Natural arsenic contamination in waters from the Pesariis village,NE Italy

High arsenic (As) concentrations, >900 μg/L, were measured in Ca–Mg–SO₄ waters from springs and drainages in the village of Pesariis in the Carnic Alps (NE Italy). Oxidation of the outcropping arsenian marcasite ore deposits of the area is proposed as the mechanism for As release into oxygenated waters during runoff. Nevertheless, the limited extension of the ore deposit and the relatively low As content of the mineralization suggest that sulfide weathering might not be the only process responsible for the highest As concentration in groundwaters. An additional mechanism involves As adsorption onto ferric iron particulate during oxidation, the drawdown in reducing environment at depth during water infiltration, and the release of ferrous iron and sorbed arsenic to the water columns by reductive dissolution of hydrous ferric oxides (HFO). This yields the observed Fe–As correlation. Newly formed HFO precipitates when groundwaters discharge to aerated conditions, leading to the removal of As, which strongly partitions into the iron-rich sediments, adsorbed onto the surface of amorphous Fe₂O₃·xH₂O. The calculated and measured As concentration in sediments exceeds 10% by weight. Furthermore, geochemical and isotopic data indicate that the As-rich reservoir partly mixes with shallower aquifers, commonly tapped for drinking supply, representing a natural hazard for inhabitants.     

Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada

Several methods were evaluated and compared for the estimation of pyrite oxidation rates (POR) in waste rock at Mine Doyon, Quebec, Canada. Methods based on data collected in situ, such as the interpretation of temperature and oxygen concentration profiles (TOP) measured in the waste rock pile and pyrite mass balance (PMB) on solid phase samples were compared with the oxygen consumption measurements (OCM) in closed chamber in the laboratory. A 1-D analytical solution to a gas and heat transport equation used temperature and oxygen profiles (TOP) measured in the pile for the preliminary POR estimates at a site close to the slope of the pile (Site 6) and in the core of the pile (Site 7). Resulting POR values were 1.1 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1 for the slope site and the core site, respectively. Oxidation rates based on pyrite mass balance (PMB) calculations for solid samples were 2.21 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 2.03 × 10^− 9 mol(O₂) kg^− 1 s^− 1, respectively, for the same slope and core sites, but the difference between sites was within the error margin. The OCM measurements in the laboratory on fresh waste rock samples yielded higher POR values than field methods, with average oxidation rate of 6.7 × 10^− 8 mol(O₂) kg^− 1 s^− 1. However, the OCM results on weathered and decomposed material from the rock stockpile (average oxidation rate 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1) were consistent with results from the field-based estimates. When POR values based on fresh material are excluded, the remaining POR values for all methods range from 1.0 × 10^− 10 to 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1. The lowest estimated value (1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1) was based on TOP estimates in the interior of the pile where oxygen transport was limited by diffusion from the surface. These results suggest that small-scale OCM laboratory experiments may provide relatively representative values of POR in the zones of waste rock piles in which oxygen transport is not dominated by diffusion.     

Thiosulphate in surficial geothermal waters, North Island, New Zealand

Thiosulphate is present in hot springs, streams and thermal pools of the Taupo Volcanic Zone and Ngawha, New Zealand, at concentrations of 1.2 (±1.3) × 10⁻⁵ M to 7.05 (±0.12) × 10⁻⁴M. Formed as a metastable product of sulphide oxidation, thiosulphate is buffered in the presence of elemental S according to, . Unless all sulphide present has been bacterially oxidised to sulphate, a steady state concentration of thiosulphate is maintained. As a soft base thiosulphate is capable of complexing several transition metals. The thermodynamically predicted speciation of Ag in Champagne Pool, for example, indicates a Ag(S₂O₃)₂⁻³ activity similar to that of AgCl₂⁻ though less than that of Ag(HS)₂⁻.     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

Balance of S in a constructed wetland built to treat acid mine drainage, Idaho Springs, Colorado, U.S.A.

