Applied Geochemistry (v.51, #C)

Corrosion of metal iron in contact with anoxic clay at 90 °C: Characterization of the corrosion products after two years of interaction by Michel L. Schlegel; Christian Bataillon; Florence Brucker; Cécile Blanc; Dimitri Prêt; Eddy Foy; Matthieu Chorro (1-14).
Chemical and mineralogical properties of solids formed upon free corrosion of two iron probes (one massive iron rod, and one model overpack made by two pipes covering the ends of a glass rod) in saturated clay rock (Callovo-Oxfordian formation, East of Paris Basin, France) at 90 °C over two years were investigated by microscopic and spectroscopic techniques (X-ray tomography, scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman microspectroscopy, micro-X-ray diffraction, and micro-X-ray Absorption Fine Structure spectroscopy). The corrosion rate of the massive rod was monitored in situ by electrochemical impedance spectrometry, and found to decrease from about 90 μm/year during the first month of reaction, to less than 1 μm/year after two years. X-ray tomography revealed the presence of several fractures suggesting the presence of preferential flow and diffusion pathways along the iron samples.Microscopic observations revealed similar corrosion interfaces for both samples. Corrosion heterogeneously affected the interface, with damaged thickness from ∼0 to 80 μm. In extensively damaged areas, an inner discontinuous layer of magnetite in contact with metal, an intermediate chukanovite (Fe2CO3(OH)2) layer (only when magnetite is present, and only for the overpack), and an outer layer of poorly ordered Fe phyllosilicate were observed. In areas with little damage, only the Fe-silicate solids are observed. The clay transformation layer is predominantly made of ankerite ((Fe,Ca,Mg)CO3) forming a massive unit near the trace of the original surface, and intermixed with clay minerals towards the bulk matrix.The average thickness of oxidized iron, as measured by the average of distances from the original to the final metal surface, was 13 ± 1 and 15 ± 1 μm for the massive rod and the micro-overpack, respectively. The corresponding Fe amount is about twice the amount of Fe present in the corrosion products. Thus a significant Fe fraction migrated in the nearby clay, likely as Fe(II), and could act as a significant buffer of the electrochemical potential.

Remediation of 56 ML of acidic, contaminant-laden Baal Gammon mine pit water was undertaken using in situ hydrotalcite formation. The pit water composition was modified via the addition of MgCl2·6H2O to form a 2.5:1 M2+:M3+ metal ion ratio followed by the addition of NaOH to increase the pH 10 to induce spontaneous hydrotalcite precipitation. As a result of the in situ hydrotalcite precipitation a broad spectrum of elements of environmental concern including Al, Cd, Co, Cr, Cu, Fe, In, Mn, Mo, Ni, V and Zn were removed from solution. Significantly, an ore grade hydrotalcite precipitate containing Cu (8.0 ± 1.0%) and Zn (3.9 ± 0.5%) was produced directly from the mine pit water column allowing for potential recovery of valuable metals to offset remediation costs. The final water quality produced after in situ remediation was of a simple Na–Cl–SO4 type.

Understanding the circulation of geothermal waters in the Tibetan Plateau using oxygen and hydrogen stable isotopes by Hongbing Tan; Yanfei Zhang; Wenjie Zhang; Na Kong; Qing Zhang; Jingzhong Huang (23-32).
With the uplift of the Tibetan Plateau, many of the world’s rarest and most unique geothermal fields have been developed. This study aims to systematically analyze the characteristics of the hydrogen and oxygen isotopic data of geothermal, river, and lake waters to understand the circulation of groundwater and to uncover the mechanism of geothermal formation in the Tibetan Plateau. Field observations and isotopic data show that geothermal water has higher temperatures and hydraulic pressures, as well as more depleted D and 18O isotopic compositions than river and lake waters. Thus, neither lakes nor those larger river waters are the recharge source of geothermal water. Snow-melt water in high mountains can vertically infiltrate and deeply circulate along some stretching tensile active tectonic belts or sutures and recharge geothermal water. After deep circulation, cold surface water evolves into high-temperature thermal water and is then discharged as springs at the surface again in a low area, under high water-head difference and cold–hot water density difference. Therefore, the large-scale, high-temperature, high-hydraulic-pressure geothermal systems in the Tibetan Plateau are developed and maintained by rapid groundwater circulation and the heat source of upwelled residual magmatic water. Inevitably, the amount of geothermal water will increase if global warming accelerates the melting of glaciers in high mountains.

