Applied Geochemistry (v.23, #9)

Groundwater from the Costa de Hermosillo aquifer has been used extensively for irrigation over the past 60 a in the Sonora region of northwestern Mexico resulting in salinization of fresh groundwater resources. Salinization of groundwater is most pronounced on the western/coastal side of the aquifer, with an aerial extent of 26.7 km2, where maximum values are reported for conductivity (31 mS/cm) and Cl concentrations (16,271 mg/L). Salinization is likely to increase if groundwater pumping continues at levels comparable to the present time. Upward incursion of marine water into the aquifer is inferred from δ2H (−7.2 ‰) and δ18O (+1.6‰) compositions of groundwater samples with the highest conductivity. Compared to modern seawater in the Gulf of California, ratios of SO4/Cl and Cl/Br are small (0.01 and 33, respectively) and the S isotopic composition of SO 4 2 - is high (+32.7%) in the most saline portions of the Costa de Hermosillo. This saline groundwater is inferred to result from an earlier phase of dissimilatory bacterial SO 4 2 - reduction coupled to decomposition of organic matter in marine blue clays deposited during the Miocene/Pliocene transgression. The isotopic composition of present-day surface discharge from agricultural fields is substantially enriched in 32S due to widespread application of (NH4)2SO4 fertilizers and potential mobilization of S from mineral resources. Surface water discharging from irrigated fields has δ34S values ranging from −2.1 to 3.3 ‰ which are distinctly different from groundwater and surface water in adjacent non-agricultural areas with δ34S values ranging from 5.2 to 13.5 ‰. Prolonged irrigation pumping that promotes the incursion of air to the subsurface could enhance the weathering of S-bearing minerals such as magmatic sulfides, producing 32S-enriched SO 4 2 - .

Single-pass flow-through tests were conducted to determine the pH (7–12) and temperature (23–90 °C) dependence of kinetic rate law parameters; k o, η, and E a, for the dissolution of glass in aqueous solution. Experiments were performed with three prototypic nuclear waste glasses that span a wide compositional range, which covers, with high probability, the expected processing composition range for candidate immobilized low-activity waste (ILAW) glasses. Comparison of the B to Na release rates for one glass was incongruent at 23 and 40 °C, and pH (23 °C) = 7.0 and 8.0, suggesting two distinct mechanisms are responsible for the Na+ release, namely Na+–H+ ion-exchange and matrix dissolution. Matrix dissolution became the dominant dissolution mechanism for all glasses at the forward rate and pH values greater than 9.0 as evident by the congruent release of Al, B, Na and Si to solution. By combining the results collected for each ILAW glass at pH values greater than 9.0, pH and temperature-dependent rate law parameters were determined for Al, B, Na and Si release. A comparison of the pH power-law coefficient for Al, B, Na and Si at each temperature suggest that η does not depend on temperature within experimental error and suggests the release of these elements into solution is controlled by the same dissolution mechanism at the forward rate of reaction. The activation energies (E a), based on B release, range from 52 ± 4 to 56 ± 6 kJ/mol which suggest that dissolution is a surface-controlled reaction mechanism. The data presented in this manuscript suggest that for these three ILAW glasses the chemical durability for each glass is similar under these test conditions. A lack of compositional dependence on the forward dissolution rate is observed even though there is as much as a 39 kJ/mol difference in the free energy of hydration (ΔG hyd) among the borosilicate waste glasses tested. This similarity in the forward dissolution rate despite the large ΔG hyd difference is almost certainly because these glasses have similar, if not identical, polymerization states. This is evident from the almost identical 29Si chemical shifts for each of these glasses. The polymerization state is an indication of the number of framework SiO4 linkages contained in the glass network. In general, the greater the number of framework SiO4 linkages the more durable the glass. Finally, in agreement with previous work, these results suggest breakage of the Si–O bond is the rate-determining dissolution mechanism under alkaline conditions [pH (23 °C) > 9.0] far from saturation with respect to an alteration phase or phases.

