Predicting arsenic concentrations in the porewaters of buried uranium mill tailings

The proposed JEB Tailings Management Facility (TMF) to be emplaced below the groundwater table in northern Saskatchewan, Canada, will contain uranium mill tailings from McClean Lake, Midwest and Cigar Lake ore bodies, which are high in arsenic (up to 10%) and nickel (up to 5%). A serious concern is the possibility that high arsenic and nickel concentrations may be released from the buried tailings, contaminating adjacent groundwaters and a nearby lake. Laboratory tests and geochemical modeling were performed to examine ways to reduce the arsenic and nickel concentrations in TMF porewaters so as to minimize such contamination from tailings buried for 50 years and longer. The tests were designed to mimic conditions in the mill neutralization circuit (3 hr tests at 25°C), and in the TMF after burial (5–49 day aging tests). The aging tests were run at, 50, 25 and 4°C (the temperature in the TMF). In order to optimize the removal of arsenic by adsorption and precipitation, ferric sulfate was added to tailings raffinates¹ having Fe/As ratios of less that 3–5. The acid raffinates were then neutralized by addition of slaked lime to nominal pH values of 7, 8, or 9.Analysis and modeling of the test results showed that with slaked lime addition to acid tailings raffinates, relatively amorphous scorodite (ferric arsenate) precipitates near pH 1, and is the dominant form of arsenate in slake limed tailings solids except those high in Ni and As and low in Fe, in which cabrerite-annabergite (Ni, Mg, Fe(II) arsenate) may also precipitate near pH 5–6. In addition to the arsenate precipitates, smaller amounts of arsenate are also adsorbed onto tailings solids.The aging tests showed that after burial of the tailings, arsenic concentrations may increase with time from the breakdown of the arsenate phases (chiefly scorodite). However, the tests indicate that the rate of change decreases and approaches zero after 72 hrs at 25°C, and may equal zero at all times in the TMF at 4°C. Consistent with a kinetic model that describes the rate of breakdown of scorodite to form hydrous ferric oxide, the rate of release of dissolved arsenate to tailings porewaters from slake limed tailings: (1) is proportional to pH above pH 6–7; (2) decreases exponentially as the total molar Fe/As ratio of tailings raffinates is increased from 1/1 to greater than 5/1; and (3) is proportional to temperature with an average Arrhenius activation energy of 13.4 ± 4.2 kcal/mol.Study results suggest that if ferric sulfate and slaked lime are added in the tailings neutralization circuit to give a raffinate Fe/As molar ratio of at least 3–5 and a nominal (initial) pH of 8 (final pH of 7–8), arsenic and nickel concentrations of 2 mg/L or less, are probable in porewaters of individual tailings in the TMF for 50 to 10,000 yrs after tailings disposal. However, the tailings will be mixed in the TMF, which will contain about 35% tailings with Fe/As = 3.0, and 65% tailings with Fe/As = 5.0–7.7. Thus, it seems likely that average arsenic pore water concentrations in the TMF may not exceed 1 mg/L.     

Arsenic mobilization from mine tailings in the presence of a biosurfactant

Batch experiments were conducted to investigate As mobilization from mine tailings in the presence of a biosurfactant (JBR425, mixed rhamnolipids) and to evaluate the feasibility of using biosurfactant in remediating As contaminated mine tailings/soils. Introduction of the biosurfactant increased As mobilization greatly. When the mass ratio was 10 mg biosurfactant/g mine tailings at pH 11, As mobilization by the biosurfactant was greatest after 24 h, with a corresponding concentration ratio (the ratio of As mobilization by the biosurfactant to that by distilled water at same adjusted pH, wt/wt) of 21.6. Selective sequential extraction indicated that As was easily mobilized from the weakly bound and relatively more mobile fractions by washing with the biosurfactant. A mobilization isotherm was developed to predict As mobilization from the mine tailings in the presence of biosurfactant. It was shown that biosurfactant sorption to the mine tailings is essential for As mobilization. Arsenic mobilization was found to be positively correlated with the mobilization of Fe and other metals (i.e., Cu, Pb and Zn), which might further enhance As mobilization by helping incorporate it into soluble complexes or micelles. Capillary electrophoresis analyses indicated that As redox or methylation reactions had insignificant effect on As mobilization. Biosurfactants might be used potentially to remove bulk As from mine tailings or contaminated soils under alkaline conditions.     