Remediation of metal-contaminated soil in polar environments: Phosphate fixation at Casey Station, East Antarctica by Erla G. Hafsteinsdóttir; Kirstie A. Fryirs; Scott C. Stark; Damian B. Gore (33-43).
Remediation of metal-contaminated soils by phosphate fixation is successful in temperate environments, whereas its efficacy in cold and freezing environments is understudied. Phosphate fixation is a low-cost technique and is potentially very useful in these remote environments where the logistics of remediation are difficult and expensive. Here we describe a field study at Casey Station, East Antarctica, where phosphate (triple superphosphate and phosphate rock) and a buffer, Emag (magnesium carbonate and magnesium oxide), were introduced to contaminated soil from nearby Thala Valley landfill. A pilot scale experiment was set up, sampled and monitored from December 2008 to February 2010. Relative to levels in the untreated landfill material, concentrations of Cd, Cu, Co, Fe, Mn, Pb and Zn in leachates were decreased by phosphate addition (fixation most effective for Mn and Zn), whereas the technique increased concentrations of As, Cr and Ni. The most successful fixation was found for the 3:2 ratio of triple superphosphate and Emag, and the least effective fixation occurred with the 2:1:1 ratio of triple superphosphate, Emag and phosphate rock. Although there was an undesirable initial flush of metals from the contaminated soil in the 24–48 h after treatment addition, concentrations in leachate were reduced and stabilised in the second summer. During a full-scale field implementation, complementary techniques would be required to contain and treat contaminated runoff until leachates have reduced to acceptable concentrations.

The production of methylmercury (MeHg), a bioaccumulative neurotoxin, in freshwater systems is primarily driven by naturally occurring sulfate reducing bacteria in anoxic sediment and waters. This research used laboratory microcosms to examine the influence of sulfate on MeHg production and partitioning in sulfate-impacted freshwater estuary sediment. A laboratory sulfate addition experiment exposed 20 cm diameter intact sediment cores with varying organic carbon content to sulfate concentrations in the overlying water ranging from 5 to 50 mg L−1. Results from the 6 month incubation suggest that net MeHg production in sediment from open-water areas of the St. Louis River Estuary was not directly related to overlying water sulfate. Mercury mobility, as indicated by porewater concentrations, appeared to be related to the quantity of organic carbon and sulfur in sediment. Laboratory flux estimates were consistent with porewater concentrations and provided a means to compare diffusion-driven MeHg loading from sediment to MeHg loading from upstream sources.

Microbial reduction of uranium(VI) in sediments of different lithologies collected from Sellafield by Laura Newsome; Katherine Morris; Divyesh Trivedi; Nick Atherton; Jonathan R. Lloyd (55-64).
The presence of uranium in groundwater at nuclear sites can be controlled by microbial processes. Here we describe the results from stimulating microbial reduction of U(VI) in sediment samples obtained from a nuclear-licensed site in the UK. A variety of different lithology sediments were selected to represent the heterogeneity of the subsurface at a site underlain by glacial outwash deposits and sandstone. The natural sediment microbial communities were stimulated via the addition of an acetate/lactate electron donor mix and were monitored for changes in geochemistry and molecular ecology. Most sediments facilitated the removal of 12 ppm U(VI) during the onset of Fe(III)-reducing conditions; this was reflected by an increase in the proportion of known Fe(III)- and U(VI)-reducing species. However U(VI) remained in solution in two sediments and Fe(III)-reducing conditions did not develop. Sequential extractions, addition of an Fe(III)-enrichment culture and most probable number enumerations revealed that a lack of bioavailable iron or low cell numbers of Fe(III)-reducing bacteria may be responsible. These results highlight the potential for stimulation of microbial U(VI)-reduction to be used as a bioremediation strategy at UK nuclear sites, and they emphasise the importance of both site-specific and borehole-specific investigations to be completed prior to implementation.

Investigation of water–rock interactions in Cambrian black shale via a flow-through experiment by Xin Liao; Masahiro Chigira; Yuki Matsushi; Xiyong Wu (65-78).
This paper summarizes the results of a flow-through experiment of our own design intended to investigate the water–rock interactions between pyrite embedded in black shale and dissolved oxygen in pore water. Deionized water in equilibrium with 3 atm of PN2 or PO2 was flowed through a cylindrical rock specimen at 25 °C. The electrical conductivity (EC) and pH values of the experimental outflow solutions were continuously monitored. First, original pore water was expelled by N2-saturated water followed by O2-saturated water. Concentrations of major ion species were determined for solutions periodically withdrawn from the experimental system. The changes in these components over time indicated that 1. The chemical composition of the original pore water in the black shale was rich in hydrogen ions, sulfate ions and iron species and that 2. Two major reactions, namely, ion exchange and pyrite oxidation, occurred during the water flow. The oxidation of pyrite in black shale was controlled by the concentration of dissolved oxygen as FeS 2 + 7 / 2 O 2 ( aq ) + H 2 O → Fe 2 + + 2 SO 4 2 - + 2 H + , where the rate law for the reaction at pH = 4.2–5.6 and T  = 25 °C was determined to be Rsp  = 10−8.42±0.06 [O2]0.5 (mol m−2  s−1). This result is consistent with the reaction rate of pyrite grains with dissolved oxygen reported by previous researchers. Hydraulic conductivity decreased by approximately 12.5% during the nitrogen-inflow stage and by 69% during the oxygen-inflow stage. This change can be attributed to the oxidizing reaction within the rock and to the probable clogging of fine weathering products in the pore space. The geochemical modeling of the experimental outflowing water and seepage samples from the field using the PHREEQC program suggested that pore water develops into an acidic solution rich in iron and sulfate due to long-term pyrite oxidation and evaporation.

