Significance of weathering and regolith/landscape evolution for mineral exploration in the NE Albany-Fraser Orogen,Western Australia

The Albany-Fraser Orogen (AFO), southeast Western Australia, is an underexplored, deeply weathered regolith-dominated terrain that has undergone complex weathering associated with various superimposed climatic events. For effective geochemical exploration in the AFO, integrating landscape evolution with mineralogical and geochemical variations of regolith and bedrock provides fundamental understanding of mechanical and hydromorphic dispersion of ore and pathfinder elements associated with the different weathering processes.In the Neale tenement, northeast of the AFO, a residual weathering profile that is 20-55 m thick was developed under warm and humid climatic conditions over undulating Proterozoic sheared granitoids, gneisses, schists and Au-bearing mafic rocks. From the base, the typical weathering profile consists of saprock, lower ferruginous saprolite, upper kaolinitic saprolite and discontinuous silcrete duricrust or its laterally coeval lateritic residuum. These types of duricrusts change laterally into areas of poorly-cemented kaolinitic grits or loose lateritic pisoliths and nodules.Lateritic residuum probably formed on remnant plateaus and was transported mechanically under arid climatic conditions over short distances, filling valleys to the southeast. Erosion of lateritic residuum exposes the underlying saprolite and, together with dilution by aeolian sands, constitutes the transported overburden (2-25 m thick). The reworked lateritic materials cover the preserved silcrete duricrusts in valleys. The lower ferruginous saprolite and lateritic residuum are well developed over mafic and sulphide-bearing bedrocks, where weathering of ferromagnesian minerals and sulphides led to enrichment of Fe, Cu, Ni, Cr, Co, V and Zn in these units. Kaolinitic saprolite and the overlying pedogenic silcrete are best developed over alkali granites and quartzofeldspathic gneisses, which are barren in Au and transition elements, and enriched in silica, alumina, rare earth and high field strength elements.A residual Au anomaly is formed in the lower ferruginous saprolite above a Au -bearing mafic intrusion at the Hercules prospect, south of the Neale tenement, without any expression in the overlying soil (< 20 cm). Conversely, a Au anomaly is recorded in the transported cover, particularly in the uppermost 3 m at the Atlantis prospect, 5 km southwest of the Hercules prospect. No anomalies have been detected in soils using five different size fractions (> 2,000 μm, 2,000-250 μm, 250-53 μm, 53-2 μm and < 2 μm). Therefore, soil cannot be efficiently applied as a reliable sampling medium to target mineralization at the Neale tenement. This is because mechanical weathering was interrupted by seasonal periods of intensive leaching under the present-day surface conditions and/or dilution by recently deposited aeolian sediments which obscure any signature of a potential Au anomaly in soils. Therefore, surface soil sampling should extend deeper than 20 cm to avoid dilution by aeolian sands and seasonal leaching processes. Regolith mapping and the distinction between the residual and transported weathering products are extremely significant to follow the distal or proximal mineralization.     

Development of unusual rock weathering features in the Cordillera Blanca,Peru

Mylonite textures in granodiorite boulders are responsible for higher rates of surface denudation of host rocks and the progressive development of unusual rock weathering features, termed weathering posts. These textures are characterized by smaller grain sizes, higher biotite content, and a higher biotite axial ratio in host rocks relative to weathering posts. Elemental concentrations do not show a significant difference between weathering posts and the host rocks in which they are found, and this reflects the absence of a weathering residue on the rock surfaces. Chemical weathering loosens the bonds between mineral grains through the expansion of biotite, and the loosened grains fall off or are blown off the boulder surface and continue their chemical alteration in the surrounding soil. The height of weathering posts on late Quaternary moraines increases at a linear rate of ~ 1.45 ± 0.45 cm (1000 yr)^? 1 until post heights reach the diameter of host rocks. Such a rate of boulder denudation, if unrecognized, would generate significant errors (> 20%) in cosmogenic exposure ages for Pleistocene moraines. Given the paucity of boulders with diameters that significantly exceed 1.5 m, the maximum age of utility of weathering posts as a numeric age indicator is ~ 100 ka.     

