Applied Geochemistry (v.72, #C)

Impact of anthropogenic geochemical change and aquifer geology on groundwater phosphorus concentrations by Paul M. McGinley; Kevin C. Masarik; Madeline B. Gotkowitz; David J. Mechenich (1-9).
Geologic and geochemical variations across a 4200 km2 area of south-central Wisconsin (USA) were used to examine their relationship to phosphorus concentrations in groundwater from more than four hundred private water supply wells. Surficial geology in the study area ranged from Cambrian sandstones to Ordovician dolomites. Groundwater phosphorus concentrations were higher in aquifers of older Cambrian age compared to the concentrations in aquifers of younger Cambrian and Ordovician age. Because iron concentrations were relatively low in these waters and agricultural land use was similar in all geologic regions, we propose that the differences in bedrock phosphorus and anthropogenic geochemical impacts explain the differences in phosphorus concentrations between aquifers. Within the older Cambrian aquifers, groundwater phosphorus concentrations were elevated in groundwater with higher nitrate-nitrogen concentrations. This finding is consistent with the presence of phosphorus within sediment in these strata and geologic conditions that weakly buffered pH reduction from anthropogenic acidification. In contrast, groundwater phosphorus concentrations in younger Cambrian and Ordovician aquifers were not elevated in samples with higher nitrate. Anthropogenic acidification in these carbonate-rich aquifers was neutralized through increased carbonate weathering, which led to higher groundwater calcium and alkalinity and would limit the dissolution of phosphate-rich minerals, such as apatite, where present. Low iron concentrations observed in most samples suggest that the phosphorus release in the Cambrian strata occurs beyond the zone of secondary mineral retention in the soil. These results have important implications for the eutrophication of inland surface waters in areas with bedrock phosphorus and anthropogenic acidity that is not neutralized before it contacts phosphatic rock.Display Omitted
Keywords: Eutrophication; Groundwater; Phosphorus; Nitrate; Watershed acidification;

Temperature dependence of the reactivity of cemented paste backfill by Z. Aldhafeeri; M. Fall; M. Pokharel; Z. Pouramini (10-19).
The environmental performance of cemented paste backfill (CPB; a mixture of tailings, water and binder), which contains sulphide mineral-bearing tailings, is strongly influenced by its reactivity. However, our understanding of the reactivity of CPB under various thermal loading conditions as well as its evolution with time is limited. Hence, a laboratory investigation is conducted to study the effects of curing and ambient (atmospheric) temperatures on the reactivity of CPB. Oxygen consumption (OC) tests are conducted on CPB specimens cured at different temperatures to study their reactivity. Furthermore, microstructural analyses (e.g., x-ray diffraction (XRD), mercury intrusion porosimetry, and thermogravimetry/derivative thermogravimetry) are performed to assess the microstructural characteristics of the tested CPBs. The results show that the reactivity of CPB is temperature-dependent. As the curing temperature increases, the reactivity generally decreases. The reactivity is also affected by the ambient temperature. The reactivity increases as the atmospheric temperature increases. However, the extent of the effect of the temperature depends on the curing time and is generally more pronounced at the early ages. Furthermore, the presence of sulphate in the pore water of CPB can significantly affect the reactivity of CPB cured at high temperatures (50 °C). The findings of this study will therefore help to better assess and predict the environmental behavior of CPB under various field thermal conditions.
Keywords: Cemented paste backfill; Tailings; Reactivity; Acid mine drainage; Mine; Temperature;

Sequestration of As and Mo in uranium mill precipitates (pH 1.5–9.2): An XAS study by Jocelyn Bissonnette; Joseph Essilfie-Dughan; Brett J. Moldovan; M. Jim Hendry (20-33).
As- and Mo- bearing secondary mineral phases formed during the neutralization of uranium mill wastes require characterization. Previous studies indicate that arsenate and molybdate adsorbed to ferrihydrite are the dominant controls in the tailings materials. A lab-scale plant was employed to characterize secondary precipitates from a variety of ore blends. Through total elemental analysis of precipitates and As and Mo K-edge X-ray absorption spectroscopy, different ratios of contributing phases were determined for each pH stage (4.2, 6.5, and 9.2) of the neutralization process. Overall, arsenate adsorbed to ferrihydrite was the dominant As mineral phase regardless of pH or sample blend (53–77%), with fractional contribution from ferric arsenates, and adsorption to aluminum phases. Molybdate adsorbed to ferrihydrite was the dominant Mo mineral phase, with fractional contribution decreasing with increasing pH (100–69%). The characterization of these phases in the secondary precipitates provides further understanding of the contributing mineral species in tailing facilities.
Keywords: Uranium milling; Precipitates; Arsenic; Molybdenum; Tailings; XAS;