The wetland constructed at the Big Five Tunnel in Idaho Springs, Colorado was designed to remove, passively, heavy metals from acid mine drainage. In optimizing the design of such a wetland, an improved understanding of the chemical processes operating there was required, particularly SO₄²⁻ reduction and sulfide precipitation. For this purpose, field and laboratory data were collected to study the balance of S in the system. Field data collected included water analyses of the mine drainage and wetland effluents and measurements of H₂S gas emissions from the wetland. The concentration of sulfide in the wetland effluent ranged from 10⁻⁴ to 10⁻³ mol/l. The average rates of H₂S emission from the surface of the substrate were 150 nmol/cm²/d in the summer and 0.17 and 0.35 nmol/cm²/d in the winter. This maximum estimated loss of sulfide was not significant in reducing the amount of sulfide available for precipitation with metals. Sequential extraction experiments for S on wetland substrates showed that acid volatile sulfides (AVS) increased with time in the wetland substrate. A serum bottle experiment was conducted to study the S balance in the Big Five wetland by quantitatively measuring the amount of S in different phases as microbial SO₄²⁻ reduction progressed. The increase in AVS reasonably balanced the decrease in SO₄²⁻ concentration in the experiment, suggesting that the decrease in SO₄²⁻ concentration represented the amount of SO₄²⁻ reduced and that nearly all of the sulfide produced was precipitated as AVS. Sulfide precipitation was determined to be the primary metal removal process in the wetland system and amorphous FeS is the primary iron sulfide formed in the substrate.     

A method for determining both diffusion and sorption coefficients of rock medium within a few days by adopting a micro-reactor technique

Migration properties characterized by physico-chemical factors such as distribution coefficient (K_d) and diffusion coefficient (D_e) are of great concern in performance assessment of high-level radioactive waste disposal in a deep geologic environment. These coefficients are normally obtained with different sample geometries using conventional methods, i.e., crushed samples by the batch sorption method for K_d determination and block samples by the through-diffusion method for D_e. A size dependence on both K_d and D_e has been reported and an additional correction due to size difference is required to maintain consistency of the data set. A fast method was developed, hereafter referred to as the micro-channel method, to determine both the sorption coefficient (R_d) and D_e using non-crushed rock sample by adopting the micro-reactor technique. In this method, a radionuclide solution is injected into a micro-channel (20 mm length, 4 mm width, 160 μm depth), which is in contact with a plate-shaped rock sample. A part of the injected radionuclide can diffuse into the rock matrix and/or adsorb on the rock surface and this results in an inlet-outlet concentration difference. A breakthrough curve is easily obtained with a short observation period because the injection amount is extremely small and is comparable to that escaping by diffusion into the matrix. The breakthrough curve is analyzed by a two-dimensional diffusion-advection equation to evaluate R_d and D_e.In the present study, tritiated water (specific activity, 1.2 × 10⁴ Bq/mL; pH, 6) was injected into the micro-channel, and the breakthrough curve of ³H obtained. A series of experiments was carried out by changing the flow rate of the tritiated water (2.6 × 10⁻⁵–7.7 × 10⁻⁴ m/s). Rock samples were biotite granite from the Makabe area, Japan. The diffusion coefficient evaluated by least squares fitting to the numerical solutions (D_e = 1.5 × 10⁻¹¹ m²/s) agreed well with that obtained by the through-diffusion method (1.3 × 10⁻¹¹ m²/s). The breakthrough curve of Cs ([Cs] = 1.0 × 10⁻⁷ mol/L, pH 6) labeled with ¹³⁴Cs (specific activity adjusted to 4.9 × 10¹ Bq/mL) was also obtained. A nearly constant R_d value (5.5 × 10⁻² m³/kg) was found when the flow rate was less than 2.5 × 10⁻⁴ m/s. This implied that the sorption equilibrium is reached and K_d is obtained by the present method. This value was almost identical to K_d obtained by the batch sorption method (5.0 × 10⁻² m³/kg), but the testing period was very different; 1 day and 7 days, respectively. It is concluded that application of the micro-channel method provided advantages when compared with the conventional methods.     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

Simultaneous determination of sulfide, polysulfides and thiosulfate as an aid to ore exploration

The interaction of water and sulfide minerals yields dissolved species which can be utilized to trace back the presence of sulfide minerals and associated minerals. Computer modeling and laboratory and field results show that the most characteristic dissolved species are hydrogen sulfide (H₂S, HS⁻), polysulfide ions (S_n²⁻) and thiosulfate (S₂O₃²⁻), derived from the hydrolysis of sulfide minerals. Typical concentration ranges are: 10⁻⁵ – 10⁻⁷ mole/l for hydrogen sulfide, 10⁻⁶ – 10⁻⁹ mole/l for polysulfides and 10⁻⁵ – 10⁻⁸ mole/l for thiosulfate. The chemical reactivity of these species at contact with air makes them difficult to assess unless determined immediately after sampling.These sulfur species can be determined rapidly and accurately in field conditions by simultaneous titration with mercuric chloride employing an Ag/Ag₂S electrode for the determination of the end points.The application to ore exploration is exemplified by the results of the research on roll-type uranium deposits in the southwest of France.     