Biogeochemical weathering of serpentinites: An examination of incipient dissolution affecting serpentine soil formation

Serpentinite rocks, high in Mg and trace elements including Ni, Cr, Cd, Co, Cu, and Mn and low in nutrients such as Ca, K, and P, form serpentine soils with similar chemical properties resulting in chemically extreme environments for the biota that grow upon them. The impact of parent material on soil characteristics is most important in young soils, and therefore the incipient weathering of serpentinite rock likely has a strong effect on the development of serpentine soils and ecosystems. Additionally, porosity generation is a crucial process in converting rock into a soil that can support vegetation. Here, the important factors affecting the incipient weathering of serpentinite rock are examined at two sites in the Klamath Mountains, California. Serpentinite-derived soils and serpentinite rock cores were collected in depth profiles from each sampling location. Mineral dissolution in weathered serpentinite samples, determined by scanning electron microscopy, energy dispersive spectrometry, electron microprobe analyses, and synchrotron microXRD, is consistent with the order, from most weathered to least weathered: Fe-rich pyroxene > antigorite > Mg-rich lizardite > Al-rich lizardite. These results suggest that the initial porosity formation within serpentinite rock, impacting the formation of serpentine soil on which vegetation can exist, is strongly affected both by the presence of non-serpentine primary minerals as well as the composition of the serpentine minerals. In particular, the presence of ferrous Fe appears to contribute to greater dissolution, whereas the presence of Al within the parent rock appears to contribute to greater stability. Iron-oxidizing bacteria present at the soil–rock interface have been shown in previous studies to contribute to the transition from rock to soil, and soils and rock cores in this study were therefore tested for iron-oxidizing bacteria. The detection of biological iron oxidation in this study indicates that the early alteration of these Fe-rich minerals may be mediated by iron-oxidizing bacteria. These findings help provide insight into the incipient processes affecting serpentinite rock weathering, important to the development of extreme serpentine soils and the biota that grow on them.     

Chemical weathering rates in the Alaknanda–Bhagirathi river basins in Himalayas,India

The Alaknanda and Bhagirathi rivers flow through the Higher and Lesser Himalayas and confluence at Devprayag, which represents the origin of the Ganga (or Ganges) river. In the present study, a vast number of temporal and spatial samples of the river waters were collected and analyzed for major cations and anions. In addition, more recent and time series water flow data have been obtained and based on these inputs, a more refined dissolved flux rates have been estimated. The Alaknanda and Bhagirathi rivers show significant variations in chemical compositions during different seasons. Carbonate rock weathering is responsible for more than 70% of the chemical compositions in the river waters. The chemical weathering rates show seasonal variations and are much higher during non-monsoon season. The dissolved flux of Alaknanda river is much higher (1.80 × 10⁶ tons yr^?1) as compared to the Bhagirathi river (0.34 × 10⁶ tons yr^?1). The chemical weathering rates in the basin vary between 85 and 155 tons km^?2 yr^?1, which is significantly higher compared to the global average of ～24 tons km^?2 yr^?1.     

Preliminary estimates of regolith generation and mobility in the Susquehanna Shale Hills Critical Zone Observatory,Pennsylvania, using meteoric 10Be

This study seeks to quantify the rate and timing of regolith generation in the Critical Zone at the Susquehanna Shale Hills Critical Zone Observatory (SSHO). Meteoric ¹⁰Be depth profiles were determined using measurements from 30 hillslope soil and bedrock core samples in an effort to constrain ¹⁰Be inventories. The SSHO is located in the temperate climate zone of central Pennsylvania and comprises a first-order watershed developed entirely on a Fe-rich, organic-poor, Silurian-aged shale. Two major perturbations to the landscape have occurred at SSHO in the geologically recent past, including significant and sustained periglacial activity until after the retreat of the Laurentide ice sheet (～21 ka) and deforestation during early colonial land-use. Bulk soil samples (n = 16) were collected at three locations along a planar hillslope on the southern ridge of the catchment, representing the ridge top, mid-slope and valley floor. Rock chip samples (n = 14) were also collected from a 24 m deep core drilled into the northern ridge top. All meteoric ¹⁰Be concentration profiles show a declining trend with depth, with most of the ¹⁰Be retained in the uppermost decimeters of the soil. Meteoric ¹⁰Be inventories are higher at the mid-slope and valley floor sample sites, at 3.71 ± 0.02 × 10¹⁰ at/cm² and 3.69 ± 0.02 × 10¹⁰ at/cm², than at the ridge top site (1.90 ± 0.01 × 10¹⁰ at/cm²). The ¹⁰Be inventory at the convex ridge top site implies a minimum residence time of ～10.6 ka, or if erosion is steady, an erosion rate of 19.4 ± 0.2 m/My.     