Dissolved organic carbon in pore waters from a hypersaline environment

Pore waters were collected from a sea-marginal, hypersaline pond in the Sinai and analyzed for dissolved organic carbon (DOC). The pore water DOC values ranged from 121 to 818 mg 1⁻¹ with maxima between 15 and 54 cm deep. These values are some of the highest observed from recent sediments and probably reflect production via abiotic as well as biotic sources.     

Release ofRa from uranium mill tailings by microbial Fe(III) reduction

Uranium mill tailings were anaerobically incubated in the presence of H₂ with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H₂ and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved²²⁶Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of²²⁶Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved²²⁶Ra from uranium mill tailings.     

Arsenic behaviour in gold-ore mill tailings,Massif Central,France: hydrogeochemical study and investigation of in situ redox signatures

Historical Au-ore exploitation at the Chéni mine in the Massif Central, France, generated 525,000 tonnes of finely ground mill tailings deposited in a heap that has spread with time into three settling basins. The tailings, which are rich in quartz (80%), mica and clay minerals (10% of illite, smectite, kaolinite and chlorite), feldspars (5%) but poor in carbonates (<1%), also contain sulphides (around 5%, mainly pyrite and arsenopyrite). Arsenic content of the tailings is around 6 g kg. This paper describes the geochemistry of drainage waters, with special attention paid to in situ values of the three major redox couples, namely Fe(II)/Fe(III), As(III)/As(V) and S(IV)/S(VI). The water samples range from acidic and oxidized (pH 2.9, E_h +700 mV) to moderate pH and weakly reducing (pH 7.6, E_h 15 mV). The waters are rich in SO₄ and Ca and have variable As (0.05–95 mg L⁻¹) and Fe concentrations (0.07–141 mg L⁻¹). Reduced As(III) species predominate over As(V) species (As(III)/As(V) up to 21), whereas oxidized forms of Fe and S are favoured (Fe(II)/Fe(III) up to 0.5, and S(IV)/S(VI) up to 1).Thermodynamic calculations were performed with the PHREEQC and EQ3NR codes based on a revised As database to evaluate saturation indices (SI) of the waters in relation to the main minerals and define which redox couples control the redox state of the system. The important role of carbonates, though only present in small amounts, explains the acid buffering generated by the oxidation of sulphides for waters in the pH 7–7.5 range. Measured E_h appears to fall between the calculated E_h of the Fe(II)/Fe(III) couple and that of the As(III)/As(V) couple, illustrating redox disequilibrium.     

Mobility of heavy metals from tailings to stream waters in local zinc smelting activities contaminated site

It has been found that stream waters were severely contaminated with wastes from a long-time smelting factory in Hezhang, Guizhou, China. The main sources of contamination are the smelting wastes stored in the open air and abandoned in the vicinity of stream. A method of lead isotope was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments were collected. Mineralogical characterizations were conducted using XRD and TEM/SEM, while acid digestion was carried out for determining metal contents. BCR sequential leaching tests were performed in order to assess metal mobility. The tremendous ‘actual＇ and ‘potential＇ mobility of heavy metals indicates that the smelting waste and stream sediments present a considerable threat to the environment. Besides the chemical remobilization of heavy metals from the sediments and the reworking of riverbed sediments act as a secondary source of pollution. Also groundwater and stream water were sampled in specific locations and were measured.     

Lithium isotope geochemistry of marine pore waters - Insights from cold seep fluids