Iron speciation in interaction with organic matter: Modelling and experimental approach

The present study aims to model iron speciation when interacting with natural organic matter. Experimental data for iron speciation were achieved with insolubilized humic acid as an organic matter analogue for 1.8 × 10^− 3 M and 1.8 × 10^− 4 M iron concentrations and 2–5 pH range. Combining EPR spectroscopy and chemical analysis allowed us to fit NICA-Donnan model parameters for both organic complexation of iron and oxides precipitation.     

Magnetic anisotropy of calcite at room-temperature

The intrinsic room temperature magnetic properties of pure calcite were determined from a series of natural crystals, and they were found to be highly dependent on the chemical composition. In general, dia-, para-, and ferromagnetic components contribute to the magnetic susceptibility and the anisotropy of magnetic susceptibility (AMS). With a combination of magnetic measurements and chemical analysis these three contributions were determined and related to their mineralogical sources. The intrinsic diamagnetic susceptibility of pure calcite is − 4.46 ± 0.16 × 10^− 9 m³/kg (− 12.09 ± 0.5 × 10^− 6 SI) and the susceptibility difference is 4.06 ± 0.03 × 10^− 10 m³/kg (1.10 ± 0.01 × 10^− 6 SI). These diamagnetic properties are easily dominated by other components. The paramagnetic contribution is due to paramagnetic ions in the crystal lattice that substitute for calcium; these are mainly iron and manganese. The measured paramagnetic susceptibility agrees with the values calculated from the known concentration of paramagnetic ions in the crystals according to the Curie law of paramagnetic susceptibility. Substituted iron leads to an increase in the AMS. The paramagnetic susceptibility difference was found to correlate linearly with the iron content for concentrations between 500 and 10,000 ppm. An empirical relation was determined: (k₁ − k₃)^para (kg/m³) = Fe-content (ppm) × (1 ± 0.1) × 10^− 12 (kg/m³/ppm). The maximum susceptibility difference (Δk = k₁ − k₃) was found to be unaffected by iron contents below 100 ppm. Ferromagnetic contributions due to inclusions of ferromagnetic minerals can dominate the susceptibility. They were detected by acquisition of isothermal remanent magnetization (IRM) and their contribution to the AMS was separated by high-field measurements.     

CO2 and sulfuric acid controls of weathering and river water composition

Reactions of CO₂ with carbonate and silicate minerals in continental sediments and upper part of the crystalline crust produce HCO₃⁻ in river and ground waters. H₂SO₄ formed by the oxidation of pyrite and reacting with carbonates may produce CO₂ or HCO₃⁻. The ratio, ψ, of atmospheric or soil CO₂ consumed in weathering to HCO₃⁻ produced depends on the mix of CO₂ and H₂SO₄, and the proportions of the carbonates and silicates in the source rock. An average sediment has a CO₂ uptake potential of ψ = 0.61. The potential increases by inclusion of the crystalline crust in the weathering source rock. A mineral dissolution model for an average river gives ψ = 0.68 to 0.72 that is within the range of ψ = 0.63 to 0.75, reported by other investigators using other methods. These results translate into the CO₂ weathering flux of 20 to 24 × 10¹²mol/yr.     

Rates of Deglaciation during the Last Glaciation and Holocene in the Cordillera Vilcanota-Quelccaya Ice Cap Region, Southeastern Perú

Moraine chronology is combined with digital topography to model deglacial rates of paleoglacier volumes in both the Huancané Valley on the west side of the Quelccaya Ice Cap and the Upismayo Valley on the northwest side of the Cordillera Vilcanota. The fastest rates of deglaciation (39×10⁻⁵ to 114×10⁻⁵ km³ yr⁻¹ and 112×10⁻⁵ to 247×10⁻⁵ km³ yr⁻¹ for each valley, respectively) were calculated for the most recent paleoglaciers, corresponding to the last few centuries. These results are consistent with observations in the Venezuelan Andes showing high rates of deglaciation since the Little Ice Age. These rates also fall within the range of 20th century rates of deglaciation measured on the Quelccaya Ice Cap (29×10⁻⁵ to 220×10⁻⁵ km³ yr⁻¹, Brecher and Thompson, 1993; Thompson, 2000). These results imply that rates of deglaciation may fluctuate significantly over time and that high rates of deglaciation may not be exclusive to the late 20th century. Equilibrium line altitude (ELA) depressions for the ice volumes of the last glaciation modeled here were computed as 230 m for the Quelccaya Ice Cap and 170 m for the Cordillera Vilcanota. Maximum ELA depressions are lower than previously published: <500 m for the Cordillera Vilcanota and <400 m for the Quelccaya Ice Cap. These lower values could imply a topographic control over paleoglacier extent.     