Comparison of dissolved inorganic and organic carbon yields and fluxes in the watersheds of tropical volcanic islands,examples from Guadeloupe (French West Indies)

Organic matter is an important factor that cannot be neglected when considering global carbon cycle. New data including organic matter geochemistry at the small watershed scale are needed to elaborate more constrained carbon cycle and climatic models. The objectives are to estimate the DOC and DIC yields exported from small tropical watersheds and to give strong constraints on the carbon hydrodynamic of these systems. To answer these questions, we have studied the geochemistry of eleven small watersheds around Basse-Terre volcanic Island in the French West Indies during different hydrological regimes from 2006 to 2008 (i.e. low water level versus floods). We propose a complete set of carbon measurements, including DOC and DIC concentrations, δ¹³C data, and less commonly, some spectroscopic indicators of the nature of organic matter. The DOC/DIC ratio varies between 0.07 and 0.30 in low water level and between 0.25 and 1.97 during floods, indicating that organic matter is mainly exported during flood events. On the light of the isotopic composition of DOC, ranging from ? 32.8 to ? 26.2‰ during low water level and from ? 30.1 to ? 27.2‰ during floods, we demonstrate that export of organic carbon is mainly controlled by perennial saprolite groundwaters, except for flood events during which rivers are also strongly influenced by soil erosion. The mean annual yields ranged from 2.5 to 5.7 t km^? 2 year^? 1 for the DOC and from 4.8 to 19.6 t km^? 2 year^? 1 for the DIC and exhibit a non-linear relationship with slopes of watersheds. The flash floods explain around 60% of the annual DOC flux and between 25 and 45% of the DIC flux, highlighting the important role of these extreme meteorological events on global carbon export in small tropical volcanic islands. From a carbon mass balance point of view the exports of dissolved carbon from small volcanic islands are important and should be included in global organic carbon budgets.     

Water–granite interaction: Clues from strontium,neodymium and rare earth elements in soil and waters

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the ⁸⁷Sr/⁸⁶Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed ⁸⁷Sr/⁸⁶Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.     

A new genetic model for the Triassic Yangyang iron-oxide–apatite deposit,South Korea: Constraints from in situ U–Pb and trace element analyses of accessory minerals

The Yangyang iron-oxide–apatite deposit in South Korea has undergone multiple episodes of igneous activity, deformation, hydrothermal alteration, and iron-oxide–apatite (IOA) mineralization. The iron orebodies occur as concordant- to discordant-layered lenticular or massive magnetite and/or magnetite–pyrite ores. The iron mineralization occurs along a N–S-trending shear zone within the Yangyang syenite, which experienced both early ductile and later brittle deformations. Alteration was caused mainly by the injection of hydrothermal fluid through the shear zone, leading to Fe–P mineralization. We recognize multiple stages of alteration in the Yangyang deposit, based on a paragenesis that is defined by distinct mineral assemblages including Na–Ca–K alteration phases (e.g., albite, diopside, actinolite, and biotite) and accessory minerals containing high field strength elements (e.g., apatite, sphene, allanite, and monazite). The alteration around the magnetite ore body shows an evolutionary trend from Ca (–Na) alteration, through K to phyllic alterations. The Fe–P mineralization is associated with the Ca–K and K alteration products. The iron orebodies are hosted by deformed and altered syenite, which intruded the Paleoproterozoic gneiss complexes at 233 ± 1 Ma (SHRIMP U–Pb zircon age) in a post-collisional tectonic setting. LA-ICP-MS U–Pb dating of REE-rich sphene and apatite from the iron ores and alteration products yields Fe mineralization ages of 216 ± 3 Ma (sphene) and 212 ± 13 Ma (apatite). This is the first time, which IOA-type mineralization in the Korean Peninsula was dated as Triassic age related to post-collisional magmatism within the Gyeonggi Massif, South Korea. The U–Pb system was subsequently reset (208 ± 3 Ma–sphene and 151 ± 13 Ma–apatite) by Jurassic and Cretaceous magmatism. This unique geological evolution was responsible for Mesozoic metal enrichment and remobilization into suitable structural traps in the Yangyang district.     

