Applied Geochemistry (v.74, #C)

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ37Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ37Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ37Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ37Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ37Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ37Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ37Cl values in certain situations; such may explain halite deposits with bulk negative δ37Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.
Keywords: Chlorine isotopes; Halite; Groundwater; Playas; Diffusion; Halophytes;

The influence of hydroxybenzoic acids (HAHn), namely p-hydroxybenzoic acid (4-hydroxybenzoic acid, HPhbH) and protocatechuic acid (3,4-dihydroxybenzoic acid, HProtoH2), on the adsorption of europium(III) onto α,γ-Al2O3 particles is studied as a function of acid concentration. After measuring the adsorption edge of the Eu(III)/α,γ-Al2O3 binary system, and using the previously studied binary component system Eu(III)/HAHn—Moreau et al. (2015) Inorg. Chim. Acta 432, 81—, and HAHn/α,γ-Al2O3—Moreau et al. (2013) Colloids Surf. A 435, 97—, it is evidenced that HPhbH does not enhance Eu(III) adsorption onto α,γ-Al2O3 in the Eu(III)/HPhbH/α,γ-Al2O3 ternary system. Conversely, HProtoH2 enhances Eu(III) adsorption onto α,γ-Al2O3 in the Eu(III)/HProtoH2/α,γ-Al2O3 ternary system. Adsorption of the acids are also found higher in the Eu(III)/acid/α,γ-Al2O3 ternary systems as compared with the corresponding binary systems assessing synergetic effects. For high HPhbH concentrations, a ternary surface species involving ≡AlOH surface sites, Eu(III), and PhbH is evidenced by time-resolved luminescence spectroscopy (TRLS). However, in the Eu(III)/HProtoH2/α,γ-Al2O3 ternary system, chemical environment of Eu(III) is found to be very close to that in the Eu(III)/HProtoH2 binary system. Ternary surface species could not be evidenced in the Eu(III)/HProtoH2/α,γ-Al2O3 ternary system with TRLS because of the very short decay time of Eu(III) in the presence of protocatechuic acid.
Keywords: Europium; Alumina; Phenolic acids; Adsorption; TRLS;

Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications by Enrica Balboni; Nina Jones; Tyler Spano; Antonio Simonetti; Peter C. Burns (24-32).
This study reports major, minor, and trace element data and Sr isotope ratios for 11 uranium ore (uraninite, UO2+x) samples and one processed uranium ore concentrate (UOC) from various U.S. deposits. The uraninite investigated represent ores formed via different modes of mineralization (e.g., high- and low-temperature) and within various geological contexts, which include magmatic pegmatites, metamorphic rocks, sandstone-hosted, and roll front deposits. In situ trace element data obtained by laser ablation-ICP-MS and bulk sample Sr isotopic ratios for uraninite samples investigated here indicate distinct signatures that are highly dependent on the mode of mineralization and host rock geology. Relative to their high-temperature counterparts, low-temperature uranium ores record high U/Th ratios (>1000), low total rare earth element (REE) abundances (<1 wt%), high contents (>300 ppm) of first row transition metals (Sc, Ti, V, Cr, Mn, Co, Ni), and radiogenic 87Sr/86Sr ratios (>0.7200). Comparison of chondrite normalized REE patterns between uraninite and corresponding processed UOC from the same locality indicates identical patterns at different absolute concentrations. This result ultimately confirms the importance of establishing geochemical signatures of raw, uranium ore materials for attribution purposes in the forensic analysis of intercepted nuclear materials.
Keywords: Uranium deposits in the United States; Uranium ore concentrate; Strontium isotopes; ICP-MS;

