南海北部陆坡西沙海槽XS-01站位沉积物孔隙水的 地球化学特征及其对天然气水合物的指示意义*

天然气水合物是近年来国际上发现的一种新型能源,大量赋存在海底沉积物中。西沙海槽位于南海北部陆坡区,周边有多个大型深水油气田区。对该区地形地貌、地质构造和沉积条件分析以及地球物理BSR分布表明,西沙海槽是我国海洋天然气水合物资源勘查的一个有利远景区。文章主要研究了位于西沙海槽最大BSR区内的XS-01站位沉积物孔隙水的地球化学特征,发现该站位孔隙水阴阳离子浓度和微量元素组成特征变化显示出可能与天然气水合物有关的明显地球化学异常,与国际上己发现有天然气水合物地区的异常相类似。因此,认为该站位是西沙海槽区最有利的天然气水合物赋存区,值得进一步的勘查工作。     

Characteristics and driving factors of surface water chemistry of Wujiang watershed

The changes in the water chemistry of rivers can reflect influence of anthropogenic activities on the water environment to some extent. To understand the relationship between the spatial distribution of the eco-environment of the watershed and the characteristics of water chemistry and geochemistry of rivers, firstly, the digital Wujiang watershed was built, and then the sub-watersheds were delineated, taking the sample points as sub-watershed outlets based on GIS. Secondly, using the function of spatial analyst of GIS, the statistical features of eco-environment (such as lithology and land use/cover) of each sub-watershed were calculated according to their respective classification. Finally, the correlation between the spatial distribution of lithology of the sub-watersheds and their corresponding ⁸⁷Sr/⁸⁶Sr ratio of river water, the correlation between NO₃ ⁻/HCO₃ ⁻, Cl⁻/HCO₃ ⁻, SO₄ ²⁻/HCO₃ ⁻ and anthropogenic activities, respectively, and the correlation between the fraction of green vegetation of the sub-watershed and their corresponding flux of TDS (total dissolved solids) were analyzed quantitatively. The results justify that the ⁸⁷Sr/⁸⁶Sr ratio of river water is highly dependent on the lithologic feature of the watershed and indicate that anthropogenic activities are one of the main sources of NO₃ ⁻ and SO₄ ²⁻ of river waters. The output of TDS is highly dependent on the percentage of vegetation cover of the watershed.     

南海北部琼东南海域HQ-48PC站位地球化学特征及对天然气水合物的指示意义

南海北部陆坡琼东南海域是中国天然气水合物勘探最具潜力的区域之一。对该海域的HQ-48PC站位沉积物样品的顶空气甲烷含量、孔隙水阴、阳离子及微量元素含量等地球化学特征进行综合分析,结果显示:在硫酸盐-甲烷界面(SMI,Sulfate-Methane Interface)(推算深度约为6.05 mbsf)发生了强烈的甲烷厌氧氧化反应(AMO,Anaerobic Meth-ane Oxidation),主要表现为SO24-含量线性降低接近于0、CH4含量发生骤增、有机碳和黄铁矿含量达到最大值及形成一个"钡锋"等特征。在SMI之上,HCO3-浓度随深度的增加呈明显上升的趋势,Ca2+、Mg2+、Sr2+等离子浓度随深度的增加呈降低的趋势,Mg2+/Ca2+比值随深度的增加呈明显增加的趋势,自生碳酸盐矿物以方解石为主;在SMI之下,HCO3-浓度随深度的增加呈缓慢下降的趋势,Ca2+浓度变化不大,Mg2+、Sr2+浓度和Mg2+/Ca2+比值随深度的增加呈降低的趋势,自生碳酸盐矿物以白云石为主。沉积物孔隙水的PO34-和NH4+含量较高,它们随深度的增加呈明显升高的趋势,且这种变化趋势与SO42-含量的下降趋势大致呈镜像关系。这些地球化学异常特征与国际上已发现有天然气水合物地区的地球化学特征相类似,暗示该采样站位深部沉积物中可能赋存有天然气水合物藏。     

Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution

The salt waters from the Emilia-Romagna sector of the Northern Apennine Foredeep have been investigated using major and trace element and stable isotope (δ²H, δ¹⁸O, δ³⁷Cl, δ⁸¹Br and ⁸⁷Sr/⁸⁶Sr ratio). Ca, Mg, Na, K, Sr, Li, B, I, Br and SO₄ vs. Cl diagrams suggest the subaerial evaporation of seawater beyond gypsum and before halite precipitation as primary process to explain the brine’s salinity, whereas saline to brackish waters were formed by mixing of evaporated seawater and water of meteoric origin. A diagenetic end-member may be a third component for mud volcanoes and some brackish waters. Salinization by dissolution of (Triassic) evaporites has been detected only in samples from the Tuscan side of the Apennines and/or interacting with the Tuscan Nappe. In comparison with the seawater evaporation path, Ca–Sr enrichment and Na–K–Mg depletion of the foredeep waters reveal the presence of secondary processes such as dolomitization–chloritization, zeolitization–albitization and illitization. Sulfate concentration, formerly buffered by gypsum-anhydrite deposition, is heavily lowered by bacterial and locally by thermochemical reduction during burial diagenesis. From an isotopic point of view, data of the water molecule confirm mixing between seawater and meteoric end-members. Local ¹⁸O-shift up to +11‰ at Salsomaggiore is related to water–rock interaction at high temperature (≈150°C) as confirmed by chemical (Mg, Li, Ca distribution) and isotopic (SO₄–H₂O) geothermometers. ³⁷Cl/³⁵Cl and ⁸¹Br/⁷⁹Br ratios corroborate the marine origin of the brines and evidence the diffusion of halogens from the deepest and most saline aquifers toward the surface. The ⁸⁷Sr/⁸⁶Sr ratio suggests a Miocene origin of Sr and rule out the hypothesis of a Triassic provenance of the dissolved components for the analyzed waters issuing from the Emilia-Romagna sector of the foredeep. Waters issuing from the Tuscan side of the Apennines and from the Marche sector of the foredeep show higher ⁸⁷Sr/⁸⁶Sr ratios because of the interaction with siliciclastic rocks.     

Impact of Alkaline Earth Metals on Aqueous Speciation of Uranium(VI) and Sorption on Quartz

The effect of Mg-, Ca-, and Sr–Uranyl-Carbonato complexes with respect to sorption on quartz was studied by means of batch experiments with U(VI) concentration of 0.126 × 10⁻⁶ M in the presence and absence of Mg, Ca, and Sr (each 1 mM) at pH from 6.5 to 9. In the absence of alkaline earth elements, 90% of the U(VI) sorbed on the quartz surface at all pH. In the presence of Mg, Ca, and Sr, the sorption of U(VI) on quartz decreased to 50, 10, and 30%, respectively. Sorption kinetics of U(VI) on quartz is faster in the absence of alkaline earth elements and reached equilibrium after 12 h, whereas in the presence of Mg, Ca and Sr, the kinetics of U(VI) sorption on quartz is pH dependent and attained equilibrium after 24 h. Aqueous speciation calculations for alkaline earth uranyl carbonates were carried out by using PHREEQC with the Nuclear Energy Agency thermodynamic database (NEA_2007) by adding constants for MUO₂(CO₃)₃²⁻ and M₂UO₂(CO₃)₃⁰ (M = Ca, Mg, Sr). This study reveals that alkaline earth elements can have a significant effect on the aqueous speciation of U(VI) under neutral to alkaline pH conditions and subsequently sorption behavior and mobility of U(VI) in aqueous environments.     

Thermodynamic and pore water halogen constraints on gas hydrate distribution at ODP Site 997 (Blake Ridge)