Natural 222Rn and 220Rn indicate the impact of the Water–Sediment Regulation Scheme (WSRS) on submarine groundwater discharge in the Yellow River estuary, China by Bochao Xu; Dong Xia; William C. Burnett; Natasha T. Dimova; Houjie Wang; Longjun Zhang; Maosheng Gao; Xueyan Jiang; Zhigang Yu (79-85).
Submarine groundwater discharge (SGD) in estuaries brings important influences to coastal ecosystems. In this study, we observed significant SGD in the Yellow River estuary, including a fresh component, during the Water–Sediment Regulation Scheme (WSRS) period. We used the 222Rn and 220Rn isotope pair to locate sites of significant SGD within the study area. Three apparent SGD locations were found during a non-WSRS period, one of which became much more pronounced, according to the remarkably elevated radon levels, during the WSRS. Increased river discharge (from 245 m3  s−1 to 3560 m3  s−1) and the elevated river water level (from 11 m to 13 m) during the WSRS led to a higher hydraulic head, enhancing groundwater discharge in the estuary. Our results suggest that high river discharge (>3000 m3  s−1) might be necessary for elevated fresh submarine groundwater discharging (FSGD). Vertical profiles of salinity, DO and turbidity anomalies along the benthic boundary layer also indicated significant FSGD in the estuary during the WSRS. Nutrient concentrations had positive correlations with 222Rn during a 24-h observation, which indicates that SGD is a dominant nutrient pathway in this area.

Soil–gas measurements of different gas species were performed in two distinct areas of the Corinth Gulf Rift (Greece): the Aigion-Neos Erineos-Lambiri (ANEL) fault zone and the Rion-Patras fault zone. Both zones lie in one of the most seismically active areas of the Euro-Mediterranean region, where a fast-opening continental rift is located. In particular, the geochemical investigations were focused on fault segments and fracture systems previously inferred by geomorphological, lithological and structural studies.In this work the applicability of soil–gas geochemistry surveys for the exploration of buried/hidden faults was tested by using various statistical methods. Moreover, a comprehensive geostatistical treatment of the collected data provided new insights into the control exerted by active structures on deep-seated gas migration towards the surface. In both investigated areas, the highest 222Rn and CO2 concentration peaks correspond with zones where the interaction among fracture and fault segments was inferred by structural and morphological methods. This indicates a clear correlation between the shape and orientation of the anomalies and the different attitude and kinematic behavior of the faults recognized in the two areas. Furthermore, obtained results show that gases migrate preferentially through zones of brittle deformation by advective processes, as suggested by the relatively high rate of migration needed to obtain anomalies of short-lived 222Rn in the soil pores.

The aim of this study was to investigate the dissolution and transformation characteristics of phyllosilicate under low molecular weight organic acids in the farmland environment (pH 4.0–8.0). Changes of dissolution and morphology of biotite were evaluated using chemical extraction experiments and in situ/ex situ atomic force microscopy (AFM) with fluids of citric acid (CA) solution at pH 4.0, 6.0, and 8.0. Results of extracting experiments show that CA solutions contributed to the release rate of potassium (K), silicon (Si), and aluminum (Al) from biotite relative to a control aqueous solution. In situ AFM observations indicate that the dissolution of biotite from the biotite (0 0 1) surface occurred on the terrace, segment, and fringe of pits, while new etch pits did not readily form on biotite (0 0 1) surfaces in aqueous solutions. However, dissolution rates of terraces can be greatly accelerated with the help of citrate. In pH 4.0 CA solution, 70 min dissolution reactions of biotite (0 0 1) surfaces result in more etch pits than in pH 6.0 and 8.0 solutions. In addition, the transformation of biotite occurred simultaneously with the dissolution process. Secondary coating was observed on the biotite (0 0 1) surface after 140 h of immersion in a weak acid environment. Thus, the protons have a dominant role in the dissolution process of biotite with organic (carboxyl) acting as a catalyst under acidic condition. Based on the theory of interactions on a water–mineral interface in a weak acid environment, dissolution of biotite starts from defect/kink sites on the surface, one layer by one layer, and develops along the [hk  0] direction. A secondary coating that forms on the biotite (0 0 1) surface may restrain the formation and growth of etch pits, whereas this process may have a positive role on the stability of soil structure during long-term soil management.

Tracing low-temperature aqueous metal migration in mineralized watersheds with Cu isotope fractionation by R. Mathur; L.A. Munk; B. Townley; K.Y. Gou; N. Gómez Miguélez; S. Titley; G.G. Chen; S. Song; M. Reich; F. Tornos; J. Ruiz (109-115).
Copper isotope signatures in waters emanating from mineralized watersheds provide evidence for the source aqueous copper in solution. Low-temperature aqueous oxidation of Cu sulfide minerals produces significant copper isotopic fractionation between solutions and residues. Abiotic experimental data of fractionation (defined as Δ liquid–solid ‰ = δ65Culiquid  − δ65Cusolid) are on the order of 1–3‰ and are unique for copper rich-sulfide minerals. Data presented here from ores and waters within defined boundaries of porphyry copper, massive sulfide, skarn, and epithermal ore deposits mimic abiotic experiments. Thus, the oxidation of sulfide minerals appears to cause the signatures in the waters although significant biological, temperature, and pH variations exist in the fluids. Regardless of the deposit type, water type, concentration of Cu in solution, or location, the data provide a means to trace sources of metals in solutions. This relationship allows for tracking sources and degree of metal migration in low temperature aqueous systems and has direct application to exploration geology and environmental geochemistry.

