Groundwater evolution, chemical sedimentation and carbonate brine formation on an island in the Okavango Delta swamp, Botswana

The Okavango Delta of semi-arid northern Botswana is a large alluvial fan (22,000 km²) covered by permanent and seasonal swamps from which 96% of the annual discharge is lost by evapotranspiration. Many small islands (1ha) within the permanent swamps are the sites of accumulation of sodium carbonate salts and many contain saline pans. The associated alkaline soils are toxic to vegetation. An understanding of the processes involved in alkalinization could be of potential benefit to long-term conservation planning in this unique ecosystem. The relation between soil chemistry and mineralogy, and swamp and groundwater chemistry were investigated on an island in the swamps. The study revealed that the water table beneath the island is depressed and swamp water enters the groundwater regime of the island from the margins and below, and flows toward the centre. The water becomes progressively more saline, initially owing to transpiration by trees and ultimately by evaporation in the central parts of the island. As a result of increasing salinity, amorphous SiO₂ and magnesium calcite precipitate in the soils beneath the marginal zone of the island, raising the land surface, while the more soluble alkali carbonates are concentrated in the centre of the island as surface crusts and brine ponds. Leaching of these salts into the soil during the rainy season and gravity-driven flow of saline brines in the dry season causes the downward movement of Al and Fe in the central zone of the island. K-feldspar and possibly amorphous allophane develop in the deeper soils under the central zone of the island.     

Silica Springs,Tongariro National Park,New Zealand—analyses of the spring water and characterisation of the alumino-silicate deposit

The creamy-white deposit in the stream bed below Silica Springs outlet on Mount Ruapehu, Tongariro National Park, New Zealand, has been identified as a hydrous, X-ray-amorphous, aluminosilicate (allophane). The SiO₂/Al₂O₃ mole ratio varies from close to one, to close to two. The elements K, Ca, Mn and Fe are present in low concentrations relative to those in allophanic soil clays, and tend to increase in concentration downstream from where the deposit first occurs. The concentration of S decreases downstream from 0.5% to 0.1%. Surface areas of samples, measured by the ethylene glycol desorption method, are about 200–300 m²/g. The outlet water at Silica Springs contains low dissolved solids and is undersaturated with respect to amorphous silica, but is supersaturated with respect to several alumino-silicate minerals (of which allophane may be considered the precursor) and with respect to CO₂. Gas bubbling at the outlet contains about 10% CO₂ which has a δC¹³_PDB value of ?7.5%..Silica Springs water is derived from the addition of geothermal CO₂ (and possibly H₂S) to near-surface meteoric water from the lava flow above the outlet, and the chemical attack of this water on the andesitic rocks and soil through which it passes. The pH of water at Silica Springs increases from 5.45 at the outlet, to 5.90 where deposition first occurs, to 6.80 below the region of maximum deposition. This rise in pH correlates with loss of excess CO₂ in turbulent regions of the stream, and, through surface charge effects, is probably an important influence on the site of deposition, which begins approx. 100m downstream from the outlet.     

Navajo Sandstone–brine–CO<Subscript>2</Subscript> interaction: implications for geological carbon sequestration

