Analysis and speciation of selenium ions in mine environments

 Aqueous extracts of five mine soil samples and a set of selenite (SeO₃ ^2–)–selenate (SeO₄ ^2–) solutions (0.5, 1, 5, 10 and 25 mg/l) were speciated using atomic absorption spectroscopy with hydride generation (AAS-HG) and ion chromatography (IC) to compare these methods for Se speciation. In another experiment, a SeO₃ ^2––SeO₄ ^2––SO₄ ^2– solution (25 mg/l) was reacted with CaO, MgO, MnO₂, CuO, La₂O₃, and WO₃ to evaluate the relative distribution of the Se species and SO₄ ^2– in the SORB (sorbed ions that were desorbed by NaOH), SOLN (equilibrium concentrations), CMPX (irreversibly sorbed and neutral ion pair complexes) fractions. The AAS-HG method was capable of analyzing Se as low as 0.002 mg/l, which was below the detection limit of IC. High concentration of SO₄ ^2– affected the chromatographic Se speciation either by shifting or overlapping Se peaks, in which AAS-HG was more useful. However, IC was capable of speciating aqueous SeO₃ ^2––SeO₄ ^2– directly without any sample pretreatment, whereas AAS-HG measured SeO₃ ^2–+SeO₄ ^2–, and SeO₃ ^2– in separate runs and SeO₄ ^2– was calculated from the difference, i.e., spectrophotometric speciation was an indirect method. For both Se species, AAS-HG and IC data were comparable within detection standard deviations. Ratios of different Se species at measured soil pH and pe indicated that SeO₃ ^2– or SeO₄ ^2– would be the dominant Se species; the p(SeO₄ ^2–/SeO₃ ^2–) values further suggested SeO₄ ^2– would be the major solution species. Except for CaO and MgO treatments, the %SeO₃ ^2– in the SORB fraction was ≥%SeO₄ ^2–. In the SOLN fraction %SeO₄ ^2– was ≥%SeO₃ ^2– for all oxides but CaO, whereas in the CMPX fraction this order was observed for only CaO and MnO₂. The %SeO₃ ^2– was highest in the SOLN fraction for all oxides but MgO and La₂O₃ for these two oxides SeO₃ ^2– dominated in CMPX and SORB fractions, respectively. The SOLN fraction also contained the highest %SeO₄ ^2– for all oxides but MgO which retained SeO₄ ^2– primarily in the SORB fraction. The %SeO₃ ^2– and %SeO₄ ^2– in the CMPX fraction were highest for MgO, thus, suggesting a possible formation of MgSeO₃ ⁰ and MgSeO₄ ⁰. A similar trend of SORB %SO₄ ^2– and SORB %SeO₄ ^2– was attributed to the analogous adsorption mechanisms (outer-sphere complexation). For all oxides but MgO, %SO₄ ^2– was <%SeO₄ ^2– in the SOLN fraction and ≥%SeO₄ ^2– in the CMPX fraction. Comparative ionic distributions provide an overall picture of the relative abundance of different Se species in various fractions associated with different oxides present in micro- and macrolevels in soils and geological materials. Received: 27 December 1995 · Accepted: 29 April 1997     

Synthesis of In‐House Produced Calibrated Silver Phosphate with a Large Range of Oxygen Isotope Compositions

The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag₃PO₄ in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag₃PO₄ crystals were obtained from KH₂PO₄ that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag₃PO₄. We provide a calculation sheet that computes the δ¹⁸O of precipitated Ag₃PO₄ as a function of time, temperature and δ¹⁸O of both reactants KH₂PO₄ and H₂O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ¹⁸O from ?20 to +15‰ VSMOW.     

