Tracing mechanisms controlling the release of dissolved silicon in forest soil solutions using Si isotopes and Ge/Si ratios

The terrestrial biogenic Si (BSi) pool in the soil-plant system is ubiquitous and substantial, likely impacting the land-ocean transfer of dissolved Si (DSi). Here, we consider the mechanisms controlling DSi in forest soil in a temperate granitic ecosystem that would differ from previous works mostly focused on tropical environments. This study aims at tracing the source of DSi in forest floor leachates and in soil solutions under various tree species at homogeneous soil and climate conditions, using stable Si isotopes and Ge/Si ratios. Relative to granitic bedrock, clays minerals were enriched in ²⁸Si and had high Ge/Si ratios, while BSi from phytoliths was also enriched in ²⁸Si, but had a low Ge/Si ratio. Such a contrast is useful to infer the relative contribution of silicate weathering and BSi dissolution in the shallow soil on the release of DSi in forest floor leachate solutions. The δ³⁰Si values in forest floor leachates (−1.38‰ to −2.05‰) are the lightest ever found in natural waters, and Ge/Si ratios are higher in forest floor leachates relative to soil solution. These results suggest dissolution of ²⁸Si and Ge-enriched secondary clay minerals incorporated by bioturbation in organic-rich horizons in combination with an isotopic fractionation releasing preferentially light Si isotopes during this dissolution process. Ge/Si ratios in soil solutions are governed by incongruent weathering of primary minerals and neoformation of secondary clays minerals. Tree species influence Si-isotopic compositions and Ge/Si ratios in forest floor leachates through differing incorporation of minerals in organic horizons by bioturbation and, to a lesser extent, through differing Si recycling.     

Irreversible water–rock mass transfer accompanying the generation of the neutral,Mg–HCO3 and high-pH,Ca–OH spring waters of the Genova province,Italy

In a recent survey of the spring waters of the Genova province, many neutral Mg–HCO₃ waters and some high-pH, Ca–OH waters were found in association with serpentinites. All the springs are of meteoric origin as indicated by the stable isotopes of water and dissolved N₂ and Ar. Interaction of these meteoric waters with serpentinites determines a progressive evolution in the chemistry of the aqueous phase from an immature Mg-rich, SO₄–Cl facies of low salinity to an intermediate Mg–HCO₃ facies (pH 7.0–8.5, P_CO210^−3.5–10^−2.5 bar, Eh 150–250 mV), and to a mature Ca–OH facies (pH 10–12, P_CO2 10^−9.4−10^−10.6 bar, Eh-390 to-516 mV). The irreversible water–rock mass transfer leading to these chemical changes in the aqueous phase was simulated through reaction path modeling, assuming bulk dissolution of a local serpentinite, and the precipitation of gibbsite, goethite, calcite, hydromagnesite, kaolinite, a montmorillonite solid mixture, a saponite solid mixture, sepiolite, and serpentine. The simulation was carried out in two steps, under open-system and closed-system conditions with respect to CO₂, respectively. The calculated concentrations agree with analytical data, indicating that the computed water-rock mass transfer is a realistic simulation of the natural process. Moreover, the simulation elucidates the role of calcite precipitation during closed-system serpentinite dissolution in depleting the aqueous solution of C species, allowing the concurrent increment in Ca and the acquisition of a Ca–OH composition. Calcium–OH waters, due to their high pH, tend to absorb CO₂, precipitating calcite. Therefore, these waters might be used to sequester anthropogenic CO₂, locally preventing environmental impact to the atmosphere.     

Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

Geochemical characteristics of waters in mineralised area of Peloritani Mountains (Sicily,Italy)

This paper presents the results of a study on the geochemistry of waters circulating in the mineralised area of the south-eastern sector of Mt. Peloritani (north-eastern Sicily, Italy), aimed at basic understanding of the geochemical processes influencing their chemical composition. Chemico-physical parameters and data on 26 major and minor chemical elements are reported for 103 water samples. Water chemistry is mainly dominated by dissolution of carbonates and hydrolysis of aluminosilicate minerals. Total dissolved salts (TDS) range from 80 to 1398 mg/L. All the waters exhibit E_H characteristic of an oxygenated environment. Excluding two samples, which show very high H⁺ activity (pH = 3.0 and 2.7), all the waters have pH values in the range 6.2–8.6. Cluster analysis based on major ion contents defined three main chemical water types, reflecting different hydrochemical processes. The first, group I, has low salinity (average TDS = 118 ± 30 mg/L) and abundance orders (meq/L) Na > Ca ≈ Mg > K and Cl ≈ HCO₃ > SO₄. With increased water–rock interaction, waters in groups II and III become more saline, changing composition towards SO₄–Cl-alkaline earth and HCO₃-alkaline earth types. Weathering of carbonate minerals causes waters to become saturated with respect to calcite and dolomite, whereas the incongruent dissolution of aluminosilicate minerals causes the solution to reach equilibrium with kaolinite and to form smectites. Trace element geochemistry in the analysed waters reflects interactions between waters and existing mineralisation, with elemental concentrations showing highly variable values, and higher concentrations of As, Pb, Sb and Zn near known mineralisation. Lead–Zn and As–Sb statistical associations, probably distinguishing interactions with different mineralogical phase paragenesis, were revealed by factor analysis. The main aqueous chemical forms of trace elements predicted by chemical speciation calculations are also reported. As most of the analysed spring waters provide the main source of freshwater for domestic purposes, attention should be given to As and Sb, whose concentrations exceed the recommended limits.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Ge/Si and Sr/Sr tracers of weathering reactions and hydrologic pathways in a tropical granitoid system