Lepidocrocite-catalyzed Mn(II) oxygenation by air and its effect on the oxidation and mobilization of As(III) by Xu Han; Yan-Fang Wang; Xian-Kai Tang; Hai-Tao Ren; Song-Hai Wu; Shao-Yi Jia (34-41).
Manganese (oxy)hydroxides (MnOX) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnOX in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnOX species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.
Keywords: Mn(II); Abiotic oxidation; As(III) oxidation; Lepidocrocite;

Rates of microbial hydrogen oxidation and sulfate reduction in Opalinus Clay rock by Alexandre Bagnoud; Olivier Leupin; Bernhard Schwyn; Rizlan Bernier-Latmani (42-50).
Hydrogen gas (H2) may be produced by the anoxic corrosion of steel components in underground structures, such as geological repositories for radioactive waste. In such environments, hydrogen was shown to serve as an electron donor for autotrophic bacteria. High gas overpressures are to be avoided in radioactive waste repositories and, thus, microbial consumption of H2 is generally viewed as beneficial. However, to fully consider this biological process in models of repository evolution over time, it is crucial to determine the in situ rates of microbial hydrogen oxidation and sulfate reduction. These rates were estimated through two distinct in situ experiments, using several measurement and calculation methods. Volumetric consumption rates were calculated to be between 1.13 and 1.93 μmol cm−3 day−1 for H2, and 0.14 and 0.20 μmol cm−3 day−1 for sulfate. Based on the stoichiometry of the reaction, there is an excess of H2 consumed, suggesting that it serves as an electron donor to reduce electron acceptors other than sulfate, and/or that some H2 is lost via diffusion. These rate estimates are critical to evaluate whether biological H2 consumption can negate H2 production in repositories, and to determine whether sulfate reduction can consume sulfate faster than it is replenished by diffusion, which could lead to methanogenic conditions.
Keywords: Deep geological repository; Mt Terri Underground Rock Laboratory; Anoxic steel corrosion; Sulfate-reducing bacteria; Geomicrobiology;

Hydrogen sulfide measurements in air by passive/diffusive samplers and high-frequency analyzer: A critical comparison by S. Venturi; J. Cabassi; F. Tassi; F. Capecchiacci; O. Vaselli; S. Bellomo; S. Calabrese; W. D’Alessandro (51-58).
In this study, hydrogen sulfide (H2S) measurements in air carried out using (a) passive/diffusive samplers (Radiello® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H2S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H2S generally varied over 5 orders of magnitude (from 10−1–103 μg/m3), the H2S values measured with the Radiello® traps (H2SR) being significantly higher than the average values measured by the Thermo® 450i during the trap exposure (H2STa), especially when H2S was <30 μg/m3. To test the reproducibility of the Radiello® traps, 8 passive/diffusive samplers were contemporaneously deployed within an 0.2 m2 area in an H2S-contaminated site at Mt. Amiata (Tuscany, Italy), revealing that the precision of the H2SR values was ±49%. This large uncertainty, whose cause was not recognizable, is to be added to that related to the environmental conditions (wind speed and direction, humidity, temperature), which are known to strongly affect passive measurements. The Thermo® 450i analyzer measurements highlighted the occurrence of short-term temporal variations of the H2S concentrations, with peak values (up to 5732 μg/m3) potentially harmful to the human health. The Radiello® traps were not able to detect such temporal variability due to their large exposure time. The disagreement between the H2SR and H2STa values poses severe concerns for the selection of an appropriate methodological approach aimed to provide an accurate measurement of this highly toxic air pollutant in compliance with the WHO air quality guidelines. Although passive samplers may offer the opportunity to carry out low-cost preliminary surveys, the use of the high-frequency H2S analyzer is preferred when an accurate assessment of air quality is required. In fact, the latter provides precise real-time measurements for a reliable estimation of the effective exposure to hazardous H2S concentrations, giving insights into the mechanisms regulating the dispersion of this air pollutant in relation to the meteorological parameters.
Keywords: Active analyzers; Passive/diffusive samplers; Gaseous contaminants; Air quality monitoring; Hydrogen sulfide;

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions by Julie K. Pearce; Grant K.W. Dawson; Alison C.K. Law; Dean Biddle; Suzanne D. Golding (59-76).
Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO2, O2, and NOx, may be present in CO2 streams from coal combustion sources. SO2 and O2 have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO2 fluid may also come into contact with the base of cap-rock after CO2 injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO2 storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO2 reactions with industrial impurities SO2 and O2 at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO2 containing SO2, or SO2 and O2, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO2 dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO2 containing SO2 or in pure supercritical CO2. In the presence of SO2, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO2-CO2 reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO2 was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.Display Omitted
Keywords: CO2 storage; Cap-rock; SO2 and O2 impurities; Gas-water-rock reaction;