An experimental investigation on diffusion of water in haplogranitic melts

  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz₂₈Ab₃₈Or₃₄ (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D _water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D _water with pressure indicates an average activation volume of about 9 cm³/mole. The diffusivity (in cm²/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by

Long-Term and Seasonal Changes in Nutrients,Phytoplankton Biomass,and Dissolved Oxygen in Deep Bay,Hong Kong

Deep Bay is a semienclosed bay that receives sewage from Shenzhen, a fast-growing city in China. NH₄ is the main N component of the sewage (>50% of total N) in the inner bay, and a twofold increase in NH₄ and PO₄ concentrations is attributed to increased sewage loading over the 21-year period (1986–2006). During this time series, the maximum annual average NH₄ and PO₄ concentrations exceeded 500 and 39 μM, respectively. The inner bay (Stns DM1 and DM2) has a long residence time and very high nutrient loads and yet much lower phytoplankton biomass (chlorophyll (Chl) <10 μg L⁻¹ except for Jan, July, and Aug) and few severe long-term hypoxic events (dissolved oxygen (DO) generally >2 mg L⁻¹) than expected. Because it is shallow (~2 m), phytoplankton growth is likely limited by light due to mixing and suspended sediments, as well as by ammonium toxicity, and biomass accumulation is reduced by grazing, which may reduce the occurrence of hypoxia. Since nutrients were not limiting in the inner bay, the significant long-term increase in Chl a (0.52–0.57 μg L⁻¹ year⁻¹) was attributed to climatic effects in which the significant increase in rainfall (11 mm year⁻¹) decreased salinity, increased stratification, and improved water stability. The outer bay (DM3 to DM5) has a high flushing rate (0.2 day⁻¹), is deeper (3 to 5 m), and has summer stratification, yet there are few large algal blooms and hypoxic events since dilution by the Pearl River discharge in summer, and the invasion of coastal water in winter is likely greater than the phytoplankton growth rate. A significant long-term increase in NO₃ (0.45–0.94 μM year⁻¹) occurred in the outer bay, but no increasing trend was observed for SiO₄ or PO₄, and these long-term trends in NO₃, PO₄, and SiO₄ in the outer bay agreed with those long-term trends in the Pearl River discharge. Dissolved inorganic nitrogen (DIN) has approximately doubled from 35–62 to 68–107 μM in the outer bay during the last two decades, and consequently DIN to PO₄ molar ratios have also increased over twofold since there was no change in PO₄. The rapid increase in salinity and DO and the decrease in nutrients and suspended solids from the inner to the outer bay suggest that the sewage effluent from the inner bay is rapidly diluted and appears to have a limited effect on the phytoplankton of the adjacent waters beyond Deep Bay. Therefore, physical processes play a key role in reducing the risk of algal blooms and hypoxic events in Deep Bay.     

Biogeochemical characteristics of the lower Mississippi River, USA, during June 2003

During June 2003, a period of mid level discharge (17,400 m⁻³ s⁻¹), a parcel of water in the lower Mississippi River was sampled every 2 h during its 4-d transit from river km 362 near Baton Rouge to km 0 at Head of Passes, Louisiana, United States. Properties measured at the surface during each of the 48 stations were temperature, salinity, dissolved organic carbon (DOC), total dissolved nitrogen, dissolved macronutrients (NO₃+NO₂, PO₄, Si(OH)₄), chlorophylla (chla; three size fractions: < 5 μm, 5–20 μm, and > 20 μm) pigment composition by HPLC, total suspended matter (TSM), particulate organic carbon (POC), and particulate nitrogen (PN). Air-water CO₂ flux was calculated from surface water dissolved inorganic carbon and pH. During the 4 d transit, large particles appeared to be settling out of the surface water. Concentrations of chla containing particles > 20 μm declined 37%, TSM declined 43%, POC declined 42% and PN declined 57%. Concentrations of the smaller chla containing particles did not change suggesting only large particulate materials were settling. There was no measurable loss of dissolved NO₃, PO₄, or Si(OH)₄, consistent with the observation that chla did not increase during the 4-d transit. DOC declined slightly (3%). These data indicate there was little autotrophic or heterotrophic activity in the lower Mississippi River at this time, but the system was slightly net heterotrophic.     

Controls on the chemical composition of groundwater from alluvial aquifers in the Wanaka and Wakatipu basins, Central Otago, New Zealand