The injection of CO₂ into deep saline aquifers is being considered as an option for greenhouse gas mitigation. However, the response of an aquifer to the injected CO₂ is largely unknown. Experiments involving the reaction of Navajo Sandstone with acidic brine were conducted at 200°C and 25 or 30 MPa to evaluate the extent of fluid–rock interactions. The first experiment examined sandstone interaction with CO₂-impregnated brine; the second experiment examined sandstone dissolution in CO₂-free acidic brine; the third one is carried out in a mixed-flow reactor and designed to measure sandstone dissolution rates based on time-series Si concentrations. The solution chemistry data indicate that the SiO₂(aq) increases gradually and pH increases slowly with reaction progress. Silicate minerals in the sandstone display textures (dissolution features, secondary mineralization), indicating that these phases are reacting strongly with the fluid. Dissolution of feldspars and conversion of smectite to illite are likely to be the two reactions that contribute to the release of SiO₂(aq). The product minerals present at the end of the experiments are illite, illite/smectite, allophane, and carbonate minerals (for the CO₂-charged system). Dissolved CO₂ is likely to acidify the brine and to provide a source of carbon for the precipitation of carbonate minerals. Mineral trapping through the precipitation of carbonate minerals is favored thermodynamically and was observed in the experiments. The chemical reactions likely increase the bulk porosity of the sandstone due to dissolution of silicate minerals. However, allophane and illite/smectite fill voids in sandstone grains. There is no evidence for the removal of clay coatings due to chemical reactions. It is uncertain whether the mechanical forces near an injection well would mobilize the smectite and allophane and clog pore throats. Trace amounts of metals, including Cu, Zn, and Ba, were mobilized.     

Groundwater composition,hydrochemical evolution and mass transfer in a regional detrital aquifer (Baza basin,southern Spain)

The physical–chemical characteristics of the groundwater in the Baza–Caniles detrital aquifer system indicate that a wide diversity of hydrochemical conditions exists in this semiarid region, defining geochemical zones with distinct groundwater types. The least mineralized water is found closest to the main recharge zones, and the salinity of the water increases significantly with depth towards the center of the basin. Geochemical reaction models have been constructed using water chemistry data along flow paths that characterize the different sectors of the aquifer system, namely: Quaternary aquifer, unconfined sector and shallow and deep confined sectors of the Mio–Pliocene aquifer. Geochemical mass–balance calculations indicate that the dominant groundwater reaction throughout the detrital system is dedolomitisation (dolomite dissolution and calcite precipitation driven by gypsum dissolution); this process is highly developed in the central part of the basin due to the abundance of evaporites. Apart from this process, there are others which influence the geochemical zoning of the system. In the Quaternary aquifer, which behaves as a system open to gases and which receives inputs of CO₂ gas derived from the intensive farming in the area, the interaction of the CO₂ with the carbonate matrix of the aquifer produces an increase in the alkalinity of the water. In the shallow confined sector of the Mio–Pliocene aquifer, the process of dedolomitisation evolves in a system closed to CO₂ gas. Ca²⁺/Na⁺ cation exchange and halite dissolution processes are locally important, which gives rise to a relatively saline water. Finally, in the deep confined sector, a strongly reducing environment exists, in which the presence of H₂S and NH⁺₄ in the highly mineralized groundwater can be detected. In this geochemical zone, the groundwater system is considered to be closed to CO₂ gas proceeding from external sources, but open to CO₂ from oxidation of organic matter. The geochemical modeling indicates that the chemical characteristics of this saline water are mainly due to SO₄ dissolution, dedolomitisation and SO₄ reduction, coupled with microbial degradation of lignite.     

14C in bicarbonate and dissolved organics—a useful tracer?

The tunnel excavation at the Äspö Hard Rock Laboratory opened several fracture zones at various depths in the crystalline bedrock. One of these zones is the `Redox zone', a vertical fracture zone penetrated at 70 m depth. Except for the tunnel intersection, several boreholes were drilled to intersect the zone at various depths (ranging from 5 to 70 m) and distances from the tunnel. The response in groundwater chemistry to the opening of the zone has been monitored in these boreholes during 3 a, starting in 1991 and for the boreholes at 70 m depth the monitoring is still ongoing. The water chemistry during this monitoring can be largely explained by mixing between fresh water and native saline groundwater (4900 ppm Cl⁻). An increase in HCO⁻₃ was recorded, which was interpreted as due to anaerobic respiration. This was supported by ¹⁴C-contents in dissolved organic Carbon and HCO⁻₃, indicating that recent organic C is transported into the zone and oxidised to CO₂. This study exemplifies the use of ¹⁴C-analyses of HCO⁻₃ in order to trace different C sources contributing to the HCO⁻₃ in the groundwater. Three sources were identified: (1) dissolved CO₂, dominantly soil-CO₂ possibly with some contribution of atmospheric CO₂; (2) dissolution of calcite, with low ¹⁴C content, which dominantly occurs in the near-surface recharge area; and (3) oxidation of organic material through anaerobic respiration. Corrections for ¹⁴C and HCO⁻₃ in the native saline water made it possible to determine 2 different fresh water components corresponding to different flow paths. The C isotope data are in accordance with the results from the tracer test and the groundwater flow model, and support that the extensive build up of HCO₃⁻ does not mainly takes place locally within the zone but is transported into the zone by dominantly lateral flow. The results from the monitoring showed that new hydrochemical stability is established, which also comprises the interaction between the organic and inorganic C cycles.     