Marine sediment sequences with CH₄ hydrate are characterized by an atypical depth profile in dissolved Cl⁻ squeezed from pore space: a shallow subsurface Cl⁻ maximum overlies a lengthy and pronounced Cl⁻ minimum. This pore water Cl⁻ profile represents a combination of multiple processes including glacial–interglacial variations in ocean salinity, advection and diffusion of ions that are excluded during gas hydrate formation at depth, and release of fresh water from dissociation of hydrate during core recovery. In situ quantities of gas hydrate can be determined from a measured pore water Cl⁻ profile provided the in situ pore water signature prior to core recovery can be separated. Ocean Drilling Program (ODP) Site 997 was drilled into a large CH₄ hydrate reservoir on the Blake Ridge in the western Atlantic Ocean. Previously we have constructed a high-resolution pore water Cl⁻ profile at this location; here we present a `coupled chloride-hydrate' numerical model to explain basic trends in the Cl⁻ profile and to isolate in situ Cl⁻ concentrations. The model is based on thermodynamic and ecological considerations, and uses established equations for describing chemical behavior in marine sediment–pore water systems. The model incorporates four key concepts: (1) most gas hydrate is formed immediately below the SO₄²⁻ reduction zone; (2) fluid, dissolved ions and gas advect upward through the sediment column; (3) CH₄ hydrate dissociates at the base of hydrate stability conditions; and (4) seawater salinity fluctuates during glacial–interglacial cycles of the late Pliocene and Quaternary. Rates of upward advection in the model are sufficient to account for measured Br⁻ and I⁻ concentrations as well as CH₄ oxidation at the base of the SO₄²⁻ reduction zone. In situ pore water Cl⁻ inferred from the model is similar to that determined by limited direct sampling; in situ CH₄ hydrate amounts inferred from the model (an average of about 4% of porosity) are broadly consistent with those determined by direct gas sampling and indirect geophysical techniques. The model also predicts production of substantial quantities of free CH₄ gas bubbles (>2.5% of porosity) at a depth immediately below the lowest accumulation of CH₄ hydrate in the sediment column. Our explanation for the pore water Cl⁻ profile at Site 997 is important because it provides a theoretical mechanism for understanding the distribution of interstitial water Cl⁻, gas hydrate, and free gas in a marine sediment column.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and ⁸⁷Sr/⁸⁶Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q_h), based on Cl mass balances, vary from 0.06 to 0.22 m yr⁻¹, resulting in fluid residence times in the terraces of 10-24 yrs.As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO₃ > HCO₃ > SO₄ reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute ⁸⁷Sr/⁸⁶Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and ⁸⁷Sr/⁸⁶Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate.Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R_solute are estimated from linear Na and Si pore weathering gradients b_solute such that

     

Hydrogeochemistry of the groundwater flow system in a crystalline terrain: a study from the Kurunegala district,Sri Lanka

Water samples collected from dug wells and tube wells from the Kurunegala District of Sri Lanka have been studied for their major hydrogeochemical parameters to understand the chemical quality of water in the terrain. The region is composed of Precambrian metamorphic rocks where groundwater is only available in the regolith and along weak structural discontinuities. The study of the major chemical constituents of groundwater revealed several relationships with the aquifer lithology. Groundwater from mafic rocks have high dissolved solids, while quartzose metaclastic rocks yield water with low dissolved solids. The study area displays very low SO₄ ²⁻ contents of the groundwater. The chloride content is higher in the dry regions and in terrains underlain by pink granite and marble/calc gneiss while areas with marble, as expected, show high concentrations of Ca and Mg ions. The waters in the region can be classified into non-dominant cations to Na + K dominant and Cl⁻ and HCO₃ ⁻ dominant types. Water from charnockite-bearing areas tends to have non-dominant cations and more CO₃ ²⁻ + HCO₃ ⁻ types. Effects such as soluble salts in the regolith, fracture intensity and climatic variations play a significant role in the behavior of the hydrogeochemistry in the area.     

The geochemical and genetic role of organic substances in postmagmatic derivatives of alkaline plutons

Solid bituminous substances (SBS) are common components of the late hydrothermal mineral assemblages of peralkaline pegmatites. SBS are formed in a reductive setting as a result of progressive sorption of minor carbon-bearing molecules (CO, CO₂, CH₄, C₂H₆, C₂H₄, etc.), their polymerization, transformation into aromatic compounds (reformation), and selective oxidation on microporous zeolite-like Ti-, Nb-, and Zrsilicates serving as sorbents and catalysts. The oxygen-bearing aromatic compounds with hydrophile functional groups (−OH, −C=O, −COOH, −COO) act as complexing agents with respect to Th, REE, U, Zr, Ti, Nb, Ba, Sr, Ca, resulting in transfer of these bitumenophile elements under low-temperature hydrothermal conditions in the form of water-soluble macroassociates of the micelle type. Th, REE, and to a lesser extent, U, Zr, Ti, and Nb concentrate at the late stage of the hydrothermal process as microphases impregnating SBS or macroscopic segregations of Th and REE minerals. At the final stage, homogeneous SBS break down into organic (partly together with Ca, Sr, Ba, and Pb) and mineral (with Th, Ln, Y, Ti, Nb, Ca, Na, K, Si) microphases.     