 Groundwater in alluvial aquifers of the Wakatipu and Wanaka basins, Central Otago, New Zealand, has a composition expressed in equivalent units of Ca²⁺≫Mg²⁺≅Na⁺>K⁺ for cations, and HCO₃ ^–≫SO₄ ^2->NO₃ ^–≅Cl^– for anions. Ca²⁺ and HCO₃ ^– occur on a 1 : 1 equivalent basis and account for >80% of the ions in solution. However, some groundwater has increased proportions of Na⁺ and SO₄ ^2-, reflecting a different source for this water. The rock material of the alluvial aquifers of both basins is derived from the erosion and weathering of metamorphic Otago Schist (grey and green schists). Calcite is an accessory mineral in both the grey and green schists at <5% of the rock. Geological mapping of both basins indicates that dissolution of calcite from the schist is the only likely mechanism for producing groundwater with such a constant composition dominated by Ca²⁺ and HCO₃ ^– on a 1 : 1 equivalent basis. Groundwater with higher proportions of Na⁺ and SO₄ ^2- occurs near areas where the schist crops out at the surface, and this groundwater represents deeper and possibly older water derived from basement fluids. Anomalously high K⁺ in the Wakatipu basin and high NO₃ ^– concentrations in the Wanaka basin cannot be accounted for by interaction with basement lithologies, and these concentrations probably represent the influence of anthropogenic sources on groundwater composition. Received, June 1996 Revised, March 1997, July 1997 Accepted, July 1997     

A geoelectrical-hydrogeochemical investigation of shallow groundwater occurrence in Ibadan, southwestern Nigeria

 An integrated geological, geoelectrical and hydrochemical investigation of shallow groundwater occurrence in the Ibadan area, southwestern Nigeria, is presented. The primary objective was to characterise the groundwater in a typical low-latitude environment underlain by Precambrian crystalline basement complex rocks. The dominant rocks comprise suites of gneisses and quartzites. Chemical analyses of the groundwater show that the mean concentration of the cations is in the order Na>Ca>Mg>K while that for the anions is Cl>HCO₃>NO₃>SO₄. Statistical analyses, using the product-moment coefficient of correlation, indicate positive correlations between the following pairs of parameters: TDS and conductivity (r=0.96); Na⁺+Mg²⁺ and Cl^– (r=0.95); Na⁺+K⁺ and Ca²⁺ (r=0.43); Na⁺+K⁺ and HCO₃ ^– (r=0.17); Ca²⁺ and Mg²⁺ (r=0.74); Ca²⁺ and HCO₃ ^– (r=0.33); Ca²⁺+Mg²⁺ and HCO₃ ^– (r=0.31) and pH and HCO₃ ^– (r=0.54). A very weak negative correlation was recorded between pH and Cl^–, with r=–0.003. Five groundwater groups have been identified, namely, (1) the Na-Cl, Na-Ca-Cl, Na-Ca-(Mg)-Cl; (2) the Ca-(Mg)-Na-HCO₃-Cl, Na-Ca-HCO₃-Cl, and Ca-HCO₃-Cl; (3) the Ca-(Mg)-Na-HCO₃, Ca-Na-HCO_3; (4) Ca-Na-Cl-(SO₄)-HCO₃ and (5) the Ca-(Mg)-Na-SO₄-HCO₃. The different groups reflect the diversity of bedrock types and consequently also of the products of weathering. Most of the water sampled is unfit for drinking on account of the high NO₃ ^– content. It can, however, be used for irrigation purposes as the sodium hazard is low while the salinity hazard ranges from low to medium. Resistivity soundings indicate the presence of a thick weathering profile, which could be up to 60 m. Such sites should be the target for any long-term and sustainable groundwater development in the area. Received: 15 April 1998 · Accepted: 4 July 1998     

Hydrogeochemical processes in the groundwater environment of Heihe River Basin,northwest China

The Heihe River Basin is a typical arid inland river basin for examining stress on groundwater resources in northwest China. The basin is composed of large volumes of unconsolidated Quaternary sediments of widely differing grain size, and during the past half century, rapid socio-economic development has created an increased demand for groundwater resources. Understanding the hydrogeochemical processes of groundwater and water quality is important for sustainable development and effective management of groundwater resources in the Heihe River basin. To this end, a total of 30 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions and its quality for irrigation. Chemical analysis shows that water presents a large spatial variability of chemical facies (SO₄ ²⁻–HCO₃⁻, SO₄ ²⁻–Cl⁻, and Cl⁻–SO₄ ²⁻) as groundwater flow from recharge area to discharge area. The ionic ratio indicates positive correlation between the flowing pairs of parameters: Cl⁻ and Na⁺(r = 0.95), SO₄ ²⁻ and Na⁺ (r = 0.84), HCO₃ ⁻ and Mg²⁺(r = 0.86), and SO₄ ²⁻ and Ca²⁺ (r = 0.91). Dissolution of minerals, such as halite, gypsum, dolomite, silicate, and Mirabilite (Na₂SO₄·10H₂O) in the sediments results in the Cl⁻, SO₄ ²⁻, HCO₃ ⁻, Na⁺, Ca²⁺ and Mg²⁺ content in the groundwater. Other reactions, such as evaporation, ion exchange, and deposition also influence the water composition. The suitability of the groundwater for irrigation was assessed based on the US Salinity Laboratory salinity classification and the Wilcox diagram. The results show that most of the groundwater samples are suitable for irrigation uses barring a few locations in the dessert region in the northern sub-basin.     