Ge/Si and ⁸⁷Sr/⁸⁶Sr data from primary and secondary minerals, soil waters, and stream waters in a tropical granitoid catchment quantitatively reflect mineral alteration reactions that occur at different levels within the bedrock–saprolite–soil zone. Near the bedrock–saprolite interface, plagioclase to kaolinite reaction yields low Ge/Si and 87Sr/86Sr. Higher in the regolith column, biotite weathering and kaolinite dissolution drive Ge/Si and 87Sr/86Sr to high values. Data from streams at base flow sample the bedrock–saprolite interface zone, while at high discharge solutes are derived from upper saprolite–soil zone. Coupled Ge/Si and 87Sr/86Sr can be effective tools for quantifying the importance of specific weathering reactions, and for geochemical hydrograph separation.     

Crude oil in a shallow sand and gravel aquifer—I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed ∼1 pH unit, and the concentrations of Ca, Mg and HCO₃⁻ increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO₂, Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO₂ precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix.The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.     

Genesis of arsenic/fluoride-enriched soda water: A case study at Datong,northern China

The high As and F⁻ groundwaters from Datong Basin are mostly soda waters with a Na/(Cl+SO₄) (meq) ratio greater than unity, As and F⁻ up to 1550 μg/L and 10.4 mg/L, respectively, and with pH between 7.6 and 9.1. Geochemical modeling indicates that the waters are oversaturated with respect to calcite and clay minerals such as kaolinite, and undersaturated with respect to primary rock-forming minerals such as anorthite and albite. The water chemistry also is affected by evapotranspiration. The degree of evaporative enrichment is up to 85 in terms of Cl⁻. Results of the hydrogeochemical studies indicate that the occurrence of soda water at Datong is the result of incongruent dissolution of aluminosilicates at one stage of their interaction with groundwater when the water is oversaturated with respect to calcite and evapotranspiration-related salt accumulation is not too strong. Studying the genesis of soda waters provides new insights into mechanism of As and F⁻ enrichment in the aquifer system. Due to CaF₂ solubility control and OH⁻–F⁻ exchange reactions, F⁻ can be enriched in soda water. And the high pH condition of soda water favors As desorption from oxyhydroxide surfaces, thereby increasing the concentration of As in the aqueous phase.     

Arsenic in surface- and up to 90°C ground waters in a basalt area,N-Iceland: processes controlling its mobility

The concentrations of As in surface- and up to 90 °C ground waters in a tholeiite flood basalt area in N-Iceland lie in the range <0.03–10 μg/kg. With few exceptions surface waters contain <0.5 μg/kg As whereas ground waters generally contain >0.5 μg/kg As. The As content of ground waters increases on the whole with rising temperature. Arsenic is highly mobile in the basalt-water environment of the study area. An insignificant fraction of the As dissolved from the rock is taken up into secondary minerals. Arsenic is less mobile than B but considerably more mobile than Na which has the highest mobility among the major aqueous components. A significant fraction of the As in the basalt occurs in an easily soluble form. The As hosted in the primary minerals is expected to be concentrated in the titano-magnetite. This mineral is stable in contact with both surface- and ground waters and does not, therefore, supply As to the water, explaining the difference in mobility between As and B. Aqueous As concentrations are a reflection of water/rock ratios, i.e. how much rock a given quantity of water has dissolved. This ratio increases with increasing temperature and increasing residence time of the water in contact with the rock. The distribution of As species has been calculated on the assumption of equilibrium at the redox potential retrieved from measurement of aqueous Fe(II) and Fe(III) concentrations. These calculations indicate that pentavalent As is stable in surface waters and in ground waters with an in situ pH of <10 and would occur mostly as H₂AsO₄⁻ and HAsO₄⁻². In higher pH ground waters the concentrations of the arsenite species H₂AsO₃⁻ is significant at equilibrium, up to 65% of the total dissolved As.     

Acidification processes and soil leaching influenced by agricultural practices revealed by strontium isotopic ratios

In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH₄ acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH₄ acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low ⁸⁷Sr/⁸⁶Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na⁺. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na⁺ in streams. However, Ca²⁺ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na⁺, 5-40% of Sr²⁺ and 20-100% of Ca²⁺ found in streams can be directly derived from the application of organic fertilizers.     