Adsorption of metals and protons on Gloeocapsa sp. cyanobacteria: A surface speciation approach by O.S. Pokrovsky; R.E. Martinez; S.V. Golubev; E.I. Kompantseva; L.S. Shirokova (2574-2588).
The purpose of the present work is to extend our knowledge of metal–cyanobacteria interactions and to contribute to the database on adsorption parameters of aquatic microorganisms with respect to metal pollutants. To this end, the surface properties of the cyanobacteria (Gloeocapsa sp. f-6gl) were studied using potentiometric acid–base titration methods and ATR-FTIR (attenuated total reflection infrared) spectroscopy. The electrophoretic mobility of viable cells was measured as a function of pH and ionic strength (0.01 and 0.1 M). Surface titrations at 0.01–1.0 M NaCl were performed using limited residence time reactors (discontinuous titration) with analysis of Ca, Mg and dissolved organic C for each titration point in order to account for alkali-earth metal–proton exchange and cell degradation, respectively. Results demonstrate that the cell-wall bound Ca and Mg from the culture media contribute to the total proton uptake via surface ion-exchange reactions. This has been explicitly taken into account for net proton balance calculations. Adsorption of Zn, Cd, Pb and Cu was studied at 25 °C in 0.01 M NaNO3 as a function of pH and metal concentration. The proportion of adsorbed metal increases as a function of culture age with cells of 44 days old having the largest adsorption capacities. A competitive Langmuir sorption isotherm in conjunction with a linear programming method (LPM) was used to fit experimental data and assess the number of surface sites and adsorption reaction constants involved in the binding of metals to the cyanobacteria surface. These observations allowed the determination of the identity and concentration of the major surface functional groups (carboxylate, amine, phosphoryl/phosphodiester and hydroxyl) responsible for the amphoteric behavior of cyanobacterial cell surfaces in aqueous solutions and for metal adsorption. Results of this work should allow better optimizing of metal bioremediation/biosequestration processes as they help to define the most efficient range of pH, cell biomass and duration of exposure necessary for controlled metal adsorption on cyanobacteria cultures. It follows from comparison of adsorption model parameters between different bacteria that technological application of cyanobacteria in wastewater bioremediation can be as efficient as other biological sorbents.

Identifying “free” and “bound” lipid fractions in stalagmite samples: An example from Heshang Cave, Southern China by Xianyu Huang; Jingwei Cui; Yang Pu; Junhua Huang; Alison J. Blyth (2589-2595).
Stalagmites are good archives for paleoecological change, as they are easy to date, and contain multiple environmental proxy records, including climatic records from oxygen isotopes. Lipid biomarkers preserved within stalagmites have recently been used to investigate changes in the overlying soil and vegetation. However, the understanding of lipid records from stalagmites is still at an early stage, and is hindered by the low abundances of lipids preserved and the complexity of the organic matter signal. Here the first results of a sequential extraction procedure are presented, that enables examination of the distribution patterns of “free” (solvent extraction) and “bound” (including physically bound within the calcite matrix and chemically bound to macromolecules) lipids in a stalagmite from southern China. In both groups the dominant compounds are saturated fatty acids, which are an order of magnitude more abundant in the “bound” phase. n-alkanes and n-alcohols chiefly appear in the “free” lipids. In contrast, 3-hydroxy acids are predominantly released under strong acid reflux conditions, suggesting a principal input from bacterial membrane compounds. A direct comparison between the present results and the published data from an Ethiopian stalagmite shows significant differences in the lipid signals from separate sites, with a stronger microbial signal in the Chinese sample. This preliminary investigation of lipid distributions in different modes highlights the importance of microbial geochemical processes in karst systems and supports the use of stalagmites in paleoecological reconstruction.

Regulatory authorities require estimates of ambient background concentrations (ABCs) of potentially harmful elements (PHEs) in topsoil; such data are currently not available in many countries. High resolution soil geochemical data exist for only part of England and Wales, whilst stream sediment data cover the entire landscape. A novel methodology is presented for estimating soil equivalent ABCs for PHEs from high-resolution (HR) stream sediment geochemical data grouped by common parent materials (PM), using arsenic (As) as an example. Geometric mean (GM) values for local PM groups are used to investigate different approaches for transforming sediment to soil equivalent concentrations. Holdout validation is used to assess: (i) the optimum number of samples for calculating local GM values, and (ii) the optimum scale at which to group data when using linear regression analysis to estimate GM soil ABCs from local sediment geochemical values. Holdout validation showed that the smallest differences were generally observed when five observations were used to calculate the GM and that these should be grouped over the smallest possible area in order to encompass soils over PMs with elevated GM As concentrations. Geometric mean ABCs are estimated and mapped for As in mineral soil across all of England and Wales within delineations of PM polygons. Errors for the estimation of soil equivalent GM As ABCs based on sediment data for an independent validation set were of a similar magnitude to those from holdout validation applied to the original data suggesting the approach is robust. The estimates of soil equivalent ABCs suggest that As exceeds the regulatory threshold used in risk assessments for residential land use (20 mg kg−1) across 16% of the landscape of England and Wales. The applicability of the method for cognate landscapes, and potential refinements is discussed.