Geochemical and flow modelling as tools in monitoring managed aquifer recharge by Paula Niinikoski; Sami Saraperä; Nina Hendriksson; Juha A. Karhu (33-43).
Due to a growing world population and the effects of anthropogenic climate change, access to clean water is a growing global concern. Managed aquifer recharge (MAR) is a method that can help society's response to this increasing demand for pure water. In MAR, the groundwater resources are replenished and the quality of the recharged surface water is improved through effects such as the removal of organic matter. This removal occurs through mechanisms such as microbial decomposition, which can be monitored by studying the isotopic composition of dissolved inorganic carbon (DIC). Nevertheless, the monitoring can be difficult when there are other factors, like dissolving calcite, affecting the isotopic composition of DIC.The aims of this study were to establish a method for monitoring the decomposition of organic matter (dissolved organic carbon – DOC) in cases where calcite dissolution adds another component to the DIC pool, and to use this method to monitor the beginning and amount of DOC decomposition on a MAR site at Virttaankangas, southwestern Finland. To achieve this, we calculated the mean residence times of infiltrated water in the aquifer and the fractions of this water reaching observation wells. We conducted geochemical modelling, using PHREEQC, to estimate the amount of DOC decomposition and the mineral reactions affecting the quality of the water.
Keywords: Managed aquifer recharge; Geochemical modelling; Water purification; Isotopes; DIC; DOC;

The Lovozero nepheline-syenite massif in the north-eastern Fennoscandian Shield, well-known to mineralogists and petrologists, is also interesting with its high contents of hydrogen-hydrocarbon gases in different forms of presence, which is untypical of magmatic rocks. The article systematizes and generalizes little known and unpublished data on the composition, location, character and scale (intensity) of the free gases (FG) emission within a major loparite deposit confined to the massif. СН4 and Н2 are dominant in the FG composition. The molecular weight distribution of hydrocarbon gas components corresponds to the classic Anderson–Schulz–Flory distribution with a steep gradient. Carbon and hydrogen of the gases are characterized by rather heavy isotope compositions, becoming lighter from the transition of methane to ethane. The FG volume has been estimated as 0.2–1.6 m3 of gas per 1 m3 of undisturbed rock. The gas recovery of walls in underground workings has been up to 0.2 ml/min/m2 for СН4 and 0.5 ml/min/m2 for Н2 in several years after their heading. The discharge of some shot holes that characterizes the gas emission intensity (1.8–2 m deep and 40 mm in diameter) is up to 300 ml/min, but its 1–2 orders lesser values dominate. The discharge time in some sections varies from several days to 20 years. The overpressure of gases towards the air mainly does not increase 100 hPa, sometimes reaching 120 kPa. It has been defined, that FG distribute irregularly (at the distance of centimeters to hundreds of meters) and their composition and particularly emission intensity perform different temporal fluctuations. The abiogenic origin of FG has been proposed, with FG appearing as a mixture of gases in various proportions: (a) gases remaining in microfissures at the massif's consolidation after the capture by fluid inclusions and those lost during degassing and (b) gases occurred in mechanic-chemical reactions, partial emission and concentration of occluded and diffusely scattered gases under the unstable stress-strain mode of the rock mass. Combustible and explosive hydrogen-hydrocarbon FG can accumulate in the air of underground workings and cause accidents, disrupting the workflow. The background for using characteristics of spatial-temporal variations of the FG emission as precursors of dangerous geodynamic phenomena has been indicated.
Keywords: Free gases; Methane; Hydrogen; Gas emission; Underground workings; Nepheline syenites;

Soil O and C horizon samples (N = 752) were collected at a sample density of 1 site/36 km2 in Nord-Trøndelag and parts of Sør-Trøndelag (c. 25,000 km2), and analysed for Pb and three of the four naturally occurring Pb isotopes (206Pb, 207Pb and 208Pb) in a HNO3/HCl extraction. Soil O and C horizons are decoupled in terms of both Pb concentrations and Pb isotope ratios. In the soil C horizon the Grong-Olden Culmination, a continuous exposure of the Precambrian crystalline basement across the general grain of the Caledonian orogen, is marked by a distinct 206Pb/207Pb isotope ratio anomaly. No clear regional or even local patterns are detected when mapping the Pb isotope ratios in the soil O horizon samples. Variation in the isotope ratios declines significantly from the soil C to the O horizon. On average, Pb concentrations in the O horizon are four times higher and the 206Pb/207Pb isotope ratio is shifted towards a median of 1.15 in comparison to 1.27 in the C horizon. It is demonstrated that natural processes like weathering in combination with plant uptake need to be taken into account in order to distinguish anthropogenic input from natural influences on Pb concentration and the 206Pb/207Pb isotope ratio in the soil O horizon.
Keywords: Soil geochemistry; Aqua regia; O horizon; C horizon; Lead isotopes; Long-range transport;

