The double solid reactant method: II. An application to the shallow groundwaters of the Porto Plain,Vulcano Island (Italy)

This paper presents an example of application of the double solid reactant method (DSRM) of Accornero and Marini (Environmental Geology, 2007a), an effective way for modeling the fate of several dissolved trace elements during water–rock interaction. The EQ3/6 software package was used for simulating the irreversible water–rock mass transfer accompanying the generation of the groundwaters of the Porto Plain shallow aquifer, starting from a degassed diluted crateric steam condensate. Reaction path modeling was performed in reaction progress mode and under closed-system conditions. The simulations assumed: (1) bulk dissolution (i.e., without any constraint on the kinetics of dissolution/precipitation reactions) of a single solid phase, a leucite-latitic glass, and (2) precipitation of amorphous silica, barite, alunite, jarosite, anhydrite, kaolinite, a solid mixture of smectites, fluorite, a solid mixture of hydroxides, illite-K, a solid mixture of saponites, a solid mixture of trigonal carbonates and a solid mixture of orthorhombic carbonates. Analytical concentrations of major chemical elements and several trace elements (Cr, Mn, Fe, Ni, Cu, Zn, As, Sr and Ba) in groundwaters were satisfactorily reproduced. In addition to these simulations, similar runs for a rhyolite, a latite and a trachyte permitted to calculate major oxide contents for the authigenic paragenesis which are comparable, to a first approximation, with the corresponding data measured for local altered rocks belonging to the silicic, advanced argillic and intermediate argillic alteration facies. The important role played by both the solid mixture of trigonal carbonates as sequestrator of Mn, Zn, Cu and Ni and the solid mixture of orthorhombic carbonates as scavenger of Sr and Ba is emphasized.

Budgets of Mn,Cd and Cu in the macrotidal Gironde estuary (SW France)

The behavior and budget of Mn, Cd and Cu in the Gironde estuary were investigated through data from both the water column (WC) and sediment depth profiles. In the estuarine freshwater reaches, Mn and Cd removal from and Cu addition to the dissolved phase occurs with a magnitude equivalent to 10%, 30% and 25% of their respective annual fluvial gross dissolved input, respectively. In the saline estuary, diffusive benthic outflow is the main source of dissolved Mn (74% of the total gross dissolved input within the estuary) to the WC. In contrast, Cd (96%) and Cu (89%) are mainly released into the dissolved phase of the WC from fluvial, estuarine and dredging-related particles through complexation (Cd) and organic carbon mineralization (Cu). Anthropogenic activities (sediment dredging) induce pore water inputs, particulate sulfide oxidation and sediment resuspension, significantly contributing to the metal budget of the WC. The related amounts of metals released could be equivalent to 20–50% (Cd) and up to 70% (Cu) of their respective net dissolved addition. Mass balances suggest that a large part of the metals previously released into the dissolved phase from processes within the estuary are removed by suspended particles due to (co-)precipitation of Fe/Mn (oxy)hydroxides and scavenging on autochthonous organic matter. On an annual basis, the Gironde estuary acts as a net sink of dissolved Mn, removing 60% of the dissolved fluvial inputs, and as a net source of dissolved Cd and Cu, contributing ∼ 85% and 20–45% to the dissolved Cd and Cu fluxes to the ocean.     

The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Lake Sediment Core Records of Sulphur Accumulation and Sulphur Isotopic Composition in Central Ontario, Canada Lakes

Stable isotopic compositions and concentrations of total sedimentary sulphur (S) were determined in cores from 6 lakes in the acid-sensitive Muskoka-Haliburton region of south-central Ontario. The isotopic composition of S in deep sediment (> ~ 20 cm) was approximately constant in all lakes, and indicated a pre-industrial δ ³⁴S value between +4.0 and +5.3‰, which is similar to current bulk deposition. Similarly, total S concentrations in deep sediment were relatively low (1.9–5 mg S g⁻¹ dwt) and approximately constant with depth within cores. All lakes exhibited up-core increases in total S and decreases in δ ³⁴S at a depth corresponding to the beginning of industrialization in the Great Lakes region ( ~ 1900), resulting in a generally reciprocal depth pattern between total S concentration and δ ³⁴S ratios. While initial shifts in total S and δ ³⁴S were likely due to enhanced SO₄ reduction of newly available anthropogenic SO₄, both the magnitude and pattern of up-core S enrichment and shifts in δ ³⁴S varied greatly among lakes, and did not match changes in S deposition post 1900. Differences between lakes in total S and δ ³⁴S were not related to any single hydrologic (e.g., residence time) or physical (e.g., catchment-area-to-lake area ratio) lake characteristic. This work indicates that sediment cores do not provide consistent records of changes in post-industrial S deposition in this region, likely due to redox-related mobility of S in upper sediment.     