Lithium concentration and isotope data (δ⁷Li) are reported for pore fluids from 18 cold seep locations together with reference fluids from shallow marine environments, a sediment-hosted hydrothermal system and two Mediterranean brine basins. The new reference data and literature data of hydrothermal fluids and pore fluids from the Ocean Drilling Program follow an empirical relationship between Li concentration and δ⁷Li (δ⁷Li = −6.0(±0.3) · ln[Li] + 51(±1.2)) reflecting Li release from sediment or rocks and/or uptake of Li during mineral authigenesis. Cold seep fluids display δ⁷Li values between +7.5‰ and +45.7‰, mostly in agreement with this general relationship. Ubiquitous diagenetic signals of clay dehydration in all cold seep fluids indicate that authigenic smectite-illite is the major sink for light pore water Li in deeply buried continental margin sediments. Deviations from the general relationship are attributed to the varying provenance and composition of sediments or to transport-related fractionation trends. Pore fluids on passive margins receive disproportionally high amounts of Li from intensely weathered and transported terrigenous matter. By contrast, on convergent margins and in other settings with strong volcanogenic input, Li concentrations in pore water are lower because of intense Li uptake by alteration minerals and, most notably, adsorption of Li onto smectite. The latter process is not accompanied by isotope fractionation, as revealed from a separate study on shallow sediments. A numerical transport-reaction model was applied to simulate Li isotope fractionation during upwelling of pore fluids. It is demonstrated that slow pore water advection (order of mm a⁻¹) suffices to convey much of the deep-seated diagenetic Li signal into shallow sediments. If carefully applied, Li isotope systematics may, thus, provide a valuable record of fluid/mineral interaction that has been inherited several hundreds or thousands of meters below the actual seafloor fluid escape structure.     

Arsenic mobility in two mine tailings drainage systems and its removal from solution by natural geochemical barriers

Sulfide-mineral-bearing mill wastes are sources of high concentrations of acid, soluble metals, and As. These are serious problems for ore mining areas such as the Kemerovo and Cheljabinsk regions in Russia. This study evaluated the distribution of the mill wastes, the mobility of As from the wastes, and the potential of natural materials to attenuate As dispersion in the broader environment. Arsenic contents in wastes of the Belovo Zn-processing (Kemerovo) and the Karabash Cu-smelting plants (Cheljabinsk) are 2–3 orders of magnitude higher than the content of continental crust. Main mineral forms of As in these wastes are arsenopyrite (FeAsS) and scorodite (FeAsO₄·2H₂O). High dissolved As concentrations are found in water draining the wastes and in rivers adjacent to the mill sites. The water concentrations commonly exceed drinking water standards. High As concentrations in bottom sediments of the affected rivers extend a 100 m downstream of the waste drainage input. These sediments are also a source of river water contamination. Experiments were conducted to evaluate the ability of natural water to mobilize As from the wastes. The Belovo tailings released 86% of their contained As to the infiltrating water, whereas the less reactive Karabash tailings released only 22% of total As. The experimental leachates were used as influent to columns that tested the ability of limestone and natural clay to reduce the concentration of dissolved As and associated metals. Some dissolved As was precipitated with Fe, Pb and Sb initially in the limestone column. The decrease in dissolved As is consistent with the accumulation of As in yellow ferriferous sediments in the Belovo settling pond. In the pond and wetland sediments, As mobility is also decreased by the formation of sulfides and arsenides. Cubanite (CuFe₂S₃), klaprothite (Cu₃BiS₃)_, rammelsbergite (NiAs₂), maucherite (Ni₁₁As₈), semseyite (Cu₉Sb₈S₂₁), and skutterudite (CoAs₃) were found in the chemically reducing lower sediments of the Belovo settling pond.     

全球变化背景下北方泥炭地释放溶解有机碳的驱动机制

泥炭地（peatland）是一类储碳效率很高的特殊陆地生态系统,其碳储量约占全球土壤碳库的近1／3,对全球碳循环有着举足轻重的作用。有证据表明在过去20余年,北半球大范围的天然水体中溶解有机碳的浓度呈显著增升趋势。普遍认为与全球变化背景下北方泥炭地大规模释放溶解有机碳有关,但其驱动机制尚不十分清楚。已经提出的具有代表性...     