Effect of chemical fertilizers on the fractionation of Cu,Cr and Ni in contaminated soil

Effect of chemical fertilizers (urea, NH₄Cl, Ca(NO₃)₂, KCl and KH₂PO₄) on the fractionation of Cu, Cr and Ni was studied by a 4-month incubation experiment. Using sequential extraction procedure, it was found that the application of fertilizers could change the distribution of Cu, Cr and Ni in the fractions of soil. Applying urea (CO(NH₂)₂) significantly decreased the concentrations of Cu, Cr and Ni in water soluble plus exchangeable (WE) fraction, but increased those in Fe–Mn oxides bound (FM) fraction (p < 0.01). However, application of NH₄Cl caused an increase in the WE fraction by 27.7% for Cu, 111.5% for Cr and 20.4% for Ni. The CO(NH₂)₂ raised the soil pH from 4.51 to 4.96, whereas NH₄Cl lowered the pH of soil by 0.44 units. The WE fraction of the three heavy metals was significantly increased, while the FM fraction was significantly decreased by adding KCl (p < 0.01). Moreover, the supply of KH₂PO₄ reduced the WE and carbonate bound (CB) fractions of Cu, Cr and Ni in the soil, however, it raised Cu and Ni in the residual (RS) fraction and Cr in the FM fraction. In addition, the mobility index indicated that KCl and NH₄Cl increased the mobility of Cu, Cr and Ni in the soil, whereas urea and KH₂PO₄ decreased the mobility of the three metals in the soil. These results suggest that applying chemical fertilizers does not only provide plant nutrients, but may also change the speciation and mobility of heavy metals in the soil.     

Evaluation of Jordanian zeolite tuff as a controlled slow-release fertilizer for NH4 +

 The exchange and release properties of the natural phillipsite tuff from the Aritain area in Jordan were evaluated by studying the exchange properties of this natural zeolite in the NH₄ ⁺–Na⁺ system. Exchange isotherms at 18, 35, and 50  °C showed that phillipsite exchanged NH₄ ⁺ preferably over Na⁺ at all temperatures. However, the selectivity coefficient for NH₄ ⁺ decreased with decreasing temperature. The release of NH₄ ⁺ from phillipsite saturated with ammonium sulfate took place in two stages characterized by different SO₄ ^2– : NH₄ ⁺ ratios. Aritain phillipsite from NE Jordan could be processed and used as NH₄ ⁺ slow-release fertilizers. The use of NH₄ ⁺-phillipsite tuff offers an option to the widely used soluble NH₄-fertilizers in agciculture to avoid environmental problems associated with nitrogen contamination of surface water and groundwater. Received: 19 December 1996 · Accepted: 13 May 1997     

Interstitial water and hydrochemistry of a mangrove forest and adjoining water system, south west coast of India

 Eh, pH, salinity, total alkalinity, dissolved O₂, NO₂ ^–, PO₄ ^–3, SiO₂ and NH₄ ⁺ of waters from a mangrove forest, an estuary and a creek connecting the mangrove forest and the estuary have been measured. Further, the chemistry of interstitial waters of surficial and core sediments from the mangrove forest have been analyzed for the above parameters, except dissolved oxygen. To understand the flux of nutrients from the mangrove forest to the adjoining estuary, creek waters were monitored during tidal phases. PO₄ ^–3, SiO₂ and NH₄ ⁺ were found to be at elevated levels in mangrove waters whereas NO₂ ^– shows no variation compared to the estuary. Dissolved O₂ is low in mangrove waters. PO₄ ^–3, NH₄ ⁺ and SiO₂ are several times higher in interstitial waters than in overlying waters. Several fold enrichment of PO₄ ^–3, NH₄ ⁺ and, to some extent, SiO₂ were measured in creek waters during ebbing relative to flooding, indicating that mangroves act as a perennial source for the above nutrients. Received: 26 May 1998 · Accepted: 21 July 1998     