Attenuation of landfill leachate at two uncontrolled landfills

Attenuation characteristics of landfill leachate were examined for two uncontrolled landfills in Korea. The two landfills containing municipal wastes without appropriate bottom liner and leachate treatment system have different landfill age, waste volume, and most importantly different hydrogeologic settings. One landfill (Cheonan landfill) is situated in an open flat area while the other (Wonju landfill) is located in a valley. Variations of various parameters including dissolved organic carbon (DOC), dissolved oxygen (DO), alkalinity, pH, electrical conductivity (EC), redox potential (ORP), ammonia (NH₃), nitrate (NO₃⁻), sulfate (SO₄²⁻), and chloride (Cl⁻) were examined along groundwater flow path. All these parameters were analyzed every month for a year. In the interior of the landfills, typical anaerobic conditions revealed by low DO and NO₃ concentrations, negative ORP values, high NH₃, alkalinity, and Cl⁻ concentrations were observed. Generally, higher levels of contaminants (DOC, NH₃, and Cl⁻) were detected in the dry season while they were greatly lowered in the wet season. Significantly, large decrease of Cl^- concentration in the wet season indicates that the dilution or mixing is one of dominant attenuation mechanisms of leachate. But detailed variation behaviors in the two landfills are different and they were largely dependent on permeability of surface and subsurface layers. The intermediately permeable surface of the landfills receives part of direct rainfall infiltration but most rainwater is lost to fast runoff. The practically impermeable surface of clayey silt (paddy field) at immediately adjacent to the Cheonan landfill boundary prevented direct rainwater infiltration and hence redox condition of the ground waters were largely affected by that of the upper landfill and the less permeable materials beneath the paddy fields prohibited dispersion of the landfill leachate into down gradient area. In the Wonju landfill, there are three different permeability divisions, the landfill region, the sandy open field and the paddy field. Roles of the landfill and paddy regions are very similar to those at the Cheonan. The very permeable sandy field receiving a large amount of rainwater infiltration plays a key role in controlling redox condition of the down gradient area and contaminant migration. This paper reports details of the attenuation and redox conditions of the landfill leachates at the two uncontrolled landfills.     

Chemical characterization of the Neogene Aquifer, Belgium

The evolution of groundwater chemistry along the direction of groundwater flow was studied using hydrochemical data from samples collected along a flow line in the Neogene Aquifer, Belgium. Infiltrating water was found to have a very low mineral content and low pH because the sediments are strongly decalcified. Increasing SiO₂ and cation concentrations along the groundwater flow line indicate silicate-weathering processes, confirmed with the aid of saturation indices, calculated with PHREEQC, and stability diagrams. A classification system based on redox sensitive species was developed and shows that an extensive redox sequence is present in the aquifer. At a shallow depth, pyrite oxidation has caused an increase in sulphate, while iron is precipitated as hydroxides. Elevated arsenic concentrations are related to the reduction of these iron hydroxides at a relatively shallow depth and to the dissolution of siderite at greater depth. Dissolution of carbonate in the aquifer material, present in deep layers and to the north, has lead to increased Ca²⁺ and HCO₃ ^? concentrations. The Ca²⁺ from the groundwater is exchanged for Na⁺, Mg²⁺ and K⁺ adsorbed to the clay surfaces at the bottom of the groundwater reservoir. Although the Neogene Aquifer is well flushed, there are still some marine influences present in the deepest parts.     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

沉积盆地流体—岩石相互作用研究的现状

沉积盆地流体－岩石相互作用研究主要是通过实验地球化学和岩石学，地球化学模拟方法开展的，综述了这一领域的研究现状，主要包括有机酸来源和分布及期 对矿物稳定性的影响，地层水成因与演化、烃类与岩石间的氧化还原反应、以及储层润湿性的变化等，并展望了其 发展趋势。     

138铀矿床成矿地质及物化条件分析

１３８矿床是中生代火山－沉积改造型铀矿床。本文对矿床的铀源、矿区地层岩性、岩相古地理及古气候、构造和改造再生等地质条件，以及铀的吸附还原剂，岩石的有效孔隙度、化学成分、酸碱度、氧化还原电位等物理化学条件进行探讨。