Use of Sr isotopes as a tool to decipher the soil weathering processes in a tropical river catchment,southwestern India

River water composition (major ion and ⁸⁷Sr/⁸⁶Sr ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L⁻¹) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L⁻¹), with radiogenic ⁸⁷Sr/⁸⁶Sr isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and ⁸⁷Sr/⁸⁶Sr and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotopic ratio show strong seasonal variation in the river water, i.e., low SiO₂/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO₂/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin.     

Soil formation in Phobjikha Valley,Central Bhutan with special regard to the redistribution of loessic sediments

Soil development and landscape evolution were studied in the basin-shaped Phobjikha Valley at 2900–3200 m a.s.l., to the west of the Black Mountain Range, West Central Bhutan. The local environmental setting with strong along-valley winds, frequent freeze–thaw cycles, extensive dry periods and sparse vegetation cover seems to encourage the generation and short-distance transport of silt-sized particles. The effects of this process are evidenced in the smooth valley morphology and in the nature of the examined pedons. Their involvement in continuing redistribution of local sediments is reflected by a homogeneous silty-clayey and stone-free texture, varying profile depths, buried topsoils and weakly developed recent A horizons. In protected locations, in situ weathering of metamorphic parent materials results in alu-andic features with bulk densities <0.9 g cm^?3, (Al_o + ½Fe_o) > 2%, and phosphate retention >95%. Dominance by Al-hydroxy interlayered clay minerals and large amounts of well-crystallised iron oxides indicate an advanced stage of weathering. In areas of preferred eolian deposition, argic and ferralic features emerge, with clay contents of up to 60% and surface areas of >50 m² g^?1. Under forest, umbric horizons can develop. CEC_eff is below 10 cmol_c kg^?1 at all sites. Cluster and factor analyses of soil chemical and physical parameters confirm the redistribution of local sediments as a dominant factor behind the measured variables. No clear indication of glacial activities in the area was found, whereas the massive silty sediments in the lower parts of most profiles, the presence of debris slopes, and the asymmetric cross sections of the side valleys suggest periglacial conditions. Buried topsoils dated at about 2000 conventional ¹⁴C years BP indicate a weakening or absence of sediment influx under wetter conditions towards the end of the Holocene climate optimum. Charcoal on top of paleosols suggests that human activities of deforestation, grazing and arable agriculture may have contributed to the reactivation of local sediment redistribution until today.     

Natural spatial and temporal variations in groundwater chemistry in fractured,sedimentary rocks: scale and implications for solute transport

Natural tracers (major ions, δ¹⁸O, and O₂) were monitored to evaluate groundwater flow and transport to a depth of 20 m below the surface in fractured sedimentary (primarily shale and limestone) rocks. Large temporal variations in these tracers were noted in the soil zone and the saprolite, and are driven primarily by individual storm events. During nonstorm periods, an upward flow brings water with high TDS, constant δ¹⁸O, and low dissolved O₂ to the water table. During storm events, low TDS, variable δ¹⁸O, and high dissolved O₂ water recharges through the unsaturated zone. These oscillating signals are rapidly transmitted along fracture pathways in the saprolite, with changes occurring on spatial scales of several meters and on a time scale of hours. The variations decreased markedly below the boundary between the saprolite and less weathered bedrock. Variations in the bedrock units occurred on time scales of days and spatial scales of at least 20 m. The oscillations of chemical conditions in the shallow groundwater are hypothesized to have significant implications for solute transport. Solutes and colloids that adsorb onto aquifer solids can be released into solution by decreases in ionic strength and pH. The decreases in ionic strength also cause thermodynamic undersaturation of the groundwater with respect to some mineral species and may result in mineral dissolution. Redox conditions are also changing and may result in mineral dissolution/precipitation. The net result of these chemical variations is episodic transport of a wide range of dissolved solutes or suspended particles, a phenomenon rarely considered in contaminant transport studies.     