Geochemical detection of carbon dioxide in dilute aquifers

Background  

Carbon storage in deep saline reservoirs has the potential to lower the amount of CO₂ emitted to the atmosphere and to mitigate global warming. Leakage back to the atmosphere through abandoned wells and along faults would reduce the efficiency of carbon storage, possibly leading to health and ecological hazards at the ground surface, and possibly impacting water quality of near-surface dilute aquifers. We use static equilibrium and reactive transport simulations to test the hypothesis that perturbations in water chemistry associated with a CO₂ gas leak into dilute groundwater are important measures for the potential release of CO₂ to the atmosphere. Simulation parameters are constrained by groundwater chemistry, flow, and lithology from the High Plains aquifer. The High Plains aquifer is used to represent a typical sedimentary aquifer overlying a deep CO₂ storage reservoir. Specifically, we address the relationships between CO₂ flux, groundwater flow, detection time and distance. The CO₂ flux ranges from 10³ to 2 × 10⁶ t/yr (0.63 to 1250 t/m²/yr) to assess chemical perturbations resulting from relatively small leaks that may compromise long-term storage, water quality, and surface ecology, and larger leaks characteristic of short-term well failure.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

Saline groundwater seepage zones and their impact on soil and water resources in the Spicers Creek catchment,central west,New South Wales,Australia

Saline seepage zone development and hence dryland salinity is a major environmental problem which many arid to semiarid landscapes in Australia are experiencing. Due to the geological complexity of the regional aquifer system and the heterogeneous nature of the local groundwater system, each groundwater seepage zone in the Spicers Creek catchment, central west, New South Wales, Australia possesses different mechanisms which control its development. Saline seepage zones have formed adjacent to a fault zone, and two experimental sites were established through these groundwater discharge zones to understand geochemical processes which have led to the development of soil sodicity, gully erosion and the flushing of salts into the surface water systems. Seepage zone groundwaters contain a distinctive geochemical signature with elevated concentrations of Na, Cl, HCO₃, Ca, Sr, B, As and Li. The mixing of deep saline groundwaters together with ion exchange processes lead to a distinctive seepage zone groundwater chemistry being developed. Altering the landscape features within this rural groundwater system has developed water toxicity for crops, soil sodicity leading to land degradation, and waterlogging problems.     

Geochemistry of regional aquifer systems hosted by carbonate-evaporite formations in Umbria and southern Tuscany (central Italy)