Kinetic reactive transport modelling of column tests for uranium In Situ Recovery (ISR) mining by Rose Ben Simon; Médard Thiry; Jean-Michel Schmitt; Vincent Lagneau; Valérie Langlais; Michel Bélières (116-129).
Display OmittedThe In Situ Recovery (ISR) mining method consists in mining ore by in situ chemical leaching with acid or alkaline solutions. Numerical modelling of the interaction between solution and rock is examined in order to improve the management of this process. Three different phenomena have to be taken into account in a numerical reactive transport simulation of uranium ISR mining: (1) the geochemical reactions; (2) the kinetics of these reactions, and (3) the hydrodynamic transport rate compared to the reaction kinetics. Two ‘classical’ types of leaching experiments were performed: (1) tests in batch reactors; and (2) extraction in flow-through columns. A comprehensive interpretation of the complete leaching test results (mineralogy of the samples and chemical analysis of leachates) led to the development of a conceptual model with reasonable assumptions about dissolution and precipitation reactions during the acid leach of the columns. This conceptual model was tested and validated by numerical modelling of the two types of laboratory experiments. Batch experiments were simulated with the geochemical code CHESS in order to model the leachate solutions and to calibrate the geochemical reaction paths and their kinetic laws. Column experiments were simulated with the coupled hydrodynamic and geochemical code HYTEC by using kinetic laws calibrated on batch experiments. The geochemical models with kinetics successfully simulated the trend of leachate’ chemistry in the two types of experimental tests (batch and column). Numerical simulation of leaching tests enabled us to translate the chemical release sequence, observed during experiments, into a sequence of dissolution–precipitation reactions. Finally, it resulted in a proposal of a 1D hydrogeochemical transport model of the ISR process at laboratory-scale. Furthermore, a sensitivity analysis conducted on the 1D-calibrated model made it possible (1) to determine factors controlling leaching reactions; and (2) to quantify their respective influence on the uranium recovery in terms of acid consumption and leachate volume to treat in the plant. Although experimental and numerical simulation results do not perfectly fit the field-scale observations, it was possible to define not only the factors controlling uranium dissolution and the precipitation of secondary mineral phases in the deposit, but also to determine the relative importance of these factors.

Jarosite quantification in soils: An enhanced sequential extraction procedure by Chamindra L. Vithana; Leigh A. Sullivan; Richard T. Bush; Edward D. Burton (130-138).
A two-step sequential extraction procedure established for the quantification of acidity producing ferric and ferrous sulfate minerals such as melanterite and jarosite in acid mine wastes was evaluated for quantification of jarosite spiked in soils. The procedure involves in sequence anoxic water extraction, roasting the solid residue after anoxic water extraction at 550 °C for 1 h, and 4 M HCl extraction of the roasted solid. Soil and quartz samples were spiked with known amounts of synthetic and natural jarosite and their recovery was measured using the suggested two-step sequential extraction procedure. The recoveries of synthetic and natural jarosite were calculated on the basis of the S contents of the initially spiked jarosite in soil and quartz samples. Less than 50% of the spiked jarosite was recovered. The missing S is partially attributable to the retention of jarosite by the Teflon filter membrane used during the filtration of the anoxic water extract. Further investigations also demonstrated a lower 4 M HCl-S extractability from jarosite samples roasted at 550 °C than those roasted at 450 °C. S recovery from jarosite-spiked quartz samples increased to 45–70% by replacing the Teflon filter membrane with the Cellulose Acetate filter membrane and including this filter paper in the second step roasting. This modified method is a step forward in the development of methods to accurately and reliably quantify jarosite in soil materials.

Isotope geochemistry of waters affected by mining activities in Sierra Minera and Portman Bay (SE, Spain) by Mari Luz García-Lorenzo; María José Martínez-Sánchez; Carmen Pérez-Sirvent; Inés Agudo; Clemente Recio (139-147).
The objective of this work was to evaluate processes affecting waters from Portman Bay by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. In addition, surface waters from Sierra Minera were examined for the purpose of determining if these waters are affected by similar processes. The results obtained indicate that Portman Bay waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe3+ was predominant in the surface, and controlled by Acidithiobacillus ferrooxidans, while at depth, sulfate reduction occurred.

Elevated concentrations of uranium (U) from natural sources have been measured in drinking water from private drilled wells in Sweden and many other countries world-wide. Although U is a radioactive element, radioactivity is not the main concern, but rather chemical toxicity, e.g. kidney damage. Uranium chemistry is complex and U in water has a very high tendency to form complexes with other compounds. Since speciation is crucial for the properties of U, and therefore the removal efficiency, this study determined theoretical U species in drinking water from private drilled wells using the geochemical model Visual MINTEQ. The drinking water samples used in modelling were from two datasets: (1) 76 water samples selected from a previous survey of 722 wells; and (2) samples of drinking water from 21 private wells sampled in May 2013. The results showed that neutrally charged U complexes dominated in the pH range 6.7–7.8, which is common in private drilled wells. This has important implications for removal method, since charge is an important factor for U removal efficiency. In the alkaline pH range, one of two calcium-UO2 carbonate complexes dominated and calcium (Ca) concentration proved to be a key factor determining the Ca-UO2 carbonate complex formed: the neutral Ca2UO2(CO3)3 0(aq) or the negative CaUO2(CO3)3 2 . Complexes with organic carbon (C) varied greatly in the acidic range, indicating that it is crucial to measure organic C content in the water since it is critical for the dissolved organic matter (DOM)-UO2 complex formation. Therefore before U removal method is selected, some crucial parameters for complex formation should be measured. Based on our results, such measurements should include pH, Ca, alkalinity and organic C concentration, as these determine the type of complexes formed and their charge.