Soil-geochemical factors controlling the distribution and oral bioaccessibility of nickel,vanadium and chromium in soil

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.     

Tectonics and thermal structure of western Satpura,India

Increased seismicity and occurrences of hot springs having surface temperature of 36–58 °C are observed in the central part of India (74–81° E, 20–25° N), where the NE trending Middle Proterozoic Aravalli Mobile Belt meets the ENE trending Satpura Mobile Belt. Earlier Deep Seismic Sounding (DSS) studies along Thuadara-Sendhwa-Sindad profile in the area has showed Mesozoic Sediments up to around 4 km depth covered by Deccan Trap and the Moho depth with a boundary velocity (P_n) of 8.2 km/s. In the present study, surface heat flow of 48 ± 4 mW m^?2 has been estimated based on P_n velocity, which agrees with the value of heat flow of 52 ± 4 mW m^?2 based on Curie point isotherms estimates. The calculated temperature-depth profile shows temperature of 80–120 °C at the basement, which is equivalent to oil window temperature in Mesozoic sediments and around 570–635 °C at Moho depth of 38–43 km and the thermal lithosphere is about 110 km thick, which is comparatively higher than those of adjoining regions. The present study reveals the brittle–ductile transition zone at 14–41 km depth (temperature around 250–600 °C) where earthquake nucleation takes place.     

Constraints of Sr isotopic compositions of apatite and carbonates on the origin of Fe and Cu mineralizing fluids in the Lala Fe-Cu-(Mo,LREE) deposit,SW China

Numerous Fe-Cu deposits with mineralization styles similar to iron oxide-copper gold (IOCG) deposits form the Kangdian Fe-Cu metallogenic province, southwestern (SW) China. As one of the largest deposits in the region, the ~ 1.0 Ga Lala Fe-Cu deposit is hosted in a Paleoproterozoic volcanic-sedimentary succession named the Hekou Group which is alternately intruded by ~ 1.0 Ga doleritic plutons. This deposit has a paragenetic sequence evolving from Stage I of Na-alteration to Stage II of Fe mineralization, and finally to Stage III of Cu-(Mo, REE) mineralization, coeval with mafic-felsic intra-plate magmatism in the region. This study conducted in-situ Sr isotopic analyses on apatite and carbonate, aiming to resolve the long controversial issue regarding the origin of the Fe and Cu mineralizing fluids in the deposit. Apatite of Stage II has ⁸⁷Sr/⁸⁶Sr ratios varying from 0.71380 to 0.72733, much higher than those of synchronous igneous rocks in the region (0.7074 to 0.7091), but similar to the Paleoproterozoic host rocks (0.71368 to 0.71837 at ~ 1.0 Ga). This similarity indicates that radiogenic Sr of the Fe mineralizing fluid was dominantly sourced from the host rocks. Apatite and calcites of Stage III have ⁸⁷Sr/⁸⁶Sr ratios (0.75758–0.79293) much higher than apatite of Stage II and the host rocks but similar to the Archean basement rocks (as high as 0.80 at ~ 1.0 Ga) beneath the cover of the Yangtze Block, suggesting that the highly radiogenic Sr isotopic composition of the Cu mineralizing fluid was mainly inherited from the old basement rocks. In combination with previous C-O-S isotopic data indicating a magma-hydrothermal origin, it was suggested that the Fe mineralizing fluid was exsolved from a mafic magma that generated the ~ 1.0 Ga doleritic plutons, and inherited radiogenic Sr from the host rocks during fluid-rock interaction. By contrast, the Cu mineralizing fluid might have been sourced from another pulse of magmatic, Cu-Mo-REE- and CO₂-rich fluid which have once interacted with Archean basement rocks prior to mineralization. The source of such a Cu-Mo-REE-rich fluid was not well constrained in current study but was inferred to be exsolved from a hidden felsic magma. We propose that intrusions of the bimodal magmas in Kangdian are responsible for regional hydrothermal circulation which led to Fe-Cu-(Mo, REE) mineralization in the Kangdian province.     