Use of multiple age tracers to estimate groundwater residence times and long-term recharge rates in arid southern Oman by Th. Müller; K. Osenbrück; G. Strauch; S. Pavetich; K.-S. Al-Mashaikhi; C. Herb; S. Merchel; G. Rugel; W. Aeschbach; W. Sanford (67-83).
Multiple age tracers were measured to estimate groundwater residence times in the regional aquifer system underlying southwestern Oman. This area, known as the Najd, is one of the most arid areas in the world and is planned to be the main agricultural center of the Sultanate of Oman in the near future. The three isotopic age tracers 4He, 14C and 36Cl were measured in waters collected from wells along a line that extended roughly from the Dhofar Mountains near the Arabian Sea northward 400 km into the Empty Quarter of the Arabian Peninsula. The wells sampled were mostly open to the Umm Er Radhuma confined aquifer, although, some were completed in the mostly unconfined Rus aquifer. The combined results from the three tracers indicate the age of the confined groundwater is < 40 ka in the recharge area in the Dhofar Mountains, > 100 ka in the central section north of the mountains, and up to and > one Ma in the Empty Quarter. The 14C data were used to help calibrate the 4He and 36Cl data. Mixing models suggest that long open boreholes north of the mountains compromise 14C-only interpretations there, in contrast to 4He and 36Cl calculations that are less sensitive to borehole mixing. Thus, only the latter two tracers from these more distant wells were considered reliable. In addition to the age tracers, δ2H and δ18O data suggest that seasonal monsoon and infrequent tropical cyclones are both substantial contributors to the recharge. The study highlights the advantages of using multiple chemical and isotopic data when estimating groundwater travel times and recharge rates, and differentiating recharge mechanisms.Display Omitted
Keywords: Groundwater; Stable isotopes; Groundwater residence time; 14C; 4He; 36Cl; Arid region; Groundwater flow; Groundwater recharge;

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of CrIII potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic CrIII into hazardous CrVI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of CrVI from the easily soluble CrIII and 2) the potential bioavailability of CrIII and that of CrVI species produced in the oxidation of CrIII in agricultural soil (fine sand, organic carbon 3.2%). The amount of CrVI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of CrIII into CrVI by manganese oxide (MnIVO2) and 2) the subsequent reduction of CrVI by organic matter back to CrIII. The effect of pH on this net-oxidation of CrIII and on the chemical availability of both CrIII and CrVI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO2, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO2, the net-oxidation of CrIII into CrVI (1 mM CrCl3 in soil suspensions, 1:10 w/V) was negligible. As for the MnO2-treated soils, at maximum only 4.7% of added CrIII was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of CrVI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of CrVI back to CrIII. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of CrIII, which lowered the overall amount of CrIII susceptible for oxidation. Moreover, the oxidation reactions by MnO2 were inhibited by formation of Cr(OH)3 coverage on its surface. The pH-dependent chemical bioavailability of added CrIII differed from that of the CrVI formed. At elevated pHs the chemical availability of CrIII decreased, whereas that of CrVI produced increased. However, the risk of CrVI formation through oxidation of the easily soluble inorganic CrIII was considered to be low in agricultural soils high in organic matter and low in innate MnO2.Display Omitted
Keywords: Chromium; Oxidation; Speciation; Soil; Bioavailability; Chromate; pH; Cr; VI; III; Species;

