern China, indicating weak evaporation. No direct relationship existed between recharge and discharge of groundwater in the middle and lower reaches based on the isotope ratios, d‐excess, and ¹⁴C values. On the basis of tritium in precipitation and by adopting an exponential piston‐flow model, we evaluated the mean residence time of shallow groundwater with high tritium activities, which was around 50 years (a). Furthermore, based on the several popular models, it is calculated that the deep groundwaters in piedmont alluvial fan zone of the middle reaches and in southern part of the lower reaches are modern water, whereas the deep groundwaters in the edge of the middle reaches and around Juyan Lake in the lower reaches of Heihe river basin are old water. Copyright © 2010 John Wiley & Sons, Ltd.     

Chemical and isotopic investigation of warm springs associated with normal faults in Utah

Thermal springs associated with normal faults in Utah have been analyzed for major cations and anions, and oxygen and hydrogen isotopes. Springs with measured temperatures averaging greater than 40°C are characterized by Na + K- and SO₄ + Cl-rich waters containing 10³ to 10⁴ mg/l of dissolved solids. Lower temperature springs, averaging less than 40°C, are more enriched in Ca + Mg relative to Na + K. Chemical variations monitored through time in selected thermal springs are probably produced by mixing with non-thermal waters. During the summer months at times of maximum flow, selected hot springs exhibit their highest temperatures and maximum enrichments in most chemical constituents.Cation ratios and silica concentrations remain relatively constant through time for selected Utah thermal springs assuring the applicability of the geothermometer calculations regardless of the time of year. Geothermometer calculations utilizing either the quartz (no steam loss), chalcedony or Mg-corrected Na/K/Ca methods indicate that most thermal springs in Utah associated with normal faults have subsurface temperatures in the range of 25 to less than 120°C. This temperature range suggests fluid circulation is restricted to depths less than about three kilometers assuming an average thermal gradient of about 40°C/km.Thermodynamic calculations suggest that most thermal springs are oversaturated with respect to calcite, quartz, pyrophyllite, (Fe, Mg)-montmorillonite, microcline and hematite, and undersaturated with respect to anhydrite, gypsum, fluorite and anorthite. Chalcedony and cristobalite appear to be the only phases consistently at or near saturation in most waters. Theoretical evaluation of mixing on mineral saturation trends indicates that anhydrite and calcite become increasingly more undersaturated as cold, dilute groundwater mixes with a hot (150°C), NaCl-rich fluid. The evolution of these thermal waters issuing from faults appears to be one involving the dissolution of silicates such as feldspars and micas by CO₂-enriched groundwaters that become more reactive with increasing temperature and/or time. Solution compositions plotted on mineral equilibrium diagrams trend from product phases such as kaolinite or montmorillonite toward reactant phases dominated by alkali feldspars.Isotopic compositions indicate that these springs are of local surface origin, either meteoric (low TDS, < 5000 mg/l) or connate ground water (high TDS, > 5000 mg/l). Deviations from the meteoric water line are the result of rock-water isotopic exchange, mixing or evaporation. Fluid source regions and residence times of selected thermal spring systems (Red Hill, Thermo) have been evaluated through the use of a σ D-contour map of central and western Utah. Ages for waters in these areas range from about 13 years to over 500 years. These estimates are comparable to those made for low-temperature hydrothermal systems in Iceland.     

Geochemical evolution of groundwater in hard-rock aquifers of South India using statistical and modelling techniques

ABSTRACT

Multivariate statistical analysis and inverse geochemical modelling techniques were employed to deduce the mechanism of groundwater evolution in the hard-rock terrain of Telangana, South India. Q-mode hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to extract the hydrogeochemical characteristics and classify the groundwater samples into three principal groups. Use of thermodynamic stability diagrams and inverse geochemical modelling in PHREEQC identified the chemical reactions controlling hydrogeochemistry of each of the groups obtained from statistical analysis. The model output showed that a few phases are governing the water chemistry in this area and the geochemical reactions responsible for evolution of groundwater chemistry along the flow path are (i) dissolution of evaporite minerals (dolomite, halite); (ii) dissolution of primary silicate minerals (albite, anorthite, K-feldspar, biotite); (iii) precipitation of secondary silicate minerals (kaolinite, quartz, gibbsite, Ca-montmorillonite) along with anhydrite and calcite; and (iv) reverse ion exchange processes.     