In central Italy Mesozoic carbonates represent the principal reservoir of freshwater of the region. The hydrogeological setting is linked to the geological evolution of the Apennine chain and is generally characterised by a lower aquifer and one or more shallower aquifers separated by thin aquicludes. In these systems, groundwater composition is the result of a complex array of regional and local geochemical processes. The main geochemical processes are the dissolution of calcite, the influx of deeply derived CO₂ related to a regional process of mantle degassing, dedolomitization and mixing with deep saline fluids. The occurrence of saline fluids, characterised by a Na–Cl(HCO₃) composition, is related to the presence of a deep regional aquifer at the base of Mesozoic carbonates. The extremely high pCO₂ values computed for the saline waters suggest that the deep aquifer is also a structural trap for the mantle derived CO₂ during its ascent towards the surface. In central Italy, geological and geophysical data highlight the presence of two different crustal sectors: the eastern sector, where the geometry of the Apennine thrust belt is still preserved, and the western sector, where the compressive structures are dislocated by important extensional deformations. In the western sector, the normal faults disrupting the compressive structures allow the mixing of the deep Na–Cl(HCO₃) fluids with the shallow groundwater causing a salinity increase and the natural deterioration of groundwater quality.     

Natural and anthropogenic factors affecting groundwater quality of an active volcano (Mt. Etna,Italy)

New geochemical data on dissolved major and minor constituents in 276 groundwater samples from Etna aquifers reveal the main processes responsible for their geochemical evolution and mineralisation. This topic is of particular interest in the light of the progressive depletion of water resources and groundwater quality in the area. Multivariate statistical analysis reveal 3 sources of solutes: (a) the leaching of the host basalt, driven by the dissolution of magma-derived CO₂; (b) mixing processes with saline brines rising from the sedimentary basement below Etna; (c) contamination from agricultural and urban wastewaters. The last process, highlighted by increased concentrations of SO₄, NO₃, Ca, F and PO₄, is more pronounced on the lower slopes of the volcanic edifice, associated with areas of high population and intensive agriculture. However, this study demonstrates that natural processes (a) and (b) are also very effective in producing highly mineralised waters, which in turn results in many constituents (B, V, Mg) exceeding maximum admissible concentrations for drinking water.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

Hydrochemical variation in the springs water between Jerusalem–Ramallah Mountains and Jericho Fault,Palestine

The spatial and temporal changes of the composition of the groundwater from the springs along the Wadi Qilt stream running from the Jerusalem–Ramallah Mountains towards the Jericho Plain is studied during the hydrological year 2006/2007. The residence time and the intensity of recharge play an important role in controlling the chemical composition of spring water which mainly depends on distance from the main recharge area. A very important factor is the oxidation of organics derived from sewage and garbage resulting in variable dissolved CO₂ and associated HCO₃ ⁻ concentration. High CO₂ yields lower pH values and thus under-saturation with respect to calcite and dolomite. Low CO₂ concentrations result in over-saturation. Only at the beginning and at the end of the rainy season calcite saturation is achieved. The degradation of dissolved organic matter is a major source for increasing water hardness. Besides dissolution of carbonates dissolved species such as nitrate, chloride, and sulfate are leached from soil and aquifer rocks together with only small amounts of Mg. Mg not only originates from carbonates but also from Mg–Cl waters are leached from aquifer rocks. Leaching of Mg–Cl brines is particularly high at the beginning of the winter season and lowest at its end. Two zones of recharge are distinguishable. Zone 1 represented by Ein Fara and Ein Qilt is fed directly through the infiltration of meteoric water and surface runoff from the mountains along the eastern mountain slopes with little groundwater residence time and high flow rate. The second zone is near the western border of Jericho at the foothills, which is mainly fed by the under-groundwater flow from the eastern slopes with low surface infiltration rate. This zone shows higher groundwater residence time and slower flow rate than zone 1. Groundwater residence time and the flow rate within the aquifer systems are controlled by the geological structure of the aquifer, the amount of active recharge to the aquifer, and the recharge mechanism. The results of this study may be useful in increasing the efficiency of freshwater exploitation in the region. Some precautions, however, should be taken in future plans of artificial recharge of the aquifers or surface-water harvesting in the Wadi. Because of evaporation and associated groundwater deterioration, the runoff water should be artificially infiltrated in zones of Wadis with high storage capacity of aquifers. Natural infiltration along the Wadis lead to evaporation losses and less quality of groundwater.     