Concentration levels of some inorganic contaminants in streams and sediments in areas of pyrometallurgical and hydrometallurgical activities at the Obuasi gold mine,Ghana

This study assessed the levels of selected inorganic contaminants in streams and stream sediments in the effluent areas relating to the pyrometallurgical and hydrometallurgical treatment of gold ores in the Obuasi gold mine, Ghana. Water and stream sediment samples were taken from specific locations during the consecutive rainy and dry seasons, and concentrations of phosphate (PO₄ ³⁻), nitrate (NO₃ ⁻), chloride (Cl⁻), sulphate (SO₄ ²⁻), sodium (Na⁺), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), arsenic (As), copper (Cu), iron (Fe), zinc (Zn) and lead (Pb), were determined. Alkalinity, pH, temperature and specific electrical conductivity were also measured. In the water samples, the average pH range for both the seasons is 6.9–7.4, most anions and metals have relatively higher concentrations in the wet season than in the dry season at both the metallurgical sites. Trace metals concentrations were comparatively low (<0.01–5.00 mg/l), higher in the dry season at the pyrometallurgical sites. Irrespective of seasons, SO₄ ²⁻ (0.80–949.50 mg/l) and PO₄ ³⁻ (<0.01–6.30 mg/l) were pronounced at the pyrometallurgical sites, while NO₃ ⁻ (0.01–98.45 mg/l) and Cl⁻ (1.88-49.05 mg/l) were higher at the hydrometallurgical sites. In water samples, Ca²⁺ and SO₄ ²⁺ were the dominant cation and anion, respectively. In the stream sediments, except pH, NO₃ ⁻, Cl⁻, Na⁺ and Mg²⁺, all other parameter values were relatively higher at the hydrometallurgical areas. The average concentrations of Ca²⁺, Mg²⁺, As and Fe are remarkably high at both metallurgical sites (3,217–46,026 mg/kg). Overall, the level of parameters in the water samples are pronounced at pyrometallurgical sites, whereas the levels in sediments are higher at the hydrometallurgical sites.     

Variations and net transport of dissolved inorganic nutrients in the South Passage of the Changjiang （Yangtze River） Estuary

Dissolved inorganic nutrient elements were analyzed from the samples collected in the South Passage of the Changjiang (Yangtze River) Estuary in March 2003, including NH4 , NO3-, NO2- and PO43-. The water samples were collected with a Niskin sampler hourly at the near-surface, middle and near-bottom depths at the three stations -A1, A2 and A3-during two complete tidal cycles of neap tide and spring tide. Results showed that 1) the concentrations of NH4 , NO3- and NO2- were a little higher respectively during the neap tide than those during the spring tide, while PO43- showed an opposite trend, and each was higher in the ebb tide than in the flood tide, either for the neap tidal cycle or the spring tidal cycle; 2) higher stratification of the nutrients existed obviously in this area, with the concentrations of which increased from the bottom to the surface, especially for NH4 and NO3-; 3) the coefficient of variation (C.V.) values of all dissolved inorganic nutrients varied from 4.06% to 36.8% beyond different influences of the tidal current and Changjiang runoff; 4) with increasing suspended matter in the water column, the concentrations of PO43- became lower in the filtered water; and 5) the total transport of each tidal cycle was much more in the spring tide than in the neap tide, and the positive values indicated that the nutrients had been exported to the East China Sea. Studies on the variations and net transport of dissolved inorganic nutrients in the South Passage of the Changjiang Estuary will provide the scientific basis for the study of the mechanism of red tide in the East China Sea.     