The molecular character of organic matter (OM) present in Triassic clays of the Upper Silesia Basin and NW border of the Holy Cross Mountains was determined using GC–MS analysis. Oxidation processes were the major cause of the main changes of extractable OM molecular composition during sedimentation and early diagenesis of the Triassic clays. They resulted in a very significant decrease in the OM content of the clays and transformation of n-alkanes, triterpanes and steranes. Despite the changes in biomarker composition resulting from the disappearance of unsaturated and ββ hopanes and dominance of αβ and βα hopanes as well as preponderance of αββ over ααα steranes, the aromatic ketones were identified. Such PACs as benzophenone, fluorenone, cyclopenta(def)phenanthrenone, antracenone and benzanthrone were among the compounds identified in the red clays. These commonly originate during oxidation of sedimentary organic matter. Moreover, the aromatic fraction is characterized by the presence of phenyl derivatives (phenylnaphthalenes, terphenyls, phenyldibenzofurans and phenylphenanthrenes) that are also products of the abiotic oxidation of organic matter. Periods of terrestrial sedimentation have been interrupted by long phases of OM weathering and oxidation during arid conditions, and OM might only have survived without significant oxidation changes when the sedimentation was fast and/or long-lasting.

Metal corrosion and argillite transformation at the water-saturated, high-temperature iron–clay interface: A microscopic-scale study by Michel L. Schlegel; Christian Bataillon; Keltoum Benhamida; Cécile Blanc; Denis Menut; Jean-Luc Lacour (2619-2633).
In this study, microscopic and spectroscopic techniques (scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman microspectroscopy, micro X-ray fluorescence spectroscopy, micro X-ray fine structure adsorption spectroscopy, and micro laser-induced breakdown spectroscopy) were combined to decipher the chemical and mineralogical properties of a saturated Fe–clay interface reacted at 90 °C and 50 bar for 8 months. The results collectively confirm the presence of a corrosion layer and a clay transformation layer. The corrosion layer is made of a magnetite-containing internal sublayer and a Fe-phyllosilicate external sublayer enriched in Na, with traces of goethite presumably resulting from sample reaction with air. The clay transformation layer is made of predominantly Ca-rich siderite (FeCO3). It is depleted in Al and K, suggesting dissolution of rock-forming minerals. The corroded thickness determined from the amount of Fe in corrosion and transformation layers and assuming zero porosity equals 19 ± 9 μm. These data indicate that the interfacial clay was transformed by dissolution of calcite and clay minerals and precipitation of siderite close to the original surface. Silica released upon clay dissolution diffused into the corrosion layer and coprecipitated with oxidized Fe to form Fe-phyllosilicate.

Samples of groundwater, spring water and stream water contaminated by acid mine drainage (AMD), and uncontaminated stream water were collected and allowed to evolve in contact with air in the laboratory for 15–88 days. The objective of this study was to (1) document temporal changes in dissolved inorganic C (DIC) concentrations and stable isotopic composition (δ 13CDIC) and (2) to determine the reaction mechanism and resulting isotopic fractionation (13C/12C) accompanying the chemical evolution of AMD. The contaminated spring and stream samples and one groundwater sample (with no HCO 3 - ) showed temporal decreases in pH, Fe2+, alkalinity, and DIC, and enrichment in δ 13CDIC. One contaminated groundwater sample (with HCO 3 - between 529 and 630 mg/L) showed a temporal increase in pH despite observed decreases in Fe2+, alkalinity and DIC, and enrichment in δ 13CDIC. The uncontaminated stream samples showed a continuous temporal increase in pH, relatively constant alkalinity and DIC, and enrichment in δ 13CDIC. The results suggest that proton production related to Fe2+ transformation is the driving force for DIC loss in AMD-contaminated samples, and that DIC loss can be described by first order kinetics. The C isotope enrichment rates associated with DIC loss in the contaminated samples varied between 1.0‰ and 1.8‰ for stream water, 2.1‰ and 2.6‰ for the spring, 1.0‰ and 1.2‰ for groundwater with no HCO 3 - , and 7.6‰ and 9.3‰ for groundwater with high HCO 3 - . Variations in 13C enrichment in the contaminated samples are attributed to differences in the initial Fe 2 + : HCO 3 - ratio. The effect of proton production on 13C enrichment in the AMD-contaminated samples was modeled as a Rayleigh-type distillation, whereby isotope fractionation was constant and occurred in an “equilibrium closed system”. In the uncontaminated stream samples, C exchange between DIC and atmospheric CO2 resulted in an overall enrichment in δ 13CDIC of ∼6‰. It is concluded that C isotope enrichment induced by the chemical evolution of AMD in contaminated streams should range from 1.0‰ to 3.0‰ in the absence of in-stream processes that may affect DIC.

Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model by Wooyong Um; R. Jeffrey Serne; Christopher F. Brown; Kenton A. Rod (2649-2657).
Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent–sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO_UO2HCO3 and SO_UO2OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions.

Application of heavy stable isotopes in forensic isotope geochemistry: A review by Jugdeep Aggarwal; Judith Habicht-Mauche; Chelsey Juarez (2658-2666).
Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers.

A new method for the speciation of Fe and Mn at mineral surfaces is proposed using X-ray absorption fine structure in conversion electron yield mode (CEY-XAFS). This method generally reflects information on the species at the sub-μm scale from the particle surface due to the limited escape depth of the inelastic Auger electron. The surface sensitivity of this method was assessed by experiments on two samples of granite showing different degrees of weathering. The XANES spectra of the Fe-K and Mn-K edge clearly gave different information for CEY and fluorescence (FL) modes. These XANES spectra of Fe and Mn show a good fit upon application of least-squares fitting using ferrihydrite/MnO2 and biotite as the end members. The XANES spectra collected by CEY mode provided more selective information on the secondary phases which are probably present at the mineral surfaces. In particular, CEY-XANES spectra of Mn indicated the presence of Mn oxide in unweathered granite despite a very small contribution of Mn oxide being indicated by FL-XANES and selective chemical-extraction analyses. Manganese oxide could not be detected by micro-beam XANES (beam size: 5 × 5 μm2) in unweathered granite, suggesting that Mn oxide thinly and ubiquitously coats mineral surface at a sub-μm scale. This information is important, since Mn oxide can be the host for various trace elements. CEY-XAFS can prove to be a powerful tool as a highly sensitive surface speciation method. Combination of CEY and FL-XAFS will help identify minor phases that form at mineral surfaces, but identification of Fe and Mn oxides at mineral surfaces is critical to understand the migration of trace elements in water-rock interaction.

Radon transfer from groundwater used in showers to indoor air by David S. Vinson; Ted R. Campbell; Avner Vengosh (2676-2685).
Estimation of Rn transfer from water to indoor air based on multi-day measurements may underestimate alpha exposure that occurs at short time scales in confined spaces, such as from showering, in houses with high Rn activities in the water supply. In order to examine one such incremental increase in exposure, variations in Rn in water and indoor air in 18 houses with private wells in western North Carolina (USA) were investigated. Radon in well water ranged from 158 to 811 Bq L−1 (median 239 Bq L−1). After 20-min showers in bathrooms with closed doors, peak Rn in air increases (above background) ranged from 71 to 4420 Bq m−3 (median 1170 Bq m−3). Calculated transfer coefficients at the scale of a 40-min closed bathroom (20-min shower plus 20 min post-shower) are described by a lognormal distribution whose geometric mean exceeds the widely-used ∼10−4 whole-house transfer coefficient by about one order of magnitude. As short-lived decay products grow from shower-derived Rn, short-term alpha energy exposure occurs in bathrooms in addition to the exposure caused by Rn mixed throughout the volume of the house. Due to the increasing ratio of Rn decay products to Rn, alpha energy exposure is greatest several minutes after the shower is turned off. For a 7.2-min shower with 10 min of additional exposure before opening the door, a geometric mean 5.6% increase in exposure over the ∼10−4 whole-house transfer coefficient derived from longer measurement periods was estimated. In addition to Rn activity in water, short-term shower exposure to Rn progeny depends on exposure time, ventilation, attachment and deposition, among other variable factors that characterize individual houses and residents.