Groundwater,Acid and Carbon Dioxide Dynamics Along a Coastal Wetland,Lake and Estuary Continuum

Coastal wetlands are hotspots for biodiversity and biological productivity, yet the hydrology and carbon cycling within these systems remains poorly understood due to their complex nature. By using a novel spatiotemporal approach, this study quantified groundwater discharge and the related inputs of acidity and CO₂ along a continuum of a modified coastal acid sulphate soil (CASS) wetland, a coastal lake and an estuary under highly contrasting hydrological conditions. To increase the resolution of spatiotemporal data and advance upon previous methodologies, we relied on automated observations from four simultaneous time-series stations to develop multiple radon mass balance models to estimate groundwater discharge and related groundwater inputs of acidity and dissolved inorganic carbon (DIC), along with surface water to atmosphere CO₂ fluxes. Spatial surveys indicated distinct acid hotspots with minimum surface water pH of 2.91 (dry conditions) and 2.67 (flood conditions) near a non-remediated (drained) CASS area. Under flood conditions, groundwater discharge accounted for ～14.5 % of surface water entering the lake. During the same period, acid discharge from the acid sulphate soil section of the continuum produced ～4.8 kg H₂SO₄?ha^?1 day^?1, a rate much higher than previous studies in similar systems. During baseflow conditions, the low pH water was rapidly buffered within the estuarine lake, with the pH increasing from 4.22 to 6.07 over a distance of ～250 m. The CO₂ evasion rates within the CASS were extremely high, averaging 2163?±?125 mmol m^?2 day^?1 in the dry period and 4061?±?259 mmol m^?2 day^?1 under flood conditions. Groundwater input of DIC could only account for 0.4 % of this evasion in the dry conditions and ～5 % during the flood conditions. We demonstrated that by utilising a spatiotemporal (multiple time-series stations) approach, the study was able to isolate distinct zones of differing hydrology and biogeochemistry, whilst providing more reasonable groundwater acid input estimates and air–water CO₂ flux estimates than some traditional sampling designs. This study highlights the notion that modified CASS wetlands can release large amounts of CO₂ to the atmosphere because of high groundwater acid inputs and extremely low surface water pH.     

Sources of environmental sulfur in the groundwater system,southern New Zealand

Sulfide minerals commonly occur in sediments and basement rocks in southern New Zealand, as authigenic precipitates from groundwater below the oxygenated surface zone. There are two principal potential sources for sulfur in the groundwater system: weathering of sulfide minerals in the metamorphic basement and rainwater-derived marine aerosols. We present data for these two key sulfur sources: metamorphic sulfide and associated hydrothermal Au-bearing veins within the Otago Schist (average δ³⁴S = −1.8 ± 2.4‰), and an inland saline lake (S derived entirely from rainwater, δ³⁴S = 21.4 ± 0.8‰). We use these two end member δ³⁴S values to estimate the contributions of these sources of sulfur in authigenic groundwater sulfide minerals and in waters derived from oxidation of these sulfide minerals, across a range of environments. We show that authigenic groundwater pyrite along joints in the Otago schist is derived primarily from metamorphic basement sulfur. In contrast, authigenic groundwater pyrite cementing Miocene-Recent aquifers shows a substantial marine aerosol component, and represents a distinct hydrogeological system. We suggest that marine aerosols represent a significant flux to the terrestrial sulfur cycle that has been present through the groundwater system in Otago over the past 20 million years.     

In-situ Growth of Calcite at Devils Hole, Nevada: Comparison of Field and Laboratory Rates to a 500,000 Year Record of Near-Equilibrium Calcite Growth

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO₃ solutions at 34 °C, CO₂ partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P_{CO 2}, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.     