A review of the handheld X-ray fluorescence spectrometer as a tool for field geologic investigations on Earth and in planetary surface exploration by Kelsey E. Young; Cynthia A. Evans; Kip V. Hodges; Jacob E. Bleacher; Trevor G. Graff (77-87).
X-ray fluorescence (XRF) spectroscopy is a well-established and commonly used technique in obtaining diagnostic compositional data on geological samples. Recently, developments in X-ray tube and detector technologies have resulted in miniaturized, field-portable instruments that enable new applications both in and out of standard laboratory settings. These applications, however, have not been extensively applied to geologic field campaigns. This study investigates the feasibility of using developing handheld XRF (hXRF) technology to enhance terrestrial field geology, with potential applications in planetary surface exploration missions. We demonstrate that the hXRF is quite stable, providing reliable and accurate data continuously over a several year period. Additionally, sample preparation is proved to have a marked effect on the strategy for collecting and assimilating hXRF data. While the hXRF is capable of obtaining data that are comparable to laboratory XRF analysis for several geologically-important elements (such as Si, Ca, Ti, and K), the instrument is unable to detect other elements (such as Mg and Na) reliably. While this limits the use of the hXRF, especially when compared to laboratory XRF techniques, the hXRF is still capable of providing the field user with significantly improved contextual awareness of a field site, and more work is needed to fully evaluate the potential of this instrument in more complex geologic environments.
Keywords: Handheld X-ray fluorescence spectrometer (hXRF); In situ geochemistry; Planetary field geology; In situ field geologic instrument; Field portable technology; Field spectroscopy;

Bottom ash of trees from Cameroon as fertilizer by Christoph Maschowski; Marie Claudine Zangna; Gwenaëlle Trouvé; Reto Gieré (88-96).
Utilization of wood bottom ash as fertilizer additive contributes to the return of valuable nutrients to agricultural soils, especially when no artificial mineral fertilizer is being used. In general, wood combustion ash is enriched in calcium and potash, and may also contain elevated amounts of zinc, but the concentrations of these elements depend on tree species, part of the tree, harvest season and local soil type. In this study, bottom ash samples from eight different agricultural wood species from Cameroon, Africa were investigated by using X-ray diffraction and atomic absorption spectroscopy to determine the refractory components and the concentrations of selected heavy metals and arsenic. Results show calcite, potassium salts, periclase and quartz as major components. These phase contents were used to calculate major element concentrations, which were subsequently validated by X-ray-fluorescence analysis. The chemical compositions varied within the range of common compositions of wood ashes. Six of the ashes reached sufficient concentrations of calcium to be defined as a “calcium fertilizer”. Pb contents are most variable, ranging from 0.03 to 21.1 mg/kg. Concentrations of Ni, Cu, Zn, Cd, Pb, and As are all lower than the strictest limit concentrations required for wood ash fertilizers and therefore, the studied wood ashes can be used without environmental concern.
Keywords: Biomass; Wood ash; Fertilizer; Soil amendment;

Arsenic mobilization in an oxidizing alkaline groundwater: Experimental studies, comparison and optimization of geochemical modeling parameters by Saeedreza Hafeznezami; Jacquelyn R. Lam; Yang Xiang; Matthew D. Reynolds; James A. Davis; Tiffany Lin; Jennifer A. Jay (97-112).
Arsenic (As) mobilization and contamination of groundwater affects millions of people worldwide. Progress in developing effective in-situ remediation schemes requires the incorporation of data from laboratory experiments and field samples into calibrated geochemical models.In an oxidizing aquifer where leaching of high pH industrial waste from unlined surface impoundments led to mobilization of naturally occurring As up to 2 mg L−1, sequential extractions of solid phase As as well as, batch sediment microcosm experiments were conducted to understand As partitioning and solid-phase sorptive and buffering capacity. These data were combined with field data to create a series of geochemical models of the system with modeling programs PHREEQC and FITEQL. Different surface complexation modeling approaches, including component additivity (CA), generalized composite (GC), and a hybrid method were developed, compared and fitted to data from batch acidification experiments to simulate potential remediation scenarios. Several parameters strongly influence the concentration of dissolved As including pH, presence of competing ions (particularly phosphate) and the number of available sorption sites on the aquifer solids. Lowering the pH of groundwater to 7 was found to have a variable, but limited impact (<63%) on decreasing the concentration of dissolved As. The models indicate that in addition to lowering pH, decreasing the concentration of dissolved phosphate and/or increasing the number of available sorption sites could significantly decrease the As solubility to levels below 10 μg L−1. The hybrid and GC modeling results fit the experimental data well (NRMSE<10%) with reasonable effort and can be implemented in further studies for validation.
Keywords: Arsenic; Mobilization; Groundwater contamination; Remediation; Geochemical modeling; Surface complexation modeling; Acidification; Adsorption; Natural attenuation; PHREEQC; FITEQL;