Mineralogy and origin of stichtite in chromite-bearing serpentinites

Stichtite, a rare (14 known localities worldwide) hydrated carbonate-hydroxide of Mg and Cr with ideal formula Mg₆Cr₂ (OH)₁₆ CO₃ · 4H₂O, occurs exclusively in Cr-rich serpentinites of ophiolites or greenstone belts. Physical properties (hardness = 1.5–2, specific gravity = 2.16–2.2, perfect basal [0001] cleavage, grain size commonly < 100 μm) resemble talc, but the mineral has an attractive purple to lilac color; chemical analyses demonstrate it to be a non-silicate. Stichtite generally occurs as irregular to rounded masses (< 1 cm – 30 cm across) and as veinlets (< 1 mm – > 2 cm wide) within serpentinite. Macroscopic and microscopic textures, such as crosscutting veinlets and stringers, demonstrate that stichtite formation invariably post-dated serpentinization. In some specimens stichtite surrounds relict grains of Cr-rich spinel; in others stichtite has completely replaced euhedral or subhedral chromites. Chemical analyses of stichtites reveal substantial substitution of Al and Fe³⁺ for Cr in specimens from many localities, reflecting a possible compositional continuum between stichtite and rhombohedral polymorphs hydrotalcite (Mg₆Al₂ (OH)₁₆ CO₃ · 4H₂O) and pyroaurite (Mg₆Fe₂ (OH)₁₆ CO₃ · 4H₂O). We report the first electron microprobe analyses of stichtites from seven localities, and summarize all available published chemical data. Stichtites very likely inherited part of their trivalent cation chemistry from precursor Cr-rich spinels, but stichtite growth apparently post-dated characteristic “ferritchromit” alteration, as demonstrated by the depletion of Al and enrichment in Fe³⁺ in stichtite relative to primary chromite core compositions. Stichtite appears to form by reaction between serpentine and altered chromite, during addition of substantial fluid, either as separate H₂O and CO₂ phases, or as a mixed volatile phase. Such reactions must involve removal of substantial SiO₂, possibly by transport and remote deposition of silica by throughgoing aqueous and carbonic fluid. Received: 4 April 1996 / Accepted: 16 September 1996     

Behavior of Uranium in the Yellow River Plume (Yellow River Estuary)

The Yellow River (Huanghe) is the second largest river in China and is known for its high turbidity. It also has remarkably high levels of dissolved uranium (U) concentrations (up to 38 nmol 1^-1). To examine the mixing behavior of dissolved U between river water and seawater, surface water samples were collected along a salinity gradient from the Yellow River plume during September 2004 and were measured for dissolved U concentration,²³⁴U:²³⁸U activity ratio, phosphate (PO₄ ^3–), and suspended particulate matter. Laboratory experiments were also conducted to simulate the mixing process in the Yellow River plume using unfiltered Yellow River water and filtered seawater. The results showed a nonconservative behavior for dissolved U at salinities < 20 with an addition of U to the plume waters estimated at about 1.4 X 10⁵ mol yr^–1. A similarity between variations in dissolved U and PO₄ ^3– with salinity was also found. There are two major mechanisms, desorption from suspended sediments and diffusion from interstitial waters of bottom sediments, that may cause the elevated concentrations of dissolved U and PO₄ ^3– in mid-salinity waters. Mixing experiments indicate that desorption seems more responsible for the elevated dissolved U concentrations, whereas diffusion influences more the enrichment of PO₄ ^3–.     

The first deep Quaternary groundwater capture in Switzerland: combined use and environmental benefits

 Foresighted and determined local authorities, purposeful exploration (i.e. by seismic reflection) and extensive testing led to the discovery of a substantial groundwater resource near the community of Seon (Switzerland) at a depth of 268–305 m. Production tests revealed a hydraulic conductivity of ∼5.10–5 m/s, transmissivity of ∼5.10–4 m²/s and a storage coefficient of ∼2% in the aquifer. Pumping up to 1500 l/min is sustainable; the water quality complies chemically and bacteriologically with drinking-water requirements. The residence time of several 10³ years, determined by isotope techniques, guarantees protection from surface contamination. The elevated temperature of 19.5  °C of the produced water enables combined use for drinking water and space heating. The environmental benefits are substantial: the emission reduction amounts up to 780 tons/year CO₂ and 1 ton/year SO₂. Received: 21 September 1998 · Accepted: 10 February 1999     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

The stability of primary alluaudites in granitic pegmatites: an experimental investigation of the Na2(Mn2−2x Fe1+2x )(PO4)3 system