Magnesium recovery from magnesite tailings by acid leaching and production of magnesium chloride hexahydrate from leaching solution by evaporation

The recovery of magnesium from magnesite tailings in aqueous hydrochloric acid solutions by acid leaching was studied in a batch reactor using hydrochloric acid solutions. Subsequent, production of magnesium chloride hexahydrate (MgCl₂.6H₂O) from leaching solution was also investigated. The effects of temperature, acid concentration, solid-to-liquid ratio, particle size and stirring speed on the leaching process were investigated. The pseudo-second-order reaction model seemed to be appropriate for the magnesium leaching. The activation energy of the leaching process was estimated to be 62.4 kJ mol^− 1. Finally, MgCl₂.6H₂O in a purity of 91% was produced by evaporation of leaching solution obtained at a temperature of 40 °C, 1.0 M acid, solid-to-liquid ratio of 10 g/L, particle size of 100 µm, stirring speed of 1250 rpm and leaching time of 60 min.     

High-field cantilever magnetometry as a tool for the determination of the magnetocrystalline anisotropy of single crystals

Cantilever torque magnetometry is utilized widely in physics and material science for the determination of magnetic properties of thin films and semiconductors. Here, we report on its first application in rock magnetism, namely the determination of K₁ and K₂ of single crystal octahedra of natural magnetite. The design of cantilever magnetometers allows optimization for the specific research question at hand. For the present study, a cantilever magnetometer was used that enables measurement of samples with a volume up to 64 mm³. It can be inserted into an electromagnet with a maximum field of 2 T. The cantilever spring is suitable for torque values ranging from 7.5 × 10^− 7 N·m to 5 × 10^− 6 N·m. The torque is detected capacitively; the measured capacitance is converted into torque by using a calibrated feedback coil. The magnetometer allows in-situ rotation of the sample in both directions and is, therefore, also suitable to analyze rotational hysteresis effects.The evaluation of the magnetite anisotropy constants involved Fourier analysis of the torque signal on the magnetite crystals' (001) and (110) planes. The absolute anisotropy constant has been computed using the extrapolation-to-infinite-field method. The value of K₁ at room temperature is determined at − 1.28 × 10⁴ [J m^− 3] (± 0.13, i.e. 10%) and that of K₂ at − 2.8 × 10³ [J m^− 3] (± 0.1, i.e. 2%). These values concur with earlier determinations that could not provide an instrumental error, in contrast with this work.The cantilever magnetometer performs four times faster than other torque magnetometers used for rock magnetic studies. This makes the instrument also suitable for magnetic fabric analysis.     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Some parameters of rockbursts derived from underground seismological measurements

A total of 240 three-component recordings from 80 rockbursts, which occurred in various coal mines in the Ostrava-Karviná Coal Basin (Czech Republic) between 1993 and 2005, was used to examine the decrease in maximum particle velocities u_i (m/s) with a scaled distance of d = d/√E (m/√J) or d/³√E (m/³√J) and the rate of predominant frequencies of body waves. The energetic span of rockbursts was within the interval of E = 6.2 × 10³ − 5.0 × 10⁸ J, while calculated hypocentral distances d of four underground seismic stations varied from 0.6 to 7 km. The slopes b of regression straight lines for the maximum particle velocities u_i (m/s) of P- and S-waves in the bilogarithmic scale correspond to the values of − 1.004, − 1.297, − 1.183 and − 1.527. The results of the linear regression are as follows:

P_max-waves u_i = 1.184 × 10^− 4 × d^− 1.004 (m/s) (square root scaling)

P_max-waves u_i = 3.055 × 10^− 3 × d^− 1.297 (m/s) (cube root scaling)

S_max-waves u_i = 5.280 × 10^− 4 × d^− 1.183 (m/s) (square root scaling)

S_max-waves u_i = 2.397 × 10^− 2 × d^− 1.527 (m/s) (cube root scaling).

The evaluation of the abovementioned dynamic parameters was based on seismic events data gathered in the database of the regional seismic array, and calculations were carried out either by using special programs applied as part of the automated data processing in the computation center, or by usual linear regression approaches. The aim of the detailed analysis of the maximum particle velocity and predominant frequencies was a) to set up input data from underground seismological observations for laboratory experiments dealing with the comparison of rock mass behaviour under modeled laboratory conditions simulating manifestation of rockbursts, and b) to incorporate particle velocity into the design of support in order to control damage and evident devastation of workings by rockbursts. The investigation of peak particle velocities was based on the recognition that they are the best criterion to assess vibration damage to surface structures and in mines.     