Iron oxide precipitate in seepage of groundwater from a landslide slip zone

Orange precipitate was collected at the mouth of groundwater drainage tubes from the Kumanashi Landslide slip zone in Toyama prefecture, Northwest Japan. Data from XRF, X-ray diffraction, and Mössbauer spectroscopy determined the precipitate as hydrous ferric oxide (HFO) bearing multi-elements such as phosphorous, silica, calcium, etc. The occurrence of HFO may indicate an oxidation of ferrous iron in the percolated groundwater from the slip zone. Moreover, the precipitate iron should be mobilized with groundwater circulation from the slip zone, whose reducing condition was determined by the iron speciation on the same type of landslide profiles within the study area in previous studies. The HFO precipitate may be considered as a secondary reliable indicator to locate the seepage of a slip zone on surface, especially for a landslide newly investigated under wet-warm climate.     

Manganese minerals and associated fine particulates in the streambed of Pinal Creek,Arizona, U.S.A.: a mining-related acid drainage problem

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O₂ is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed.Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek.In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn₃O₄ to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO₃ and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn₄O₉ · (3H₂O)) and takanelite ((Mn,Ca)Mn₄O₉ · (3H₂O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO₃ from an anoxic groundwater that contained CO₂ HCO₃, and precipitated Mn₃O₄ and subsequently MnOOH from an oxic surface water from which most of the dissolved CO₂ had been removed.It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO₃, 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.     

A shallow subsurface controlled release facility in Bozeman, Montana, USA, for testing near surface CO2 detection techniques and transport models

A controlled field pilot has been developed in Bozeman, Montana, USA, to study near surface CO₂ transport and detection technologies. A slotted horizontal well divided into six zones was installed in the shallow subsurface. The scale and CO₂ release rates were chosen to be relevant to developing monitoring strategies for geological carbon storage. The field site was characterized before injection, and CO₂ transport and concentrations in saturated soil and the vadose zone were modeled. Controlled releases of CO₂ from the horizontal well were performed in the summers of 2007 and 2008, and collaborators from six national labs, three universities, and the U.S. Geological Survey investigated movement of CO₂ through the soil, water, plants, and air with a wide range of near surface detection techniques. An overview of these results will be presented.     

Analysis of a weathered profile on sulfide mineralization at Mugga Mugga, Western Australia

The mineralogy and geochemistry of the massive pyrite-pyrrhotite mineralization, which contains minor magnetite, sphalerite and galena, the weathered profile and surface gossan at Mugga Mugga in Western Australia have been examined. Reactions between amphibolite wall rocks and acid waters from the oxidation of the iron sulfides have resulted in distinct mineralogical zonation of the weathered profile which is further modified near the surface by lateritization. At the base of the weathered zone an opaline chert (Opal-CT) has been precipitated from fluctuations of the water table. A gossanous zone from 25.14–68.80 m with boxworks after massive pyrite is modified by abundant kaolinite, dickite and an alunite-type mineral derived from amphibolite wall rocks, while above 25.14 m both plinthite and mottled clay zones of a laterite profile are evident. Some characteristics of a mature gossan profile – sulfate-phosphate-arsenate near the base, a carbonate zone higher in the profile, and an oxide zone near the surface – overprint the gross zonation.At the interface between sulfide and weathered rock Mg, Ca, K, S, Zn, Cd, Hg, Ba are depleted, As, Sb, Mo, Cr and V contents increase and in the weathered zone, SiO₂, TiO₂, P₂O₅, SO₃, Pb, Zn, Hg, Sb, Co, Ni, W, Ba, Sr and Zr decrease up the profile whilst Al₂O₃, Fe₂O₃, CO₂, Cu and As increase. Of the elements associated with the massive pyrite (Pb, Zn, Cu, Ag, As, Cd, Hg, Sb, Co, Ni) anomalous concentrations of Pb, Cu, Ag, As and Sb occur in the surface gossan despite the possibility of complete leaching by highly acidic solutions. These anomalies are similar to those found in gossans over pyrite mineralization elsewhere in the Yilgarn Block.