The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO2, including the possibility of enhanced microbial conversion of CO2 to CH4 via methanogenesis. Stable carbon isotopes of CO2, CH4 and DIC, together with mol% CO2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO2. The dominant fate of the injected CO2 appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ13C-CO2 and δ13C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

Significant amounts of sulfuric acid (H2SO4) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R Si, R Al, R Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R Si value was obtained at pH 1 and 45 °C (−9.07 mol g−1  s−1), while the lowest log R Si value was obtained at pH 4 and 25 °C (−11.20 mol g−1  s−1). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol−1 (pH 1) to 37.7 kJ mol−1 (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 (I  = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H2SO4/tonne clay/day at pH 4 (I  = 0.25 M, 25 °C). The highest ANC of 6.91 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I  = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange by Kingsley O. Odigie; Andrew S. Cohen; Peter W. Swarzenski; A. Russell Flegal (184-190).
Display OmittedLead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815–1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements – likely caused by changes in land use – over that period. For example, the flux of Pb increased by ∼300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r  = 0.77–0.99, p  < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r  = 0.82–0.98, p  < 0.01, n  = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake’s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Geochemistry of major and trace elements and Pb–Sr isotopes of a weathering profile developed on the Lower Cambrian black shales in central Hunan, China by Bo Peng; Andrew Rate; Zhaoliang Song; Changxun Yu; Xiaoyan Tang; Shurong Xie; Xianglin Tu; Changyin Tan (191-203).
Display OmittedThis paper reports a geochemical study on the major and trace elements and Pb–Sr isotopes of a weathering profile developed in the Lower Cambrian black shales in central Hunan (China). Six weathering horizons were identified and sampled vertically throughout the profile. The chemical composition of the profile consists of variable concentrations of the major elements Fe2O3, FeO, MnO, MgO, CaO, Na2O, and P2O5 and of less variable concentrations of SiO2, TiO2, Al2O3, and K2O. The chemical change caused by weathering is estimated by mass-balance calculations, and the results show that the element mobility is characterised by substantial loss of SiO2, FeO, CaO, K2O, Na2O, LOI, Cr, V, Ba, Cs, Rb, Sr, U, and Th, and moderate loss of Al2O3, MgO, Fe2O3, Ni, Cu, Pb, Tl, Sn, Sc, Ge and REE (Y). The high field strength elements TiO2, Sn, Sc, U, Ga, Ge, Zr, Hf, Nb, and Ta were immobile during weathering. The chemical changes and the Pb–Sr isotopic data suggest that four types of chemical reactions occurred: the oxidation of sulphide minerals (e.g., pyrite) and organic carbon (OS), the dissolution of less resistant clinochlore-Ia, calcite, and P-bearing minerals (DL), the dissolution of detrital albite and microcline (DA), and the transformation of clay (TC) minerals (e.g., muscovite and illite–smectite). These chemical reactions then led to two stages of geochemical processes, an early stage of chemical differentiation and a later stage of chemical homogenisation. The chemical differentiation dominated by the OS, DL, and DA reactions, led to the leaching of mobile elements (e.g., MgO, Na2O, K2O, P2O5, Sr, and REE) and the redistribution of some less mobile elements (e.g., SiO2 and Al2O3). In contrast, the chemical homogenisation, which was caused by TC reactions, led to the leaching of both mobile and less mobile elements from the system and ultimately transformed the weathered black shales into soil. Soils derived from black shales in South China might result from the above two geochemical processes.

Alpha-emitting isotopes and chromium in a coastal California aquifer by Jill N. Densmore; John A. Izbicki; Joseph M. Murtaugh; Peter W. Swarzenski; Thomas D. Bullen (204-215).
The unadjusted 72-h gross alpha activities in water from two wells completed in marine and alluvial deposits in a coastal southern California aquifer 40 km north of San Diego were 15 and 25 picoCuries per liter (pCi/L). Although activities were below the Maximum Contaminant Level (MCL) of 15 pCi/L, when adjusted for uranium activity; there is concern that new wells in the area may exceed MCLs, or that future regulations may limit water use from the wells. Coupled well-bore flow and depth-dependent water-quality data collected from the wells in 2011 (with analyses for isotopes within the uranium, actinium, and thorium decay-chains) show gross alpha activity in marine deposits is associated with decay of naturally-occurring 238U and its daughter 234U. Radon activities in marine deposits were as high as 2230 pCi/L. In contrast, gross alpha activities in overlying alluvium within the Piedra de Lumbre watershed, eroded from the nearby San Onofre Hills, were associated with decay of 232Th, including its daughter 224Ra. Radon activities in alluvium from Piedra de Lumbre of 450 pCi/L were lower than in marine deposits. Chromium VI concentrations in marine deposits were less than the California MCL of 10 μg/L (effective July 1, 2014) but δ53Cr compositions were near zero and within reported ranges for anthropogenic chromium. Alluvial deposits from the nearby Las Flores watershed, which drains a larger area having diverse geology, has low alpha activities and chromium as a result of geologic and geochemical conditions and may be more promising for future water-supply development.