11 Å tobermorite from cement bypass dust and waste container glass: A feasibility study

A novel one-step hydrothermal synthesis of 11 Å tobermorite, a cation exchanger, from a unique combination of waste materials is reported. 11 Å tobermorite was prepared from stoicheiometric quantities of cement bypass dust and waste container glass at 100 °C in water. The product also comprised 10 wt.% calcite and trace quartz as residual parent phases from the cement bypass dust. In a batch sorption study at 20 °C the uptakes of Cd²⁺ and Pb²⁺ by the waste-derived tobermorite product were found to be 171 mg g^− 1 and 467 mg g^− 1, respectively, and in both cases the removal process could be described using a simple pseudo-second-order rate model (k₂ = 2.30 × 10^− 5 g mg^− 1 min^− 1 and 5.09 × 10^− 5 g mg^− 1 min^− 1, respectively). The sorption characteristics of the 11 Å tobermorite are compared with those of other waste-derived sorbents and potential applications are discussed.     

Kinetics of leaching of oxidized and reduced ilmenite in dilute hydrochloric acid solutions

Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]³. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)^2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.     

Correlation between dissolved He concentration and Cl in groundwater at Äspö, Sweden

Tunnel excavation at Äspö Island, Sweden, has caused severe groundwater disturbance, gradually extending deeper into the tunnel as present-day Baltic seawater intrudes through fractures connecting to the surface. However, the paleo-hydrogeochemical conditions have remained in the deep highly saline waters that have avoided mixing. A correlation has been observed between dissolved ⁴He concentration and Cl⁻ ion concentration, measured every two years from 1995 to 2001 at Äspö. Groundwater mixing conditions can be examined by the correlations between 1/Cl, ³⁶Cl/Cl, and ³H concentrations. Subsurface production is responsible for the majority of the ³⁶Cl and excess dissolved ⁴He of interstitial groundwater in fractures. The secular equilibrium ratio of ³⁶Cl/Cl in rock was theoretically estimated to be (5.05 ± 0.82) × 10⁻¹⁴ based on the neutron flux intensity, a value comparable to the measured ³⁶Cl/Cl ratio in rock and groundwater. The degassing crustal ⁴He flux was estimated to be 2.9 × 10⁻⁸  1.3 × 10⁻⁶ (ccSTP/cm²a) using the HTO diffusion coefficient for the Äspö diorite. The ⁴He accumulation rate ranges from 6.8 × 10⁻¹⁰ (for the in situ accumulation rate) to 7.0 × 10⁻⁹ (ccSTP/(g_water · a) considering both ⁴He in situ production and the degassing flux, assuming ⁴He is accumulated constantly in groundwater. By comparing the subsurface ³⁶Cl increase with ⁴He concentrations in groundwater, the ⁴He accumulation rate was determined from data for groundwater arriving at the secular equilibrium of ³⁶Cl/Cl. The ⁴He accumulation rate was found to be (1.83 ± 0.72) × 10⁻⁸ ccSTP/(g_water · a) without determining the magnitude of degassing ⁴He flux.     

Mineralogical and chemical characterization of wastes from the sulfuric acid industry in Falun, Sweden

 Wastes from the sulfuric acid industry are an environmental concern, because of the emission of acids, heavy metals, and sulfate to the environment. The wastes in Falun consist of 70–80% iron oxides, 10–20% silicates, less than 10% residual sulfides, and small amounts of secondary precipitates (iron hydroxides and Fe-, Zn- and Cu-sulfates). Due to the different behavior of sulfides during the roasting process, pyrrhotite and sphalerite are the major sulfide residues associated with lesser amounts of pyrite, chalcopyrite, and galena. The leachates are low-pH and enriched in Zn, Fe, and SO₄. The acid ferric Fe-rich solution promotes the dissolution of sphalerite and favors the formation of Pb-sulfate coatings on galena, providing an armoring effect which slows down the further oxidation of the galena. The residual sulfides are the potential source for acid generation and metal release. During the roasting process, iron oxides retain small amounts of sulfur and sphalerite forms alteration rims containing Zn-oxides. The iron oxides and Zn-oxides are important contributors to SO₄ and Zn in the leachates. The conditions in the waste deposit are favorable for the precipitation of Zn-, Cu-Fe-sulfates (e.g. gunningite, chalcanthite, Zn-copiapite). The highly soluble sulfates play important roles in controlling the concentrations of Cd, Cu, Fe, Zn, and SO₄ in the leachates. The mineralogical and geochemical data help to develop the reclamation strategies of this type of industrial wastes. Received: 26 April 1996 · Accepted: 27 July 1996