Controls on Ground Water Chemistry in the Central Couloir Sud Rifain,Morocco

Irrigation, urbanization, and drought pose challenges for the sustainable use of ground water in the central Couloir sud rifain, a major agricultural region in north-central Morocco, which includes the cities of Fès and Meknès. The central Couloir is underlain by unconfined and confined carbonate aquifers that have suffered declines in hydraulic head and reductions in spring flow in recent decades. Previous studies have surveyed ground water flow and water quality in wells and springs but have not comprehensively addressed the chemistry of the regional aquifer system. Using graphical techniques and saturation index calculations, we infer that major ion chemistry is controlled (1) in the surficial aquifer by cation exchange, calcite dissolution, mixing with deep ground water, and possibly calcite precipitation and (2) in the confined aquifer and warm springs by calcite dissolution, dolomite dissolution, mixing with water that has dissolved gypsum and halite, and calcite precipitation. Analyses of ²H and ¹⁸O indicate that shallow ground water is affected by evaporation during recharge (either of infiltrating precipitation or return flow), whereas deep ground water is sustained by meteoric recharge with little evaporation. Mechanisms of recharge and hydrochemical evolution are broadly consistent with those delineated for similar regional aquifer systems elsewhere in Morocco and in southern Spain.     

Cation distribution in low-calcium pyroxenes: Dependence on temperature and calcium content and the thermal history of lunar and terrestrial pigeonites

Four pyroxenes with compositions En₄₈Fs₄₈Wo₄, En_47·5Fs_47·5Wo₅, En₄₅Fs₄₅Wo₁₀ and En₄₀Fs₄₀Wo₂₀, synthesized at 1200°C at atmospheric pressure, were heat-treated at 500, 600, 700, and 800°C for various lengths of time. These pyroxenes are variously ordered with respect to Fe²⁺ and Mg²⁺ without unmixing. The Fe²⁺-Mg²⁺ distribution over the two nonequivalent sites M1 and M2, determined through Mössbauer spectroscopy, is found to be a function of both temperature and concentration of Ca²⁺ at the M2 site. The preference of Fe²⁺ for the M2 site increases with decreasing temperature and increasing Ca²⁺. These data can be used to determine cation equilibration temperatures of lunar and terrestrial pigeonites. The lunar pigeonites usually indicate equilibration temperatures of 700–860°C, except the pigeonite from rock 14053, which may have been subjected to shock heating due to meteoritic impact.     

Deciphering groundwater flow between the Complex Terminal and Plio-Quaternary aquifers in Chott Gharsa plain (southwestern Tunisia) using isotopic and chemical tools

Abstract

The Complex Terminal (CT) and Plio-Quaternary (P-Q) aquifers in the Chott Gharsa plain in southwestern Tunisia have been investigated with the aid of chemical and isotopic tools. It has been demonstrated that groundwater from the CT is mainly of palaeo-origin, especially in the western and central parts of the plain where the most negative values of δ¹⁸O and δ²H were observed (between??8.1 and??7.6‰ for δ¹⁸O, and??60 to??57‰ for δ²H), combined with low concentrations of radiocarbon (6.8–7.5 pmc) and absence of tritium. Modern recharge of the aquifer occurs only in the eastern part of the system where younger waters were observed, as indicated by their stable isotope composition, relatively high radiocarbon content and presence of tritium. Groundwater from the P-Q multi-layer aquifer represents mixtures of ascending deep CT waters and modern water recharging the P-Q aquifer system. Isotope mass balance was used to quantify mixing proportions. The calculations showed that the contribution of deep CT groundwater to the P-Q aquifer system reaches about 75% in the western and central parts of the plain where the CT aquifer remains strongly artesian. This contribution decreases to about 15% towards the eastern part of the plain, as a consequence of significant reduction of artesian pressure in this area of the CT aquifer. Chemical data suggest that mineralization of the studied groundwater systems is controlled mainly by dissolution of evaporative minerals (halite, anhydrite and gypsum) and cation exchange reactions with the matrix, possibly enhanced by recent anthropogenic disturbance of the system caused by lowering of the water table due to heavy exploitation and return flow of saline irrigation water into the P-Q aquifer.

Editor D. Koutsoyiannis; Associate editor E. Custodio

Citation Yangui, H., Abidi, I., Zouari, K., and Rozanski, K., 2012. Deciphering groundwater flow between the Complex Terminal and Plio-Quaternary aquifers in Chott Gharsa plain (southwestern Tunisia) using isotopic and chemical tools. Hydrological Sciences Journal, 57 (5), 967–984.     