Environmental geochemistry and quality assessment of mine water of Jharia coalfield,India

A long mining history and unscientific exploitation of Jharia coalfield caused many environmental problems including water resource depletion and contamination. A geochemical study of mine water in the Jharia coalfield has been undertaken to assess its quality and suitability for domestic, industrial and irrigation uses. For this purpose, 92 mine water samples collected from different mining areas of Jharia coalfield were analysed for pH, electrical conductivity (EC), major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺), anions (F⁻, Cl⁻, HCO₃ ⁻, SO₄ ²⁻, NO₃ ⁻), dissolved silica (H₄SiO₄) and trace metals. The pH of the analysed mine water samples varied from 6.2 to 8.6, indicating mildly acidic to alkaline nature. Concentration of TDS varied from 437 to 1,593 mg L⁻¹ and spatial differences in TDS values reflect the variation in lithology, surface activities and hydrological regime prevailing in the region. SO₄ ²⁻ and HCO₃ ⁻ are dominant in the anion and Mg²⁺ and Ca²⁺ in the cation chemistry of mine water. High concentrations of SO₄ ²⁻ in the mine water of the area are attributed to the oxidative weathering of pyrites. Ca–Mg–SO₄ and Ca–Mg–HCO₃ are the dominant hydrochemical facies. The drinking water quality assessment indicates that number of mine water samples have high TDS, total hardness and SO₄ ²⁻ concentrations and needs treatment before its utilization. Concentrations of some trace metals (Fe, Mn, Ni, Pb) were also found to be above the desirable levels recommended for drinking water. The mine water is good to permissible quality and suitable for irrigation in most cases. However, higher salinity, residual sodium carbonate and Mg-ratio restrict its suitability for irrigation at some sites.     

Climatic significance of seasonal trace element and stable isotope variations in a modern freshwater tufa

We present a continuous ∼14-yr-long (1985 to 1999) high-resolution record of trace element (Mg, Sr, Ba, U) and stable isotope (δ¹³C, δ¹⁸O) variations in a modern freshwater tufa from northwestern Queensland, Australia. By utilizing the temperature dependence of the δ¹⁸O signal, an accurate chronology was developed for the sampled profile, which allowed a comparison of the chemical records with hydrological and meteorological observations. As a consequence, it was possible to constrain the relevant geochemical processes relating climate variables, such as temperature and precipitation, to their chemical proxies in the tufa record. Temperatures calculated from the Mg concentrations of the tufa samples provide close approximations of average annual water temperature variations. Furthermore, we demonstrate that temporal changes in (Mg/Ca)_water can be estimated using an empirically derived equation relating (Mg/Ca)_water to the (Sr/Ba) ratio measured in the tufa samples. By means of this relationship, it is theoretically possible to determine the (Mg/Ca) ratio of paleowaters, and hence to derive reliable estimates of former water temperatures from the Mg concentrations of fossil tufas from the study area. Sympathetic variations in Sr, Ba, and δ¹³C along the sampled profile record changes in water chemistry, which are most probably caused by variable amounts of calcite precipitation within the vadose zone of the karst aquifer. This process is thought to be markedly subdued whenever the amount of wet-season precipitation exceeds a given threshold. Accordingly, distinct minima in Sr, Ba, and δ¹³C are interpreted to reflect years with above-average rainfall. The pronounced seasonal and annual variability of the U concentration along the profile is thought to primarily record changes in the U flux from the soil to the water table. We suggest that during intensive rain events U is transported to the phreatic zone by complexing organic colloids, giving rise to conspicuous U maxima in the tufa after above-average wet seasons. This study demonstrates the potential of freshwater tufas to provide valuable information on seasonal temperature and rainfall variations. If tufa deposits turn out to be reasonably resistant to secondary processes, combined investigation of speleothems and tufas from the same area could become a promising approach in future research. While speleothems offer continuous records of long-term paleoenvironmental changes, tufas could provide high-resolution time windows into selected periods of the past.     

Regional hydrogeochemical patterns in ground water of Northwestern Ohio and their relation to Mississippi valley—type mineral occurrences

A cluster of minor Mississippi Valley-type deposits occurs in northwestern Ohio. The district, which forms a northeasterly trending belt that cuts across the Findlay Arch, extends from the Indiana border to the Lake Erie Islands. The minerals of the deposits — chiefly celestite, fluorite and sphalerite with lesser amounts of barite and galena — show variation in both geographic and stratigraphic distribution. Dolomites of Middle Silurian to Middle Devonian age, which are the host rocks, also form an important aquifer system. The deposits are of interest because they might be indicators of economic mineralization at depth.Through a reconnaissance study, one-hundred ground-water samples from shallow wells (less than 50 m deep) were collected across an area of approximately 19 000 km². Recharge takes place in the southern part of the area while ground-water flow is northward towards Lake Erie. The majority of the samples are high in sulfate with the source being evaporites within the carbonate sequence. The remainder of the water samples are rich in bicarbonate. Trend surface maps for the major constituents indicate that the ground-water chemistry for the region is established chiefly by the lithology and the flow system. Trend surface maps for F⁻, Sr and Ba reflect the geographic distribution of the minerals in the deposits. Correlations are weakened, however, due to the influence of geochemical barriers such as SO₄²⁻ on Ba and Sr, and Ca on F⁻. The map for Pb follows the trends of the major constituents instead of the mineralization.In a detailed study across northwestern Sandusky County, which lies near the center of the district, 46 samples were collected in an area of 78 km². Trend surface maps for Ca, Mg, SO₄²⁻ and total dissolved solids reflect the chemistry of the bedrock and display concentrations that increase along the local flow path. Maps for F⁻, Sr and Ba correlate with mineralization in the vicinity, the first of these displaying a local trend and the last two correlating with regional trends.     