Atmospheric weathering of Scandinavian alum shales and the fractionation of C, N and S isotopes by Ernest Chi Fru; Christoffer Hemmingsson; Nolwenn Callac; Nathalie Perez; Elena G. Panova; Curt Broman; Abderrazzak El Albani (94-108).
Subaerial exposure and oxidation of organic carbon (Corg)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial Corg oxidation are expected to shift new biomass δ13Corg composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ13Corg at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, Corg-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, Corg-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of Corg without producing a δ13C shift between acid rock drainage precipitates and shale. Moreover, 13C enrichment in inorganic carbon of precipitates does not support microbial Corg oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ34S = δ34Sshale − δ34Sprecipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ15N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of Corg, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.
Keywords: Ancient organic carbon; Black shales; Carbon, Nitrogen, and Sulfur isotopes; Weathering; Sulfide oxidation; Organic matter oxidation;

Use of GEMAS data for risk assessment of cadmium in European agricultural and grazing land soil under the REACH Regulation by Manfred Birke; Clemens Reimann; Koen Oorts; Uwe Rauch; Alecos Demetriades; Enrico Dinelli; Anna Ladenberger; Josip Halamić; Mateja Gosar; Fabian Jähne-Klingberg (109-121).
Over 4000 soil samples were collected for the “Geochemical Mapping of Agricultural and Grazing Land Soil of Europe” (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. Cadmium concentrations are reported for the <2 mm fraction of soil samples from regularly ploughed fields (agricultural soil, Ap, 0–20 cm, N = 2218) and grazing land soil (Gr, 0–10 cm, N = 2127). The samples were collected in 33 European countries, covering 5.6 million km2 at a sample density of 1 sample each per 2500 km2 and were analysed in an aqua regia extraction followed by an ICP-MS finish. The median Cd value is 0.181 mg/kg for the Ap and 0.202 mg/kg for the Gr soil samples. The data allow a directly comparable country-specific regional exposure and risk characterisation for all EU countries covered. Direct risks of Cd for terrestrial organisms are only predicted for a few isolated sample sites: 2.3% of the Ap and 4.5% of the Gr sites, respectively.Display Omitted
Keywords: Agricultural soil; Grazing land soil; Risk assessment; REACH; Cadmium;

Time and temperature dependency of carbon dioxide triggered metal(loid) mobilization in soil by Judith Mehlhorn; James M. Byrne; Andreas Kappler; Britta Planer-Friedrich (122-137).
Assessing the influence of CO2 on soil and aquifer geochemistry is a task of increasing interest when considering risk assessment for geologic carbon sequestration. Leakage and CO2 ascent can lead to soil acidification and mobilization of potentially toxic metals and metalloids due to desorption or dissolution reactions. We studied the CO2 influence on an Fe(III) (oxyhydr)oxide rich, gleyic Fluvisol sampled in close vicinity to a Czech mofette site and compared the short-term CO2 influence in laboratory experiments with observations on long-term influence at the natural site. Six week batch experiments with/without CO2 gas flow at 3 different temperatures and monitoring of liquid phase metal(loid) concentrations revealed two main short-term mobilization processes. Within 1 h to 1 d after CO2 addition, mobilization of weakly adsorbed metal cations occurred due to surface protonation, most pronounced for Mn (2.5–3.3 fold concentration increase, mobilization rates up to 278 ± 18 μg Mn kgsoil −1 d−1) and strongest at low temperatures. However, total metal(loid) mobilization by abiotic desorption was low. After 1–3 d significant Fe mobilization due to microbially-triggered Fe(III) (oxyhydr)oxide dissolution began and continued throughout the experiment (up to 111 ± 24 fold increase or up to 1.9 ± 0.6 mg Fe kgsoil −1 d−1). Rates increased at higher temperature and with a higher content of organic matter. The Fe(III) mineral dissolution was coupled to co-release of incorporated metal(loid)s, shown for As (up to 16 ± 7 fold, 11 ± 8 μg As kgsoil −1 d−1). At high organic matter content, re-immobilization due to resorption reactions could be observed for Cu. The already low pH (4.5–5.0) did not change significantly during Fe(III) reduction due to buffering from sorption and dissolution reactions, but a drop in redox potential (from > +500 mV to minimum +340 ± 20 mV) occurred due to oxygen depletion. We conclude that microbial processes following CO2 induction into a soil can contribute significantly to metal(loid) mobilization, especially at optimal microbial growth conditions (moderate temperature, high organic carbon content) and should be considered for carbon sequestration monitoring and risk assessment.Display Omitted
Keywords: Mofette; Fluvisol; Carbon Capture and Storage (CCS); Microbial iron reduction; Czech Republic;