Compartmentalization of physical and chemical properties in hard-rock aquifers deduced from chemical and groundwater age analyses by Virginie Ayraud; Luc Aquilina; Thierry Labasque; Hélène Pauwels; Jérôme Molenat; Anne-Catherine Pierson-Wickmann; Véronique Durand; Olivier Bour; Corinne Tarits; Pierre Le Corre; Elise Fourre; Philippe Merot; Philippe Davy (2686-2707).
Using groundwater age determination done through CFC analysis and geochemical data obtained from seven sites in Brittany (France), a hydrogeochemical model for hard-rock aquifers is presented. According to the geological structure, three zones can be defined: the weathered layer, about 30 m thick; the weathered-fissured layer (fractured rock with a high density of fissures induced by weathering), which represents a transition zone between the weathered zone and the lower fractured zone; and the unweathered part of the aquifer. (1) The weathered layer (alterites) is often considered as a porous medium and is the only part frequently used in hard-rock aquifers. Recent apparent ages (0–10 a) are observed in the groundwater fluctuation zone in a thin layer, which is from 1–2 m-thick in the lower parts and 10–15 m-thick in the upper parts of the catchments. Below this thin layer, the groundwater apparent age is high (between 10 and 25 a) and is unexpectedly homogeneous at the regional scale. This groundwater apparent age contrast, which also corresponds to a Cl concentration contrast, is attributed to rapid lateral transfers in the fluctuation zone which limit water transfer to the underlying weathered zone. Groundwater chemistry is characterized by NO 3 - and Cl concentrations related to land uses (high in agricultural areas, low in preserved ones). (2) At the interface between the weathered and the weathered-fissured layers a strong biogeochemical reactivity is observed. Autotrophic denitrification is enhanced by a higher availability of sulfides. (3) Under this interface, in the weathered-fissured layer and the underlying fractured deep part of the aquifer, groundwater apparent age is clearly correlated to depth. The vertical groundwater velocity is estimated to be 3 m/a, whatever be the site, which seems to indicate a regional topographic control on groundwater circulation in the deep part of the aquifer. In this deep part, groundwater chemistry is modified by water–rock interaction processes as indicated by Ca and Na concentrations, and a slight sea-water contribution (from 0.1% to 0.65%) in the sites close to the seacoast. One site inland shows a saline and old end-member. The global hydrogeochemical scheme is modified when the aquifer is pumped at a high rate in the fissured-weathered layer and/or the fractured layer. The increase in water velocity leads to a homogeneous groundwater apparent age, whatever be the depth in the weathered-fissured and fractured layers.

Tissue N contents and δ 15N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ 15N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ 15N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH3 released from excretory wastes and sewage, while the less negative δ 15N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH3. With more negative values in the urban area than in the rural area, the pattern of moss δ 15N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NO x –N. Therefore, NH x –N is the dominant N form deposited in the Guiyang area, which is supported by higher NH x –N than NO x –N in local atmospheric deposition. From the data showing that moss is responding to NH x –N/NO x –N in deposition it can be further demonstrated that the variation of moss δ 15N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NH x /agriculture-NH x than the ratio of NH x –N/NO x –N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang.

Phosphorus retention by phlogopite-rich mine tailings by Salla H. Hartikainen; H. Helinä Hartikainen (2716-2723).
Sewage water rich in P poses a threat to natural water systems. In households that are not connected to a sewer network, an easily maintained purification technique is needed to remove P from domestic waste waters. In the present study, the P retention properties of phlogopite-rich mine tailings were studied to determine whether the untapped tailings can be utilised in wastewater treatment for this purpose. On the basis of its chemical and mineralogical properties, this material, produced in the enrichment process of apatite ore in Siilinjärvi, Finland, can be assumed to act as a P sorbent. The P retention capacity and the P sorption mechanisms of phlogopite-rich tailings were studied with desorption–sorption isotherms and various chemical extractions. The impact of the artificial weathering of the material as well as the reaction time and particle size on P retention were also investigated. The fluctuating shape of the isotherm determined for the untreated material suggests the operation of several sorption mechanisms. The results imply that phlogopite-rich tailings retain P efficiently through specific sorption by amorphous Al and Fe oxides and possibly also by calcite present as an accessory mineral. Acidification of the material, extended reaction time and decrease in particle-size markedly increased the P retention.