Experience is lacking with mineral scaling and corrosion in enhanced geothermal systems (EGS) in which surface water is circulated through hydraulically stimulated crystalline rocks. As an aid in designing EGS projects we have conducted multicomponent reactive-transport simulations to predict the likely characteristics of scales and corrosion that may form when exploiting heat from granitoid reservoir rocks at ∼200 °C and 5 km depth. The specifications of an EGS project at Basel, Switzerland, are used to constrain the model. The main water–rock reactions in the reservoir during hydraulic stimulation and the subsequent doublet operation were identified in a separate paper (Alt-Epping et al., 2013b). Here we use the computed composition of the reservoir fluid to (1) predict mineral scaling in the injection and production wells, (2) evaluate methods of chemical geothermometry and (3) identify geochemical indicators of incipient corrosion. The envisaged heat extraction scheme ensures that even if the reservoir fluid is in equilibrium with quartz, cooling of the fluid will not induce saturation with respect to amorphous silica, thus eliminating the risk of silica scaling. However, the ascending fluid attains saturation with respect to crystalline aluminosilicates such as albite, microcline and chlorite, and possibly with respect to amorphous aluminosilicates. If no silica-bearing minerals precipitate upon ascent, reservoir temperatures can be predicted by classical formulations of silica geothermometry. In contrast, Na/K concentration ratios in the production fluid reflect steady-state conditions in the reservoir rather than albite–microcline equilibrium. Thus, even though igneous orthoclase is abundant in the reservoir and albite precipitates as a secondary phase, Na/K geothermometers fail to yield accurate temperatures. Anhydrite, which is present in fractures in the Basel reservoir, is predicted to dissolve during operation. This may lead to precipitation of pyrite and, at high exposure of anhydrite to the circulating fluid, of hematite scaling in the geothermal installation. In general, incipient corrosion of the casing can be detected at the production wellhead through an increase in H2(aq) and the enhanced precipitation of Fe-bearing aluminosilicates. The appearance of magnetite in scales indicates high corrosion rates.

Mine tailings dams: Characteristics, failure, environmental impacts, and remediation by D. Kossoff; W.E. Dubbin; M. Alfredsson; S.J. Edwards; M.G. Macklin; K.A. Hudson-Edwards (229-245).
On a global scale demand for the products of the extractive industries is ever increasing. Extraction of the targeted resource results in the concurrent production of a significant volume of waste material, including tailings, which are mixtures of crushed rock and processing fluids from mills, washeries or concentrators that remain after the extraction of economic metals, minerals, mineral fuels or coal. The volume of tailings is normally far in excess of the liberated resource, and the tailings often contain potentially hazardous contaminants. A priority for a reasonable and responsible mining organization must be to proactively isolate the tailings so as to forestall them from entering groundwaters, rivers, lakes and the wind. There is ample evidence that, should such tailings enter these environments they may contaminate food chains and drinking water. Furthermore, the tailings undergo physical and chemical change after they have been deposited. The chemical changes are most often a function of exposure to atmospheric oxidation and tends to make previously, perhaps safely held contaminants mobile and available. If the tailings are stored under water, contact with the atmosphere is substantially reduced, thereby forestalling oxygen-mediated chemical change. It is therefore accepted practice for tailings to be stored in isolated impoundments under water and behind dams. However, these dams frequently fail, releasing enormous quantities of tailings into river catchments. These accidents pose a serious threat to animal and human health and are of concern for extractive industries and the wider community. It is therefore of importance to understand the nature of the material held within these dams, what best safety practice is for these structures and, should the worst happen, what adverse effects such accidents might have on the wider environment and how these might be mitigated. This paper reviews these factors, covering the characteristics, types and magnitudes, environmental impacts, and remediation of mine tailings dam failures.