In this study, solubility constants of hydroxyl sodalite (ideal formula, Na8[Al6Si6O24][OH]2·3H2O) from 25 °C to 100 °C are obtained by applying a high temperature Al—Si Pitzer model to evaluate solubility data on hydroxyl sodalite in high ionic strength solutions at elevated temperatures. A validation test comparing model-independent experimental data to model predictions demonstrates that the solubility values produced by the model are in excellent agreement with the experimental data.The equilibrium constants obtained in this study have a wide range of applications, including synthesis of hydroxyl sodalite, de-silication in the Bayer process for extraction of alumina, and the performance of proposed sodalite waste forms in geological repositories in various lithologies including salt formations. The thermodynamic calculations based on the equilibrium constants obtained in this work indicate that the solubility products in terms of m Σ A l × m Σ S i for hydroxyl sodalite are very low (e.g., ∼10–13 [mol·kg–1]2 at 100 °C) in brines characteristic of salt formations, implying that sodalite waste forms would perform very well in repositories located in salt formations. The information regarding the solubility behavior of hydroxyl sodalite obtained in this study provides guidance to investigate the performance of other pure end-members of sodalite such as chloride- and iodide-sodalite, which may be of interest for geological repositories in various media.
Keywords: Pitzer model; Nuclear waste disposal; Salt formations;

Bacillus anthracis is the pathogenic bacterium that causes anthrax, which dwells in soils as highly resilient endospores. B. anthracis spore viability in soil is dependent upon environmental conditions, but the soil properties necessary for spore survival are unclear. In this study we used a range of soil geochemical and physical parameters to predict the spatial distribution of B. anthracis in northwest Minnesota, where 64 cases of anthrax in livestock were reported from 2000 to 2013. Two modeling approaches at different spatial scales were used to identify the soil conditions most correlated to known anthrax cases using both statewide and locally collected soil data. Ecological niche models were constructed using the Maximum Entropy (Maxent) approach and included 11 soil parameters as environmental inputs and recorded anthrax cases as known presences. One ecological niche model used soil data and anthrax presences for the entire state while a second model used locally sampled soil data (n = 125) and a subset of anthrax presences, providing a test of spatial scale. In addition, simple logistic regression models using the localized soil data served as an independent measure of variable importance. Maxent model results indicate that at a statewide level, soil calcium and magnesium concentrations, soil pH, and sand content are the most important properties for predicting soil suitability for B. anthracis while at the local level, clay and sand content along with phosphorous and strontium concentrations are most important. These results also show that the spatial scale of analysis is important when considering soil parameters most important for B. anthracis spores. For example, at a broad scale, B. anthracis spores may require Ca-rich soils and an alkaline pH, but may also concentrate in microenvironments with high Sr concentrations. The study is also one of the first ecological niche models that demonstrates the major importance of soil texture for defining the ecological niche of B. anthracis. These results will help improve our understanding of the soil geochemical conditions most suitable for B. anthracis as well as more reliably identify areas where anthrax may be found to focus prevention and remediation efforts.
Keywords: Maximum entropy; Logistic regression; Disease; Bacteria; Ecological niche modeling; Bacillus anthracis;