Fractionation of U,Th, Ra and Pb from boreal forest soils by sequential extractions

To determine the mobility of natural radionuclides in boreal forest soil, a five-step sequential extraction procedure was carried out on soil samples taken from various depths down to 3 m on Olkiluoto Island, Finland, where there are plans to construct a spent nuclear fuel disposal repository in the bedrock. The extracted fractions studied were exchangeable, acid-soluble, reducible, oxidizable and tightly bound. It was found that the extractability of most of the radionuclides studied was dependent on the sample grain size and depth. All the elements were concentrated in the smallest grain size samples (<0.063 mm). The extraction behaviour of Th, however, did not vary with sample depth, and only about 10% of the Th was extracted by the time of the final extraction step. Stable Pb and ²¹⁰Pb, as well as Ba and Ra concentrations were strongly correlated in the extractions. Radium and Ba were leached more readily than the other elements; approximately 17% of the total Ra was found in the first fraction extracted, representing exchangeable ions. Uranium was more mobile in the topsoil horizons than in the lower horizons. In the topsoil samples, an average of 51% of the extractable U was leached in the second extraction step, representing the elements soluble in weak acids, whereas only 13% of the U in the subsoil samples was extracted in this step. This is probably due to changes in soil redox conditions lower down the soil profile. The extraction behaviour of Pb and Fe also suggests the presence of more reducing conditions in the deeper soil horizons, because the percentage of extractable Pb and Fe in the oxidizable fraction increased with sample depth.     

Environmental assessment of abandoned mine tailings in Adak,Västerbotten district (northern Sweden)

Sulfide-rich mine tailings in Adak that are exposed to weathering cause acid mine drainage characterized by low pH (2–4) and high SO₄ (up to 800 mg L⁻¹). Surface water, sediment and soil samples collected in this study contain higher concentrations of As, Cu, Fe and Zn, compared to the target and/or intervention limits set by international regulatory agencies. In particular, high As concentrations in water (up to 2900 μg L⁻¹) and sediment (up to 900 mg kg⁻¹) are of concern. There is large variability in trace element concentrations, implying that both physical (grain size) and chemical factors (pH, secondary phases as sulfides, Al-oxides or clay minerals) play an important role in their distribution. The low pH keeps the trace elements dissolved, and they are transported farther downstream. Trace element partition coefficients are low (log K_d = 0.3–4.3), and saturation indices calculated with PHREEQC are <0 for common oxide and sulfidic minerals. The sediment and soil samples indicate an enhanced pollution index (up to 17), and high enrichment factors for trace elements (As up to 38,300; Zn up to 800). Finally, leaves collected from different plant types indicate bioaccumulation of several elements (As, Al, Cu, Fe and Zn). However, some of the plants growing in this area (e.g., Salix, Equisétum) are generally resistant to metal toxicity, and hence, liming and phytoremediation could be considered as potential on-site remediation methods.     

An experimental model approach of biologically-assisted silicate dissolution with olivine and Escherichia coli – Impact on chemical weathering of mafic rocks and atmospheric CO2 drawdown

Chemical weathering of Mg, Ca-silicates and alumino-silicates contributes significantly to the drawdown of atmospheric CO₂ over long time scales. The present work focuses on how this mode of weathering may change in the presence of free-living bacteria in oligotrophic waters, which compose most of the surface freshwaters of the Earth. Forsterite (Fo90) was reacted for 1 week with a stable Escherichia coli population in water maintained at 37 °C and neutral pH in a batch reactor. Control samples with suspensions of pure olivine powders and E. coli cells in pure water were also used for reference. Olivine controls reproduce the Mg, Si and Fe release in solutions predicted from rates published in the literature with pH shifts of less than 0.5 unit. After 1 week, under abiotic conditions, weathered surfaces are enriched in Fe and Fe³⁺ relative to the initial composition of the mineral. Bacterial controls (without minerals) show decreasing Eh with increasing cell concentrations (−50 mV with 7 × 10⁷ cells/mL and −160 mV with 8 × 10⁸ cells/mL). Magnesium concentrations in bacterial control solutions are in the μg/L range and can be accounted for by the release of Mg from dead cells. More than 80% of the cells were still alive after 1 week. The solutions obtained in the experiments in which olivine reacts in the presence of cells show Mg and Si concentrations a few tens of percent lower than in the mineral control samples, with a prominent depletion of Fe(III) content of the mineral surfaces. Magnesium mass balance discounts both significant bacterial uptake and inhibition of the Mg dissolution rates as a consequence of changing pH and Eh. Coating by bacterial cell layers is also negligible. E. coli reduces the chemical weathering of olivine. This study infers that the presence of free-living Proteobacteria, a prevalent group of subsurface bacteria, should decrease the amount of riverine Mg released by chemical weathering of mafic rocks.     