Mobilization and loss of elements from roofing tiles

Deposition, leaching and chemical transformation are processes that affect roofing tile and roof runoff water. Leaching experiments, with artificial rainwater in the laboratory, showed the presence of Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₃ ⁻, SO₄ ²⁻, with a ratio of Ca²⁺ and SO₄ ²⁻ suggesting gypsum dissolution. X-ray fluorescence (XRF) of the exposed roof tile showed depletion such as Mg, Al, Si, P, Ti and K at the surface of the tile and an enrichment of Fe and Mn which hinted at a process akin to laterite formation. However, calcium appeared to be enriched at the surface as gypsum (confirmed by X-ray diffraction) and to a lesser extent calcite, which is characteristic of deposits on building surfaces in cities.     

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.     

Interaction of diamond mine waste and surface water in the Canadian Arctic

Factors controlling the chemical composition of water interacting with finely-crushed kimberlite have been investigated by sampling pore waters from processed kimberlite fines stored in a containment facility. Discharge water from the diamond recovery plant and surface water from the containment facility, which acts as plant intake water, were also sampled. All waters sampled are pH-neutral, enriched in SO₄, Mg, Ca, and K, and low in Fe. Pore-water samples, representing the most concentrated waters, are characterized by the highest SO₄ (up to 4080 mg l⁻¹), Mg (up to 870 mg l⁻¹), and Ca (up to 473 mg l⁻¹). The water discharged from the processing plant has higher concentrations of all major dissolved constituents than the intake water. The dominant minerals present in the processed fines and the kimberlite ore are serpentine and olivine, with small amounts of Ca sulphate and Fe sulphide restricted to mud xenoclasts. Reaction and inverse modeling suggest that much of the water-rock interaction takes place within the plant and involves the dissolution of chrysotile and Ca sulphate, and precipitation of silica and Mg carbonate. Evapoconcentration also appears to be a significant process affecting pore water composition in the containment facility. The reaction proposed to be occurring during ore processing involves the dissolution of CO_2(g) and may represent an opportunity to sequester atmospheric CO₂ through mineral carbonation.     

Controls on ostracod valve geochemistry, Part 1: Variations of environmental parameters in ostracod (micro-)habitats

The variations of environmental conditions (T°, pH, δ¹³C_DIC, [DIC], δ¹⁸O, Mg/Ca, and Sr/Ca) of ostracod habitats were examined to determine the controls of environmental parameters on the chemical and isotopic composition of ostracod valves. Results of a one-year monitoring of environmental parameters at five sites, with depths of between 2 and 70 m, in Lake Geneva indicate that in littoral to sub-littoral zones (2, 5, and 13 m), the chemical composition of bottom water varies seasonally in concert with changes in temperature and photosynthetic activity. An increase of temperature and photosynthetic activity leads to an increase in δ¹³C values of DIC and to precipitation of authigenic calcite, which results in a concomitant increase of Mg/Ca and Sr/Ca ratios of water. In deeper sites (33 and 70 m), the composition of bottom water remains constant throughout the year and isotopic values and trace element contents are similar to those of deep water within the lake. The chemical composition of interstitial pore water also does not reflect seasonal variations but is controlled by calcite dissolution, aerobic respiration, anaerobic respiration with reduction of sulphate and/or nitrate, and methanogenesis that may occur in the sediment pores. Relative influence of each of these factors on the pore water geochemistry depends on sediment thickness and texture, oxygen content in bottom as well as pore water. Variations of chemical compositions of the ostracod valves of this study vary according to the specific ecology of the ostracod species analysed, that is its life-cycle and its (micro-)habitat. Littoral species have compositions that are related to the seasonal variations of temperature, δ¹³C values of DIC, and of Mg/Ca and Sr/Ca ratios of water. In contrast, the compositions of profundal species are largely controlled by variations of pore fluids along sediment depth profiles according to the specific depth preference of the species. The control on the geochemistry of sub-littoral species is a combination of controls for the littoral and profundal species as well as the specific ecology of the species.     