N-nitrodimethlyamine in natural and drinking water of high cancer incidence regions of Guangdong, China by Xiuli Liu; Kuang Cen; Lunshan Zhao; Yuan Chen; Zhiying Lun; Xuefang Wu; Zhaoxue Tian; Jinjin Shi; Xuetao Zhu; Junxiao Wei; Ning Wang; Wenwen Chen (157-164).
The Guangdong province of China contains the most clearly described high-incidence of hepatocellular carcinoma (HCC) and nasopharyngeal carcinoma (NPC) areas in the world. The geographical heterogeneity of cancer incidence in the region suggests that many carcinogenic risk factors might be present in the regional geochemical environment. This paper presents the concentrations of a wide range of known carcinogens in two high cancer incidence areas in Guangdong and compared them to a low cancer incidence area in the same province. N-Nitrosamines, NO3 , NO2 , and ammonium were detected in groundwater, surface water, and drinking-water. The concentrations of the 7 trace metal and metalloid elements As, Cd, Ni, Cu, Pb, Zn, and Hg were determined in surface soil samples and all water samples. The results show that, compared with the guidelines or limit values for drinking-water quality in the world, the high cancer incidence areas have hazardous high levels of N-nitrodimethlyamine (NDMA) in all kinds of water. Oppositely, the low cancer incidence area has a safe low level of NDMA in water bodies. The levels of NO3 , NO2 , and ammonium in water have the same character, although they have different expression between the two high-risk areas. The distribution of the 7 tested trace elements in surface soil has no significant correlation with cancer incidence. On the other hand, high concentrations of carcinogenic N-Nitrosamines in drinking-water and natural water bodies were identified for the first time in the high NPC and HCC incidence area.
Keywords: N-Nitrosamines; Cancer incidence; Guangdong China; Hepatocellular carcinoma; Nasopharyngeal carcinoma;

Compacted bentonite is used as sealing and buffer material in engineered barrier systems (EBS) of high-level radioactive waste repositories. The chemical characteristics of this clay and its porewater affect the migration of radionuclides eventually released from the waste. They also determine the integrity and long-term performance of the clay barriers. Key features are the structural negative charge and the large proportion of structural (interlayer) water of the main mineral montmorillonite, which leads to exclusion of anions and a surplus of cations in a large part of the porosity space. The objective of this contribution was to assess the impact of different porosity model concepts on porewater chemistry in compacted bentonite in the context of the planned Finnish spent nuclear fuel repository at Olkiluoto. First, a structural model based on well-established crystallographic and electrostatic considerations was set up to estimate the fractions of the different porosity types. In view of the uncertainty related to the chemical properties of the interlayer water, two very different model concepts (anion-free interlayer, Donnan space), together with a well-established thermodynamic model for bentonite, were applied to derive the porewater composition of the bentonite buffer at Olkiluoto. The simulations indicate very similar results in the “free” water composition for the two models and thus support the validity of the reference porewater concept commonly used in performance assessment of waste repositories. Differences between the models are evident in the composition of the water affected by the surface charge (i.e. diffuse double layer and interlayer). These reflect the conceptual uncertainty in current multi-porosity diffusion models.
Keywords: Bentonite; Porewater chemistry; Modelling; Engineered barrier system; Nuclear waste repository;