Origin and development of tafoni in Tunnel Spring Tuff,Crystal Peak,Utah, USA

Bedding‐parallel tafoni are well developed over much of the surface of the Tunnel Spring Tuff (Oligocene) exposed in 300‐m‐high Crystal Peak, an inselberg. The Tunnel Spring Tuff is a crudely stratified, non‐welded rhyolite ash‐flow tuff with > 30 per cent porosity. Clasts of Palaeozoic dolomite, limestone and quartzite make up 10 per cent of the tuff. The tafoni are remarkable because of their size (up to 20 m wide but rarely wider than 4 m), shape of the openings (spherical, arch‐like or crescent‐shaped) and abundance (up to 50 per cent of an outcrop face). They are actively forming today. Calcite is abundant (10 to 40 per cent by weight) in tafoni as an efflorescence in spalling flakes of tuff on their roofs and walls. Halite and gypsum generally make up less than 0·01 per cent of the efflorescence. The absence of corroded quartz and feldspar grains in spall fragments indicates that chemical weathering is unimportant in development of the tafoni. Calcite, aragonite, halite and gypsum dust from modern salt pans less than 20 km from Crystal Peak are potential sources of salt in the tuff, but the prevailing winds are in the wrong direction for significant amounts of these evaporite minerals to reach the inselberg. Calcite is the only evaporite mineral present in the tafoni in more than trace amounts, and this mineral is readily available within the tuff itself as a result of rock weathering. We propose that meteoric water containing carbonic acid infiltrates the tuff, dissolves carbonate clasts, and migrates to the steep flanks (>20°) of the peak through abundant megapores and micropores. There it evaporates and precipitates calcite. Crystallization pressure spalls off grains and sheets as the physical manifestation of salt weathering. The quasi‐uniform spacing of tafoni suggests that a self‐organization process is active in the water flow. Copyright © 2000 John Wiley & Sons, Ltd.     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

Lead isotopes and age of Hawaiian lherzolite nodules

The reaction between enstatite (En_95.3Fs_4.7) and CaCO₃ has been studied at pressures between 23 and 77 kbars and at temperatures between 800° and 1400°C. At 1000°C enstatite and CaCO₃ react to form dolomite and diopside solid solutions at pressures below approximately 45 kbars and magnesite and diopside solid solutions at higher pressures. The curve for the reaction dolomite_ss + enstatite_ss ? magnesite_ss + diopside_ss lies between 40 to 45 kbars at 1000°C and between 45 and 50 kbars at 1200°C. It is very close to the graphite-diamond transition curve. These experimental results indicate that calcite (or aragonite) is unstable in the presence of enstatite, and that dolomite and magnesite are the stable carbonates at high pressures. The forsterite + aragonite assemblage is, however, stable to at least 80 kbars at 800°C. It is suggested that in the upper mantle where enstatite is present, dolomite is stable to depths of about 150 km and magnesite is stable at greater depths in the continental regions, assuming that the partial pressure of CO₂ is equal or close to the total pressure. It is also suggested that carbonate inclusions in pyroxene can be used as an indicator of the depth of their equilibration; dolomite inclusions in enstatite would be formed at depths shallower than 150 km and magnesite inclusions in diopside at greater depths. Eclogite and peridotite inclusions in kimberlite may be classified on this basis.     

Snow and stream-water chemistry of the Ganga headwater basin,Garhwal Himalaya,India

Abstract

Studies of the chemical composition of snowpack and stream water were carried out in a catchment having an area of 53km² (31°03′-30°55′N and 78°40′-78°51′E) in the Garhwal Himalaya, India. The dominant ions in the snowpack and stream water were Ca²⁺, Na⁺, NO^? ₃, SO^2- ₄ and HCO^? ₃. Solute patterns in the snowpack show preferential elution. Investigation of the chemical composition of stream water shows that meltwater changes its composition substantially as it passes through soil pathways to the stream. The groundwater flushing perhaps controls the chemical composition of meltwater in the early spring. However, in the period from July to September, the stream water carries the chemical signature of monsoonal precipitation.     