GEMAS: Source, distribution patterns and geochemical behaviour of Ge in agricultural and grazing land soils at European continental scale by Philippe Négrel; Anna Ladenberger; Clemens Reimann; Manfred Birke; Martiya Sadeghi (113-124).
Agricultural soil (Ap-horizon, 0–20 cm) and grazing land soil (Gr-horizon, 0–10 cm) samples were collected from a large part of Europe (33 countries, 5.6 million km2) as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil mapping project. GEMAS soil data have been used to provide a general view of element mobility and source rocks at the continental scale, either by reference to average crustal abundances or to normalized patterns of element mobility during weathering processes. The survey area includes a diverse group of soil parent materials with varying geological history, a wide range of climate zones, and landscapes.The concentrations of Ge in European soil were determined by ICP-MS after an aqua extraction, and their spatial distribution patterns generated by means of a GIS software.The median values of Ge and its spatial distribution in Ap and Gr soils are almost the same (0.037 vs. 0.034 mg/kg, respectively). The majority of Ge anomalies is related to the type of soil parent material, namely lithology of the bedrock and minor influence of soil parameters such as pH, TOC and clay content. Metallogenic belts with sulphide mineralisation provide the primary source of Ge in soil in several regions in Europe, e.g. in Scandinavia, Germany, France, Spain and Balkan countries.Comparison with total Ge concentrations obtained from the Baltic Soil Survey shows that aqua regia is a very selective method with rather low-efficiency and cannot provide a complete explanation for Ge geochemical behaviour in soil. Additionally, large differences in Ge distribution are to be expected when different soil depth horizons are analysed.
Keywords: Germanium; Agricultural soil; Weathering; Geochemistry;

The geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system in the northern part of the Baltic Artesian Basin (BAB) illustrates how continental glaciations have influenced groundwater systems in proglacial areas. The aquifer system contains water that has originated from various end-members: recent meteoric water, glacial meltwater and relict Na-Cl brine. The saline formation water that occupied the aquifer system prior to the glacial meltwater intrusion has been diluted by meltwaters of advancing-retreating ice sheets. The diversity in the origin of groundwater in the aquifer system is illustrated by a wide variety in δ18O values that range from −11‰ to −22.5‰. These values are mostly depleted with respect to values found in modern precipitation in the area. The chemical and isotopic composition of groundwater has been influenced by mixing between waters originating from different end-members. In addition, the freshening of a previously saline water aquifer due to glacial meltwater intrusion has initiated various types of water-rock interaction (e.g. ion exchange, carbonate mineral dissolution).
Keywords: Palaeohydrogeology; Glacial meltwater; Mixing; Freshening; Ion exchange;

The effect of pH changes on leachability of light and heavy metals from shale drill cuttings generated from unconventional shale gas production was investigated. Cuttings, being the primary byproduct generated from drilling operations, belong to the potentially hazardous type of wastes due to presence of heavy and radioactive elements and remains of drilling fluid. In this regard, assessment of potentially dangerous components (PDCs) from rock waste materials was performed by application of batch leaching tests, which has provided information on the sensitivity of leaching under externally imposed changes in pH (natural or caused by treatment) in specific scenarios. The description of shale rocks mineralogical and chemical properties was performed by means of X-ray fluorescence spectroscopy, diffractometry as well as scintillation spectrometry. The concentrations of released constituents due to the leaching tests were measured by atomic absorption spectrophotometry. Results were compared and discussed accordingly with the waste acceptable criteria of elution limits.Analysis of the substrate revealed that the elemental composition was dominated by light elements, whereas heavy metals were present in trace amounts. However, noticeable release of barium (2.0–4.6%) was also recorded, which has originated from not only rock material but also drill mud. Minor mobility was observed for transition elements such as Cr, Co, Fe, Mn, Ni, Zn, Cu and Pb. Results revealed that drill cuttings follow the requirements for other than hazardous and municipal type of deposition, with exception for barium. Moreover, content of radioactive isotopes fulfill the requirements range of acceptable concentrations.
Keywords: Shale gas; Hydraulic fracturing; Cuttings; Mobility; Leaching batch test at different pH conditions;