Arsenic remobilization from sediments contaminated with mine tailings near the Adak mine in Västerbotten district (northern Sweden)

Weathering of mine tailings have resulted in high As concentrations in water (up to 2900 μg l^− 1) and sediment (up to 900 mg kg^− 1) samples around the Adak mine. Notably, As occurs as As(III) species (15–85%) in the oxic surface and ground water samples, which is not common. Time-series based sediment incubations were set up in the laboratory with contaminated sediments to study the microbial processes involved in transformation and remobilization of As across the sediment–water interface. The microcosm experiments indicate that microorganisms are capable of surviving in As-rich sediments and reduce As(V) to As(III). A decrease in total As concentration in sediments is coupled to an increase in As(III) concentration in the aqueous media. In contrast, the controls (treated with HgCl₂ and formaldehyde) did not show growth, and As(V) concentrations increased steadily in the sediments and aqueous medium. The results imply that active metabolism is necessary for As(V) reduction. These microorganisms possess reduction mechanisms that are not necessarily coupled to respiration, but most likely impart resistance to As toxicity.     

A natural analogue of high pH cement pore waters from the Maqarin area of northern Jordan. I: introduction to the site

The highly alkaline springs of the Maqarin area of northern Jordan are currently under examination as part of an international project testing the models used to analyse the safety of repositories for low and intermediate level radioactive waste (L/ILW). The Maqarin area contains a rock-groundwater system which is an ideal natural analogue of a concrete-filled L/ILW repository emplaced in a sedimentary host rock. The high pH (12.5) groundwaters at this site are the product of interaction with naturally occurring cement minerals and not of the alteration of ultramafic minerals. Stable isotope data for the hyperalkaline groundwaters lie below both the local meteoric water line and the eastern Mediterranean water line. At least part of the shift appears to be the result of groundwater interaction with the cement minerals. This paper introduces the site of the natural analogue study and, in presenting novel data on the chemistry and stable isotopic signature of the groundwater, provides background information which is used in a companion paper (Alexander et al., 1992) on testing the predictive capabilities of geochemical thermodynamic codes (and their associated databases) which will be utilised as part of the safety assessment of a L/ILW repository.     

Cold seeps in Monterey Bay, California: Geochemistry of pore waters and relationship to benthic foraminiferal calcite

An extensive geochemical and biogeochemical examination of CH₄ seeps in the Clam Flats area of Monterey Bay provides insight into the character of relationships between seep geochemistry and benthic foraminiferal geochemistry. The area is characterized by sulfide-rich fluids. Sulfide increases are associated with large increases in alkalinity, as well as small decreases in dissolved Ca and Mg. In addition, only small increases in NH₄ are observed, but values of δ¹³C of dissolved inorganic C are as low as −60‰ at shallow depths (<3 cm). These observations indicate that all these processes are related to the bacterial oxidation of CH₄, which is transported upward by slow seepage of pore fluids. The geochemistry of the pore fluids should be relevant to the geochemistry of the carbonate tests of living and dead foraminifera. However, a profound disequilibrium of approximately an order of magnitude occurs between the δ¹³C values of stained (cytoplasm-containing) foraminiferal carbonate and the C isotope values of ambient pore water dissolved inorganic C. Reasons are unclear for this isotopic disequilibrium, but have important implications for interpretations of foraminiferal carbonate as a paleoenvironmental proxy. Much fine scale work is needed to fully understand the relationships between the biogeochemistry of benthic foraminifera and the geochemistry of the pore waters where they live.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Control of As and Ni releases from a uranium mill tailings neutralization circuit: Solution chemistry, mineralogy and geochemical modeling of laboratory study results

Processing U ores in the JEB Mill of the McClean Lake Operation in northern Saskatchewan produces spent leaching solutions (raffinates) with pH  1.5, and As and Ni concentrations up to 6800 and 5200 mg L⁻¹, respectively. Bench-scale neutralization experiments (pH 2–8) were performed to help optimize the design of mill processes for reducing As and Ni concentrations in tailings and raffinates to 1 mg L⁻¹ prior to their disposal. Precipitate mineralogy determined by chemical analysis, XRD, SEM, EM, XM and EXAFS methods, included gypsum (the dominant precipitate), poorly crystalline scorodite (precipitated esp. from pH 2–4), annabergite, hydrobasaluminite, ferrihydrite, green rust II and theophrastite. The As was mostly in scorodite with smaller amounts in annabergite and trace As adsorbed and/or co-precipitated, probably by ferrihydrite. Geochemical modeling indicated that above pH 2, the ion activity product (IAP) of scorodite lies between the solubility products of amorphous and crystalline phases (log K_sp = −23.0 and −25.83, respectively). The IAP decreases with increasing pH, suggesting that the crystallinity of the scorodite increases with pH. Forward geochemical models support the assumption that during neutralization, particles of added base produce sharp local pH gradients and disequilibrium with bulk solutions, facilitating annabergite and theophrastite precipitation.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Pore waters extracted from compacted bentonite subjected to simultaneous heating and hydration