This paper reports in situ observations on barite (0 0 1) surface dissolution behavior in 0.1–0.001 M NaCl solutions at 30 °C using atomic force microscopy (AFM). The step retreating on barite (0 0 1) surfaces changed with increasing NaCl solution concentrations. In solutions with a higher NaCl concentration (⩾0.01 M), many steps showed curved or irregular fronts during the later experimental stage, while almost all steps in solutions with a lower NaCl concentration exhibited straight or angular fronts, even during the late stage. The splitting phenomenon of the initial 〈hk  0〉 one-layer steps (7.2 Å) into two half-layer steps (3.6 Å) occurred in all NaCl solutions, while that of the initial [0 1 0] one-layer steps observed only in the 0.1 M NaCl solution. The step retreat rates increased with an increasing NaCl solution concentration. We observed triangular etch pit and deep etch pit formation in all NaCl solutions, which tended to form late in solutions with lower NaCl concentrations. The deep etch pit morphology changed with increasing NaCl solution concentrations. A hexagonal form elongated in the [0 1 0] direction was bounded by the {1 0 0}, {3 1 0}, and (0 0 1) faces in a 0.001 M NaCl solution, and a rhombic form was bounded by the {5 1 0} and (0 0 1) faces in 0.01 M and 0.1 M NaCl solutions. An intermediate form was observed in a 0.005 M NaCl solution, which was defined by {1 0 0}, a curved face tangent to the [0 1 0] direction, {3 1 0}, and (0 0 1) faces: the intermediate form appeared between the hexagonal and rhombic forms in solutions with lower and higher NaCl concentrations, respectively. The triangular etch pit and deep etch pit growth rates also increased with the NaCl solution concentration. Combining the step and face retreat rates in NaCl solutions estimated in this AFM study as well as the data on the effect of water temperature on the retreat rates reported in our earlier study, we produced two new findings. One finding is that the retreat rates increase by approximately two-fold when the NaCl solution concentration increases by one order of magnitude, and the other finding is that the retreat rate increase due to a one order of magnitude increase in the NaCl concentration corresponds to an increase of approximately 8 °C in water temperature. This correlation may help to understand and evaluate increasing dissolution kinetics induced by the different mechanisms where barite dissolution is promoted by the catalytic effect of Na+ and Cl ions (through an increase in the NaCl solution concentration) or by an increase in the hydration of Ba2+ and SO4 2− (through an increase in water temperature).

Soil-geochemical factors controlling the distribution and oral bioaccessibility of nickel, vanadium and chromium in soil by Sherry Palmer; Siobhan F. Cox; Jennifer M. McKinley; Ulrich Ofterdinger (255-267).
Geogenic nickel (Ni), vanadium (V) and chromium (Cr) are present at elevated levels in soils in Northern Ireland. Whilst Ni, V and Cr total soil concentrations share common geological origins, their respective levels of oral bioaccessibility are influenced by different soil-geochemical factors. Oral bioaccessibility extractions were carried out on 145 soil samples overlying 9 different bedrock types to measure the bioaccessible portions of Ni, V and Cr. Principal component analysis identified two components (PC1 and PC2) accounting for 69% of variance across 13 variables from the Northern Ireland Tellus Survey geochemical data. PC1 was associated with underlying basalt bedrock, higher bioaccessible Cr concentrations and lower Ni bioaccessibility. PC2 was associated with regional variance in soil chemistry and hosted factors accounting for higher Ni and V bioaccessibility. Eight percent of total V was solubilised by gastric extraction on average across the study area. High median proportions of bioaccessible Ni were observed in soils overlying sedimentary rock types. Whilst Cr bioaccessible fractions were low (max = 5.4%), the highest measured bioaccessible Cr concentration reached 10.0 mg kg−1, explained by factors linked to PC1 including high total Cr concentrations in soils overlying basalt bedrock.

Mobilisation of arsenic from bauxite residue (red mud) affected soils: Effect of pH and redox conditions by Cindy L. Lockwood; Robert J.G. Mortimer; Douglas I. Stewart; William M. Mayes; Caroline L. Peacock; David A. Polya; Paul R. Lythgoe; Alizée P. Lehoux; Katalin Gruiz; Ian T. Burke (268-277).
The tailings dam breach at the Ajka alumina plant, western Hungary in 2010 introduced ∼1 million m3 of red mud suspension into the surrounding area. Red mud (fine fraction bauxite residue) has a characteristically alkaline pH and contains several potentially toxic elements, including arsenic. Aerobic and anaerobic batch experiments were prepared using soils from near Ajka in order to investigate the effects of red mud addition on soil biogeochemistry and arsenic mobility in soil–water experiments representative of land affected by the red mud spill. XAS analysis showed that As was present in the red mud as As(V) in the form of arsenate. The remobilisation of red mud associated arsenate was highly pH dependent and the addition of phosphate to red mud suspensions greatly enhanced As release to solution. In aerobic batch experiments, where red mud was mixed with soils, As release to solution was highly dependent on pH. Carbonation of these alkaline solutions by dissolution of atmospheric CO2 reduced pH, which resulted in a decrease of aqueous As concentrations over time. However, this did not result in complete removal of aqueous As in any of the experiments. Carbonation did not occur in anaerobic experiments and pH remained high. Aqueous As concentrations initially increased in all the anaerobic red mud amended experiments, and then remained relatively constant as the systems became more reducing, both XANES and HPLC–ICP-MS showed that no As reduction processes occurred and that only As(V) species were present. These experiments show that there is the potential for increased As mobility in soil–water systems affected by red mud addition under both aerobic and anaerobic conditions.