Phosphate mining in southeastern Idaho has historically resulted in the release of dissolved metals and inorganics to groundwater and surface water, primarily due to leachate from waste rock in backfilled pits and overburden storage piles. Selenium (Se) is of particular concern due to its high concentration in leachate and its limited attenuation downgradient of source zones under oxic conditions. Assessments of potential groundwater/surface water impacts from waste rock typically involve laboratory characterization using saturated and unsaturated flow columns packed with waste rock. In this study, we compare the results of saturated and unsaturated column tests with groundwater quality data from the Mountain Fuel, Champ, South and Central Rasmussen Ridge Area (SCRRA), Smoky Canyon, Ballard, Henry, and Enoch Valley Mines, to understand the release and attenuation of Se in different geochemical environments. Column studies and field results demonstrate that the ratio of aqueous Se to aqueous sulfate (Se:SO4 ratio) is a useful metric for understanding Se release and attenuation, where the extent of sulfate reduction is much less than Se reduction. Comparison of dissolved Se and sulfate results suggests that the net leachability of Se from unsaturated waste rock is variable. Overall, Se concentrations in groundwater directly beneath waste rock dumps is not as high as would be predicted from unsaturated columns. Lower Se:SO4 ratios are observed immediately beneath waste rock dumps and backfilled pits relative to areas receiving shallow waste rock runoff. It is hypothesized that Se released in the oxic upper portions of the waste rock is subsequently attenuated via reductive precipitation at depth in unsaturated, low-oxygen portions of the waste rock. This highlights an important mechanism by which Se may be naturally attenuated within waste rock piles prior to discharge to groundwater and surface water. These results have important implications for mining practices in the region. A better understanding of Se dynamics can help drive waste rock management during active mining and capping/water management options during post-mining reclamation.
Keywords: Selenium; Natural attenuation; Southeast Idaho; Phosphate mining; Phosphoria formation;

Shale with high clay content has caused instability from hydration during the hydraulic fracturing process. Macro-level migration phenomenon of water molecules is induced by the chemical potential difference between low-salinity fracturing fluid and high-salinity formation brine. This study aims to establish the equation for the chemical potential difference between fracturing fluid and formation brine by theoretical deduction in order to investigate the effect of the aforementioned phenomenon on fracturing flowback. Accordingly, a mathematical model was established for the gas–water two-phase flow which driven by the chemical potential difference. Viscous force, capillarity and chemiosmosis were considered as the driving forces. A numerical simulation of fracturing fluid flowback with or without considering of the effect of chemiosmosis was performed. A simulation analysis of the water saturation and salinity profiles was also conducted. Results show that capillarity and chemiosmosis hinder fracturing fluid flowback in different degrees. As the condition worsens, they inhibit more than 80% of water to flow back out of the formation, forming a permanent water lock. This study contributes to improvement of the theory on shale gas–water two-phase flow, establishment of a flowback model that suitable for shale gas wells, and accurate evaluation of the fracturing treatment.
Keywords: Shale; Hydration; Chemical potential; Flowback; Chemiosmosis;

Perchlorate mobilization of metals in serpentine soils by Prasanna Kumarathilaka; Christopher Oze; Meththika Vithanage (203-209).
Natural processes and anthropogenic activities may result in the formation and/or introduction of perchlorate (ClO4 ) at elevated levels into the environment. Perchlorate in soil environments on Earth and potentially in Mars may modify the dynamics of metal release and their mobilization. Serpentine soils, known for their elevated metal concentrations, provide an opportunity to assess the extent that perchlorate may enhance metal release and availability in natural soil and regolith systems. Here, we assess the release rates and extractability of Ni, Mn, Co and Cr in processed Sri Lankan serpentine soils using a range of perchlorate concentrations (0.10–2.50 w/v ClO4 ) via kinetic and incubation experiments. Kinetic experiments revealed an increase of Ni, Mn, Co and Cr dissolution rates (1.33 × 10−11, 2.74 × 10−11, 3.05 × 10−12 and 5.35 × 10−13 mol m−2 s−1, respectively) with increasing perchlorate concentrations. Similarly, sequential and single extractions demonstrated that Ni, Mn, Co and Cr increased with increasing perchlorate concentrations compared to the control soil (i.e., considering all extractions: 1.3–6.2 (Ni), 1.2–126 (Mn), 1.4–34.6 (Co) and 1.2–6.4 (Cr) times greater than the control in all soils). Despite the oxidizing capability of perchlorate and the accelerated release of Cr, the dominant oxidation state of Cr in solution was Cr(III), potentially due to low pH (<2) and Cr(VI) instability. This implies that environmental remediation of perchlorate enriched sites must not only treat the direct hazard of perchlorate, but also the potential indirect hazard of related metal contamination.Display Omitted
Keywords: Perchlorate; Heavy metals; Serpentine soils; Dissolution rate; Bioavailability;