In order to assess the geothermometric potential of the Na₂(Mn_2−2x Fe_1+2x )(PO₄)₃ system (x = 0–1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal experiments between 400 and 800°C, at 1 kbar, under an oxygen fugacity (f(O₂)) controlled by the Ni–NiO (NNO), Fe₂O₃–Fe₃O₄ (HM), Cu₂O–CuO (CT), and Fe–Fe₃O₄ (MI) buffers. When f(O₂) is controlled by NNO, single-phase alluaudites crystallize at 400 and 500°C, whereas the association alluaudite + marićite appears between 500 and 700°C. The limit between these two fields corresponds to the maximum temperature that can be reached by alluaudites in granitic pegmatites, because marićite has never been observed in these geological environments. Because alluaudites are very sensitive to variations of oxygen fugacity, the field of hagendorfite, Na₂MnFe²⁺Fe³⁺(PO₄)₃, has been positioned in the f(O₂)–T diagram, and provides a tool that can be used to estimate the oxygen fugacity conditions that prevailed in granitic pegmatites during the crystallization of this phosphate.     

Effects of quarry mining and of other environmental impacts in the mountainous Chicam-Toctina drainage basin (Córdoba, Argentina)

 The environmental conditions prevailing in the Chicam-Toctina drainage system (approx. 138 km² in Córdoba, Argentina) are considered representative of a number of catchments in Argentina's Sierras Pampeanas Range. Two groups of ions reflect the sources of dissolved species in the catchment: a) a group (Cl^–, SO^2– ₄, and Na⁺) which recognizes natural and anthropogenic sources, and which exhibits significant correlations with N^– ₃ and NO^– ₂, and b) another group of components (Ca²⁺, Mg²⁺, and HCO^– ₃) which is clearly controlled by carbonate rocks and their waste rock products. In the headwaters, stockpiled marble quarry mining wastes provide a more open system to CO₂ gaseous exchange than the outcropping rocks, thus promoting the increase of carbonate dissolution (up to 4.88 g km^–2 s^–1 during the rainy season). This specific yield was 20% higher than the amount estimated for an area with fewer extended mining activities. The dissolved load delivered by the upper reaches is subjected in the lower drainage area to various processes, mainly controlled by the presence of the city of Alta Gracia (approx. 40,000 inhabitants). In the dry season, due to nutrient inputs supplied by the city, photosynthetic activity plays a major role controlling stream pH. Hence, the high values of calcite saturation indexes and the increase of CaCO₃ concentration in bed sediments can be explained by calcite precipitation. Such a process could be accompanied by the coprecipitation on calcium carbonate of low solubility heavy metal carbonates. Received : 17 January 1997 · Accepted : 31 March 1997     

Geochemical processes controlling the spatial distribution of selenium in soil and water,west central South Dakota,USA

Selenium (Se) is essential in the human diet, but has a low threshold for toxic concentration. It is recommended that nutrients such as Se should be consumed through foods as part of a normal diet. Se concentrations in crops and meat depend on the amount of labile Se in the soil where crops and forage are grown. Therefore, managing agriculture for optimal Se in grain crops and forage requires an understanding of the distribution and mobility of Se. Elevated concentrations of Se occur in waters, soils, and forage 120 km west of Pierre in west central South Dakota, USA. The research site lies in an elevated, dissected plain where soils developed on gently dipping Pierre Shale. Soils were sampled along catena transects and waters collected from soil, ponds, and shallow borings in areas of known elevated forage and crop Se. Soil extracts from saturated-paste extraction and acid (aqua regia and hydrofluoric acid) extraction were analyzed. Selenate was the dominant Se species in both acid and saturated-paste extracts; selenite and organic Se were below detection (<0.2 ppb) in the same soil extracts. On average, 98% of soil Se was not water-soluble. The distribution of total Se shows much less spatial variation than water-soluble Se in the areas sampled. Se shows correlation with organic carbon in soils and waters, suggesting its association with organic carbon. Ca shows some correlation to Se in acid extracts, but not in saturated-paste extracts or in waters. Total Se shows no significant correlation to Na, Mg, and total S in the soils. Se in saturated-paste extracts and water samples shows good correlations with Na, Mg, and SO₄, suggesting that evaporitic Na–Mg–sulfate minerals may temporarily concentrate water-soluble Se in shallow soils. The dissolution and precipitation of these Na–Mg–sulfate salts together with pH and oxidation–reduction conditions apparently control water-soluble Se distribution and mobilization in shallow subsurface environments.