Geochemical evolution of uraniferous soda lakes in Eastern Mongolia

Extremely high concentrations of uranium (U) were discovered in shallow, groundwater-fed hyperalkaline soda lakes in Eastern Mongolia. A representative groundwater sample in this area is dilute and alkaline, pH = 7.9, with 10 mM TIC and 5 mM Cl⁻. In contrast, a representative lake water sample is pH ~ 10 with TIC and Cl⁻ each more than 1,000 mM. Groundwater concentrations of U range from 0.03 to 0.43 μM L⁻¹. Lake water U ranges from 0.24 to >62.5 μM, possibly the highest naturally occurring U concentrations ever reported in surface water. Strontium isotopes ⁸⁷Sr/⁸⁶Sr varied in groundwaters from 0.706192 to 0.709776 and in lakes ⁸⁷Sr/⁸⁶Sr varied from 0.708702 to 0.709432. High concentrations of U, Na, Cl⁻, and K correlate to radiogenic Sr in lake waters suggesting that U is sourced from local Cretaceous alkaline rhyolites. Uranium-rich groundwaters are concentrated by evaporation and U(VI) is chelated by CO₃⁻² to form the highly soluble UO₂(CO₃)₃⁻⁴. Modeled evaporation of lakes suggests that a U-mineral phase is likely to precipitate during evaporation.     

Groundwater recharge and agricultural contamination

Agriculture has had direct and indirect effects on the rates and compositions of groundwater recharge and aquifer biogeochemistry. Direct effects include dissolution and transport of excess quantities of fertilizers and associated materials and hydrologic alterations related to irrigation and drainage. Some indirect effects include changes in water–rock reactions in soils and aquifers caused by increased concentrations of dissolved oxidants, protons, and major ions. Agricultural activities have directly or indirectly affected the concentrations of a large number of inorganic chemicals in groundwater, for example NO₃ ^–, N₂, Cl, SO₄ ^2–, H⁺, P, C, K, Mg, Ca, Sr, Ba, Ra, and As, as well as a wide variety of pesticides and other organic compounds. For reactive contaminants like NO₃ ^–, a combination of chemical, isotopic, and environmental-tracer analytical approaches might be required to resolve changing inputs from subsequent alterations as causes of concentration gradients in groundwater. Groundwater records derived from multi-component hydrostratigraphic data can be used to quantify recharge rates and residence times of water and dissolved contaminants, document past variations in recharging contaminant loads, and identify natural contaminant-remediation processes. These data indicate that many of the world's surficial aquifers contain transient records of changing agricultural contamination from the last half of the 20th century. The transient agricultural groundwater signal has important implications for long-term trends and spatial heterogeneity in discharge. Electronic Publication     

Large tank experiment on nitrate fate and transport: the role of permeability distribution

A long-term elution experiment to study the saturated transport of pre-accumulated fertilizers by-products, was conducted within a large tank (4 × 8 × 1.4 m) equipped with 26 standard piezometers. Sandy sediments (35 m³), used to fill the tank, were excavated from an unconfined alluvial aquifer near Ferrara (Northern Italy); the field site was connected to a pit lake located in a former agricultural field. To evaluate spatial heterogeneity, the tank’s filling material was characterized via slug tests and grain-size distribution analysis. The investigated sediments were characterized by a large spectrum of textures and a heterogeneous hydraulic conductivity (k) field. Initial tank pore water composition exhibited high concentration of nitrate (NO₃ ⁻) sulfate (SO₄ ²⁻) calcium (Ca²⁺), and magnesium (Mg²⁺), due to fertilizer leaching from the top soil in the field site. The initial spatial distribution of NO₃ ⁻ and SO₄ ²⁻ was heterogeneous and not related to the finer grain-size content (<63 μm). The tank’s material was flushed with purified tap water for 800 days in steady-state conditions; out flowing water was regularly sampled to monitor the migration rate of fertilizer by-products. Complete removal of NO₃ ⁻ and SO₄ ²⁻ took 500 and 600 days, respectively. Results emphasized organic substrate availability and spatial heterogeneities as the most important constraints to denitrification and nitrogen removal, which increase the time required to achieve remediation targets. Finally, the obtained clean-up time was compared with a previous column experiment filled with the same sediments.