Kaloko-Honokōhau National Historical Park (KAHO) is a coastal sanctuary on the western side of the Island of Hawai‘i that was established in 1978 to preserve, interpret, and perpetuate traditional Native Hawaiian culture and activities. KAHO contains a variety of culturally and ecologically significant water resources and water-related habitat for species that have been declared as threatened or endangered by the U.S. Fish and Wildlife Service, or are candidate threatened or endangered species. These habitats are dependent on coastal unconfined groundwater in a freshwater-lens system. The coastal unconfined-groundwater system is recharged by local infiltration of rainfall but also may receive recharge from an inland groundwater system containing groundwater impounded to high altitudes. The area inland of and near KAHO is being rapidly urbanized and increased groundwater withdrawals from the inland impounded-groundwater system may affect habitat and water quality in KAHO, depending on the extent of connection between the coastal unconfined groundwater and inland impounded-groundwater. An investigation of the geochemistry of surface-water and groundwater samples in and near KAHO was performed to evaluate the presence or absence of a connection between the inland impounded- and coastal unconfined-groundwater systems in the area. Analyses of major ions, selected trace elements, rare-earth elements, and strontium-isotope ratio results from ocean, fishpond, anchialine pool, and groundwater samples were consistent with a linear mixing process between the inland impounded and coastal unconfined-groundwater systems. Stable isotopes of water in many samples from the coastal unconfined-groundwater system require an aggregate recharge altitude that is substantially higher than the boundary between the coastal unconfined and inland impounded systems, a further indication of a hydrologic connection between the two systems. The stable isotope composition of the freshwater component of water samples from KAHO indicates that about 25–70% of the freshwater is derived from the inland impounded system.

Transformation of natural ferrihydrite aged in situ in As, Cr and Cu contaminated soil studied by reduction kinetics by Sanne Skov Nielsen; Peter Kjeldsen; Hans Christian Bruun Hansen; Rasmus Jakobsen (293-302).
Display OmittedSeveral soil remediation techniques for As, Cu and Cr contaminated soil utilize adsorption of contaminants to ferrihydrite as the removal mechanism, even though ferrihydrite will transform to secondary iron oxides and part of the sorption capacity will be lost. Transformation of ferrihydrite following 4 yr of in situ burial at a contaminated site was examined in samples of impure (Si-bearing) ferrihydrite in soil heavily polluted with As, Cr and Cu. The samples are so-called iron water treatment residues (Fe-WTR) precipitated from anoxic groundwater during aeration. The extent of transformation of ferrihydrites in the field was evaluated in the lab through experiments where the kinetics of iron and contaminant release was studied in a pH 3 ascorbic acid solution. Compared to fresh controls the aged samples had scavenged significant amounts of contaminants (up to 9.2 mmolAs/molFe and 1.5 mmolCu/molFe) and the reactivity had decreased by one order of magnitude, indicating partial transformation of ferrihydrite to more crystalline iron phases. Iron crystallinity increased during the 4 yr of aging with XRD suggesting goethite, α-FeO(OH), to be the most prominent transformation products. The study clarifies the fate of ferrihydrite and associated contaminants during burial enabling an improvement of the methods for amending contaminated soil with Fe-WTR.

Polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) in urban soils of Greater London, UK by Christopher H. Vane; Alexander W. Kim; Darren J. Beriro; Mark R. Cave; Katherine Knights; Vicky Moss-Hayes; Paul C. Nathanail (303-314).
Surface soils from a 19 km2 area in east London, UK were analysed for polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) (n  = 76). ∑16 PAH ranged from 4 to 67 mg/kg (mean, 18 mg/kg) and ∑50 PAH ranged from 6 to 88 mg/kg (mean, 25 mg/kg). ∑7 PCB ranged from 1 to 750 μg/kg (mean, 22 μg/kg) and ∑tri-hepta PCB ranged 9 to 2600 μg/kg (mean, 120 μg/kg). Compared to other international cities concentrations were similar for PAH but higher for PCB. Normal background concentrations (NBC) were calculated and compared to risk-based human health generic assessment criteria (GAC). Benzo[a]pyrene NBC for urban (6.9 mg/kg), semi-urban (4.4 mg/kg) and urban + semi urban (6 mg/kg) domains exceed residential (1 mg/kg) and allotment (2.2 mg/kg) LQM/CIEH GAC (at 6% SOM) and the Indeno[1,2,3-cd]pyrene NBC for urban (6.8 mg/kg) and urban + semi-urban (5.2 mg/kg) domains exceed the residential (4.2 mg/kg) LQM/CIEH GAC (at 6% SOM). Capsule Abstract: Normal background concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls are elevated in east London soils and in some cases exceed regulatory assessment criteria.

A modified procedure for mixture-model clustering of regional geochemical data by Karl J. Ellefsen; David B. Smith; John D. Horton (315-326).
A modified procedure is proposed for mixture-model clustering of regional-scale geochemical data. The key modification is the robust principal component transformation of the isometric log-ratio transforms of the element concentrations. This principal component transformation and the associated dimension reduction are applied before the data are clustered. The principal advantage of this modification is that it significantly improves the stability of the clustering. The principal disadvantage is that it requires subjective selection of the number of clusters and the number of principal components. To evaluate the efficacy of this modified procedure, it is applied to soil geochemical data that comprise 959 samples from the state of Colorado (USA) for which the concentrations of 44 elements are measured. The distributions of element concentrations that are derived from the mixture model and from the field samples are similar, indicating that the mixture model is a suitable representation of the transformed geochemical data. Each cluster and the associated distributions of the element concentrations are related to specific geologic and anthropogenic features. In this way, mixture model clustering facilitates interpretation of the regional geochemical data.