Electrochemical study of hydrothermal and sedimentary pyrite dissolution by Ran Liu; Amy L. Wolfe; David A. Dzombak; Colin P. Horwitz; Brian W. Stewart; Rosemary C. Capo (2724-2734).
The dissolution of pyrite is of interest in the formation of acid mine drainage and is a complex electrochemical process. Being able to measure the rate of dissolution of particular pyrite samples under particular conditions is important for describing and predicting rates of AMD generation. Electrochemical techniques offer the promise of performing such measurements rapidly and with small samples. The oxidation of pyrite and the reduction of Fe3+ ions and/or O2 half reactions involved in the pyrite dissolution process were investigated by cyclic voltammetry and steady-state voltammetry using three pyrite materials formed in both sedimentary and hydrothermal environments. For each sample, two kinds of pyrite working electrodes (conventional constructed compact solid electrode, and carbon paste electrode constructed from fine-grained pyrite particles) were employed. Results indicated that for both the hydrothermal and sedimentary pyrite samples the oxidation and reduction half reactions involved in dissolution were governed by charge transfer processes, suggesting that hydrothermal and sedimentary pyrites obey the same dissolution mechanism despite their different formation mechanisms. In addition, the results showed that it is feasible to use a C paste electrode constructed from fine-grained or powdered pyrite to study the pyrite dissolution process electrochemically and to derive approximate rate expressions from the electrochemical data.

Geochemical effects of CO2 sequestration in sandstones under simulated in situ conditions of deep saline aquifers by M. Wigand; J.W. Carey; H. Schütt; E. Spangenberg; J. Erzinger (2735-2745).
The geochemical effects of brine and supercritical CO2 (SCCO2) on reservoir rocks from deep (1500–2000 m) saline aquifers were examined via experimental simulation at in situ conditions. Dry sandstone samples were mounted in a triaxial cell and autoclave system, evacuated, and saturated with 1 M NaCl solution. The brine-rock system was allowed to react at 30 MPa confining pressure, 15 MPa pore fluid pressure, and 60 °C while SCCO2 was injected at a pressure gradient of 1–2 MPa. The experiment was conducted for a period of 1496 h, during which fluids were periodically sampled and analyzed. The pH measured in partially degassed fluid samples at 25 °C decreased from a starting value of 7.0–4.3 (9 days) and finally 5.1 after saturation with SCCO2.Fluid analyses indicate that most of the major (e.g. Ca, Mg, Fe, Mn) and trace elements (e.g. Sr, Ba, Pb) of the sandstone increase in concentration during the reaction with brine and SCCO2. These results are supported by scanning electron microscopy which indicates dissolution of dolomite cement, K-feldspar, and albite. In addition to dissolution reactions the formation of montmorillonite was observed. By adjusting surface area and reaction rates of dissolution and precipitation, geochemical modeling of the experiments could reproduce long-term trends in solution chemistry and indicated limited rates of dissolution as the system remained strongly undersaturated with most minerals, including carbonates. The geochemical models could not account for decreases in concentration of some elements, changes in solution composition resulting from changes in imposed pressure gradient, and the observed Ca/Mg and Si/Al ratios in solution.

Anion selectivity of organobentonites by Julia Behnsen; Beate Riebe (2746-2752).
The selectivity of organoclays for different anions is not well understood. It is of particular importance when potentially hazardous anions from nuclear waste matrixes or contaminated ground water are in competition with each other, or with other naturally occurring anions. This study focuses on the adsorption of I, ReO 4 - , NO 3 - , Br, SO 4 2 - - and SeO 3 2 - to hexadecylpyridinium-, hexadecyltrimethylammonium-, and benzethonium-modified bentonites (MX-80) and the understanding of the selectivity of the process. Adsorption experiments were carried out using the batch technique. Anion concentrations were determined by ion chromatography of the solution and X-ray fluorescence analysis of the organoclays. Anion adsorption to the studied organobentonites is mainly due to anion exchange with Cl. The results showed a clear selectivity of the organoclays, with the affinity sequence being ReO 4 -  > I  >  NO 3 -  > Br  > Cl  >  SO 4 2 - – >  SeO 3 2 - . This sequence corresponds to the sequence of increasing hydration energies of the anions, thus indicating that the observed selectivity of the organobentonites could be due to the process of minimisation of energy of the system.