Lithological and hydrological controls on water composition: evaporite dissolution and glacial weathering in the south central Andes of Argentina (33°–34°S)

Lithological and hydrological influence on fluvial physical and chemical erosion was studied in a glacierized sedimentary basin with high evaporite presence. Suspended particulate matter (SPM), total dissolved solids (TDS) and major ion concentrations were analysed for 2 years of different hydrologic condition: (i) 2009–2010, Q = 100% average; and (ii) 2010–2011, Q = 60% average. Annual hydrograph was simple regime‐type with one peak in summer related to snow melting. The intra‐annual SPM and TDS variations were directly and inversely associated to Q, respectively. Snow chemistry showed continental influence (Na⁺/Ca²⁺ = 0.17), and atmospheric input of TDS was <1% of the total exported flux. River water was highly concentrated in Ca²⁺ and SO₄²⁻ (~4 mmol l⁻¹) and in Na⁺ and Cl⁻ (~3 mmol l⁻¹). Ca²⁺/SO₄²⁻ and Na⁺/Cl⁻ molar ratios were ~1 and related to Q, directly and inversely, respectively. Major ion relationships suggest that river chemistry is controlled by evaporite (gypsum and halite) dissolution having a summer input from sulfide oxidation and carbonate dissolution, and a winter input from subsurface flow loaded with silicate weathering products. This variation pattern resulted in nearly chemostatic behaviour for Ca⁺, Mg²⁺ and SO₄²⁻, whereas Na⁺, Cl⁻ and SiO₂ concentrations showed to be controlled by dilution/concentration processes. During the 2009–2010 hydrological year, the fluxes of water, SPM and TDS registered in the snow melting–high Q season were, respectively, 71%, 92% and 67% of the annual total, whereas for equal period in 2010–2011, 56% of water, 86% of SPM and 54% of TDS annual fluxes were registered. The SPM fluxes for 2009–2010 and 2010–2011 were 1.19 × 10⁶ and 0.79 × 10⁶ t year⁻¹, whereas TDS fluxes were 0.68 × 10⁶ and 0.55 × 10⁶ t year⁻¹, respectively. Export rates for 2009–2010 were 484 t km² year⁻¹ for SPM and 275 t km² year⁻¹ for TDS. These rates are higher than those observed in glacierized granite basins and in non‐glacierized evaporite basins, suggesting a synergistic effect of lithology and glaciers on physical and chemical erosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterization of sulfate mineral deposits in central Thailand

In this paper we present petrographic and geochemical data of sulfate mineral deposits in northeast Nakhon Sawan, central Thailand, and provide new constraints on their age. The deposits are made up mainly of strongly deformed nodular and massive gypsum in the upper part, and less deformed layered anhydrite in the lower part. They are intruded by andesitic dikes that contain Middle Triassic zircons (ca 240 Ma). These dikes are probably part of the regional magmatic activity of the Sukhothai Arc during the Early to Middle Triassic. Sulfur (δ³⁴S) and strontium (⁸⁷Sr/⁸⁶Sr) isotopic compositions of the sulfates range from 15.86 ‰ to 16.26 ‰ and from 0.70810 to 0.70817, respectively. Comparisons with the Phanerozoic seawater isotopic evolution curve indicate that those values are best explained by precipitation of the sulfates from Carboniferous seawater, in particular seawater of late Mississippian age (ca 326 Ma), and this would be consistent with previous studies of calcareous fossils in the limestones that crop out around this site. Our interpretation is that evaporitic gypsum was originally precipitated from hypersaline seawater on a shallow lagoon or shelf on the Khao Khwang Platform during the Serpukhovian, and that this gypsum changed to anhydrite during early burial. The anhydrite was then cut by andesitic dikes during the Middle Triassic, and more recently the upper part of which was rehydrated during exhumation to form secondary gypsum near the surface.     

A preliminary stable isotope study of volcanic ashes discharged by the 1979 eruption of Ontake Volcano,Nagano, Japan

Sulphur isotopic compositions of pyrite, anhydrite and native sulphur in volcanic ashes discharged by the 1979 eruption of Ontake volcano, Nagano, Japan were determined. The isotopic data indicate that sulphate in anhydrite and a part of native sulphur were produced by the disproportionation reaction of sulphite formed by dissolution of SO₂ in volcanic gases into water which filled a mud reservoir probably located just below the crater zone. Some part of H₂S in volcanic gases was fixed as pyrite and some was oxidised to form native sulphur. Hydrothermal alteration of country rocks to form pyrite, anhydrite and clay minerals had proceeded in the mud reservoir before eruption at temperatures ranging from 110° to 185°C which were estimated by oxygen isotopic fractionation between anhydrite and water.