A compacted clay block of montmorillonite clay has been simultaneously subjected to heating and hydration by parallel and opposite fronts, in order to determine the physico-chemical effects of the thermohydraulic process on the clay and on its pore water.The pore waters of the clay have been extracted at ambient temperature after the thermal-hydration treatment by a compaction at high pressure (60 MPa) technique. They have been analyzed, and the chemistry has been evaluated by using the speciation program EQ3NR. The movement of salts towards hot areas has been observed as a result of the thermo-hydraulic gradients, but it is conditioned by anionic retention processes, which mainly affect the mobility of SO₄²⁻ anions. The distributrion of the exchangeable cations is modified by the thermal gradient.     

Form and distribution of gold mobilized into surface waters and sediments from a gossan tailings pile,Murray Brook massive sulphide deposit,New Brunswick,Canada

Stream waters and sediments draining a gossan tailings pile at the Murray Brook massive sulphide deposit were collected to investigate Au mobility. Weathering of the massive sulphides at Murray Brook during the Late Tertiary period resulted in the concentration of Au in the gossan cap overlying the supergene Cu and unoxidized massive sulphide zones of the deposit. The gossan was mined between 1989 and 1992, and Au and Ag were extracted using a cyanide vat leach process. Although stream sediments prior to mining had Au<5 ppb (the detection limit), sediments collected in 1997 had Au contents ranging up to 256 ppm with values up to 6 ppm more than 3 km downstream from the deposit. Dissolved Au contents were similarly anomalous, up to 19 μg/L and in excess of 3 μg/L 3 km downstream. The elevated Au contents in the waters and sediments are interpreted to reflect complexation of Au (as Au(CN)₂⁻) by cyanide hosted within the gossan tailings pile. Precipitation recharges through the tailings pile with groundwater flow exiting to Gossan Creek. Degradation of cyanide along the flow path and within Gossan Creek allows colloidal Au to form via reduction of Au(I) by Fe²⁺, consistent with SEM observations of Au as <1 μm subrounded particles. In the surface waters, the majority of the Au must be in a form <0.45 μm in size to account for the similarity in Au contents between the <0.45 μm and unfiltered samples. The very elevated stream sediment Au values close to the headwaters of Gossan Creek near the tailings indicate that upon exiting to the surface environment, Au(CN)₂⁻ complexes are rapidly destroyed and Au removed from solution. However, the high Au_{<0.004 μm}/Au_total in the headwaters and the extended Au dispersion in Gossan Creek waters and sediments suggest that Au(CN)₂⁻ complexes persist for the full length of Gossan Creek. The decrease in aqueous Au which is less than 0.004 μm indicates that Au is converted from a complexed form to a colloidal form with increasing distance downstream, consistent with dissolved NO₃⁻ contents which decrease from 5210 μg/L near the headwaters to 1350 μg/L at the lower end of the stream.     

A simple method for the determination of dissolved gases in natural waters. An application to thermal waters from Vulcano Island.

A new method for the determination of dissolved gas species in natural waters is presented. The method is suitable for field operations and ensures the preservation of the sample until analysis in the laboratory. This method is based on the equilibrium partition of gases between a liquid and a gaseous phase after the introduction of host gas. The host gas used depends on the gas species to be determined and on the technical features of the gas chromatograph. In this work pure Ar has been used. After shaking the sample for 5 min, a portion of gas was taken for gas chromatography analysis. From the concentration of gases in the gaseous phase and taking into account the partitioning coefficients of the various species, it is possible to derive the quantity of dissolved gases per litre of water and the partial pressures of the various gas species in equilibrium with water. This method has been applied to several samples of thermal water from Vulcano island. Helium and CO₂ partial pressures of analysed samples were appreciably higher than those typical of waters in equilibrium with the atmosphere, thus indicating processes of interaction between the volcanic gases and groundwaters.