Field validation of radon monitoring as a screening methodology for NAPL-contaminated sites by J.E. García-González; M.F. Ortega; E. Chacón; L.F. Mazadiego; E. De Miguel (2753-2758).
Screening methodologies aim at improving knowledge about subsurface contamination processes before expensive intrusive operations, i.e. drilling and core-sampling, well installation and development, sampling of groundwater and free-phase product, are implemented. Blind field tests carried out at a hydrocarbon storage and distribution center in NE Spain suggest that Rn monitoring can be effectively used to locate the boundaries of subsurface accumulations of NAPLs. Sixty seven measurements of Rn in soil air were performed with a SARAD RTM 2100 current-ionization alpha-particle spectrometer following a 10 m square grid. Reductions of 222Rn concentration above a pool of LNAPL due to the preferential partition of Rn into the organic phase were spatially analyzed and resolved to yield the surface contour of the NAPL source zone. This surface trace of the source zone agreed well with the extent and situation inferred from measurements of free-phase thickness taken at eight monitoring wells at the site. Moreover, the good repeatability (as measured by replicate measurements at the same sampling point) and spatial resolution of the technique suggest that the boundaries of the plume can be delineated at the sub-decametre level.

A simple and inexpensive chromium-reducible sulfur method for acid-sulfate soils by Edward D. Burton; Leigh A. Sullivan; Richard T. Bush; Scott G. Johnston; Annabelle F. Keene (2759-2766).
A new chromium-reducible sulfur (CRS) method suitable for the quantification of reduced inorganic S (RIS) in acid-sulfate soils is presented. The new method utilises the reduction of RIS by an acidic Cr(II) solution within a sealed reaction chamber and diffusion of the produced H2S(g) into an alkaline Zn solution. It offers rapid sample processing times, without the need for large volumes of high-purity N2(g) or for specialized, expensive glassware. Examination of pyrite-talc mixtures containing up to 11.8% pyrite, revealed that the method achieves 95–98% recovery of RIS. A comparison between CRS measured by the new diffusion-based method and that measured by a standard purge-and-trap method for 25 pyritic soil samples shows a very strong (r2  = 0.996) linear relationship with a slope of 0.995. The ability of the new diffusion-based CRS method to achieve accurate and precise quantification of RIS in acid-sulfate soils is demonstrated.

Sorption of Ni2+ on Na-rectorite studied by batch and spectroscopy methods by Xiaoli Tan; Changlun Chen; Shaoming Yu; Xiangke Wang (2767-2777).
Sorption of Ni2+ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni2+ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni2+ at low pH values, whereas no drastic effect of FA/HA on Ni2+ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni2+ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni2+ at different temperatures. The thermodynamic data (ΔH 0, ΔS 0, ΔG 0) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni2+ on rectorite was spontaneous and endothermic. The sorption and species of Ni2+ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni2+ mainly occurred on the surface and at the edge position of Na-rectorite.

The mechanism and kinetics of DTPA-promoted dissolution of barite by Christine V. Putnis; Magdalena Kowacz; Andrew Putnis (2778-2788).
The dissolution rate of natural barite, BaSO4, was measured in solutions of DTPA (diethylene triamine penta-acetic acid) to investigate the mechanism of ligand-promoted dissolution using a strong chelating agent. Experiments were carried out over a range of DTPA concentrations 0.5–0.0001 M solutions, at room temperature (22 °C), as well as a range of temperatures, 22–80 °C at 1 atm. The dissolution rate is inversely related to the DTPA concentration in solution. A more dilute DTPA solution is shown to be more efficient as a solvent in terms of the approach to the equilibrium saturation value for the dissolution of Ba2+. An analysis of the temperature dependence of the dissolution rate at high pH by the determination of activation energies indicates that the reaction is probably controlled by the pre-exponential term in the rate constant. This indicates that reaction frequency mostly controls differences in reactivity and suggests an explanation for the results in terms of stearic hindrance due to adsorbed DTPA molecules at the barite surface. The effect of DTPA on the solvation of the Ba2+ ion may also influence the dissolution rate.

Comment on “The biosphere: A homogeniser of Pb-isotope signals” by C. Reimann, B. Flem, A. Arnoldussen, P. Englmaier, T.E. Finne, F. Koller and Ø. Nordgulen by Gaël Le Roux; Jeroen E. Sonke; Christophe Cloquet; Dominique Aubert; François de Vleeschouwer (2789-2792).

Reply to the comment on “The biosphere: A homogenizer of Pb-isotope signals” by Gaël Le Roux, Jeroen Sonke, Christophe Cloquet, Dominique Aubert, and François de Vleeschouwer by Clemens Reimann; Belinda Flem; Arnold Arnoldussen; Peter Englmaier; Tor Erik Finne; Friedrich Koller; Øystein Nordgulen (2793-2798).