Factors affecting the dissolution kinetics of volcanic ash soils: dependencies on pH,CO2, and oxalate

Laboratory experiments were conducted with volcanic ash soils from Mammoth Mountain, California to examine the dependence of soil dissolution rates on pH and CO₂ (in batch experiments) and on oxalate (in flow-through experiments). In all experiments, an initial period of rapid dissolution was observed followed by steady-state dissolution. A decrease in the specific surface area of the soil samples, ranging from 50% to 80%, was observed; this decrease occurred during the period of rapid, initial dissolution. Steady-state dissolution rates, normalized to specific surface areas determined at the conclusion of the batch experiments, ranged from 0.03 μmol Si m⁻² h⁻¹ at pH 2.78 in the batch experiments to 0.009 μmol Si m⁻² h⁻¹ at pH 4 in the flow-through experiments. Over the pH range of 2.78–4.0, the dissolution rates exhibited a fractional order dependence on pH of 0.47 for rates determined from H⁺ consumption data and 0.27 for rates determined from Si release data. Experiments at ambient and 1 atm CO₂ demonstrated that dissolution rates were independent of CO₂ within experimental error at both pH 2.78 and 4.0. Dissolution at pH 4.0 was enhanced by addition of 1 mM oxalate. These observations provide insight into how the rates of soil weathering may be changing in areas on the flanks of Mammoth Mountain where concentrations of soil CO₂ have been elevated over the last decade. This release of magmatic CO₂ has depressed the soil pH and killed all vegetation (thus possibly changing the organic acid composition). These indirect effects of CO₂ may be enhancing the weathering of these volcanic ash soils but a strong direct effect of CO₂ can be excluded.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

The relationship between fluid flow and mineral weathering in heterogeneous unsaturated porous media: A physical and geochemical characterization of a waste-rock pile

The relationships between factors that control subsurface flow and the timing, duration, and intensity of acidity generation and leaching of metals from waste-rock dumps are investigated. A 12 m high waste-rock pile that had been constructed in 1994 at Key Lake, Saskatchewan, Canada was disassembled, sampled and characterized in 2000. Physical properties that control water flow were characterized by measuring soil–water suction, volumetric water content, and the grain-size distribution at 60 randomized sites within the pile. Grain-size distribution was also measured at an additional 20 grid locations within the pile. Paste pH, pore-water geochemistry, mineralogy, and water-soluble extractions were used to investigate geochemical processes and sulfide oxidation at each of the 20 grid locations. A field-based soil–water characteristic curve could not be developed from the spatially variable and hysteretic field data; consequently, the grain-size distribution was used as a relative measure of subsurface flow and of the tendency to contain water under unsaturated conditions. The geochemical characterization demonstrated that marcasite underwent preferential weathering relative to pyrite and chalcopyrite, that dolomite was the main buffering carbonate mineral, and that gypsum, jarosite, and Fe oxyhydroxides were the main secondary (supergene) minerals. The pore waters contained up to 78,000 mg L⁻¹ SO₄, 690 mg L⁻¹ Ni and 1400 mg L⁻¹ U (800, 11.7 and 6 mM, respectively), suggesting that significant weathering had occurred. The pore water chemistry varied considerably between sampling sites. However, neither a correlation of pore-water chemistry with grain-size distribution nor a spatial relationship within the sampled grid was discernible.