Flotation of germanium n and p with potassium ethyl xanthate

Steady-state potential of the germanium electrode, flotation tests and results of spectrophotometric ATR (Attenuated Total Reflection) measurements of germanium surface in the presence and absence of potassium ethyl xanthate are presented.On the basis of the steady-state potentials of the germanium electrode in ethyl xanthate solutions, the standard potential E⁰ of the reaction: Ge + 2EtX^? = Ge (EtX)₂ + 2e is estimated. The pH ranges of the dixanthogen (EtX)₂ and the germanium xanthate Ge(EtX)₂ species predominance in the bulk solution are calculated. It has been established that flotation of germanium is greater than the natural floatability (in the absence of collectors) in the pH ranges where (EtX)₂ or Ge (EtX)₂ are present in the bulk solution. Spectrophotometric results reveal the presence of (EtX)₂ and Ge (EtX)₂ on the surface in the same pH ranges as is calculated for the bulk reactions.No significant differences in the surface properties and the flotation behaviour between germanium n and p have been found.     

Spectroscopic evidence for aqueous alteration products on the surfaces of low-albedo asteroids

High-resolution IR spectra (0.9–2.5 μm) and narrowband photometry (3.0–3.5 μm) are presented for asteroids 1 Ceres, 2 Pallas and 324 Bamberga. Laboratory experiments with hydrated minerals indicate that the 3 μm absorption feature observed on asteroids is largely due to interlayer water molecules in clay minerals, with a possible contribution from water molecules bound to salts. The depth of the 3 μm band as a function of 2.2 μm albedo is a useful measure of the amount of hydrated mineral present on these asteroids. 1 Ceres must consist mostly of a clay mineral like that in CM chondrites, with some contribution to the strength of the 3 μm band by hydrated salts. These salts, which are products of aqueous alteration, may also be responsible for Ceres' high albedo relative to other C-type asteroids. 2 Pallas must have a low abundance of hydrated minerals relative to 1 Ceres, with the bulk of its composition being spectrally featureless minerals such as the iron-free silicates in CM chondrules. 324 Bamberga probably contains clay minerals, but their abundance cannot be determined at present. The spectrum of Bamberga below 2.5 μm shows evidence for abundant magnetite, which can be a product of aqueous alteration. The presence of magnetite on Bamberga and possibly other C-type asteroids may be responsible for their low albedos. The spectra of C-type asteroids may be reconcilable with those of carbonaceous chondrites if the asteroids surfaces have undergone alteration by aqueous or other analogous processes.     

The products of the interaction of feldspars with aqueous solutions at 25°C

Chemical analyses of 300 solutions produced by the artificial weathering of eight different feldspars in fourteen experiments of up to 1200hr duration were used to study the evolution of water during weathering. The range of pH was between 4 and 5·5. Within 4 hr of dissolution, the activity of Al was controlled by the pH and the solubility of microcrystalline gibbsite. After 100 hr of dissolution, the pH and microcrystalline halloysite controlled the activities of Al and silicic acid in all of the solutions.Microcrystalline halloysite was the only phase identified in the weathering of plagioclases in distilled water and 1 atm CO₂ partial pressure. Montmorillonites, halloysite and other clay minerals were produced from oligoclase in aqueous solutions containing high initial concentrations of Ca. Mg, K and SiO₂.The experimentally determined log solubility product of microcrystalline gibbsite was ?32·78 ± 0·04 and log $\text{K}$ for the hydrolysis of microcrystalline halloysite was 11.58 ± 0·05. The results suggest that very poorly crystalline metastable phases may control the initial compositions of some waters in contact with rocks containing feldspar minerals.     

How do mineral coatings affect dissolution rates? An experimental study of coupled CaCO3 dissolution—CdCO3 precipitation

Coupled CaCO₃ dissolution-otavite (CdCO₃) precipitation experiments have been performed to 1) quantify the effect of mineral coatings on dissolution rates, and 2) to explore the possible application of this coupled process to the remediation of polluted waters. All experiments were performed at 25°C in mixed-flow reactors. Various CaCO₃ solids were used in the experiments including calcite, aragonite, and ground clam, mussel, and cockle shells. Precipitation was induced by the presence of Cd(NO₃)₂ in the inlet solution, which combined with aqueous carbonate liberated by CaCO₃ dissolution to supersaturate otavite. The precipitation of an otavite layer of less than 0.01 μm in thickness on calcite surfaces decreases its dissolution rate by close to two orders of magnitude. This decrease in calcite dissolution rates lowers aqueous carbonate concentrations in the reactor such that the mixed-flow reactor experiments attain a steady-state where the reactive fluid is approximately in equilibrium with otavite, arresting its precipitation. In contrast, otavite coatings are far less efficient in lowering aragonite, and ground clam, mussel, and cockle shell dissolution rates, which are comprised primarily of aragonite. A steady-state is only attained after the precipitation of an otavite layer of 3-10 μm thick; the steady state CaCO₃ dissolution rate is 1-2 orders of magnitude lower than that in the absence of otavite coatings. The difference in behavior is interpreted to stem from the relative crystallographic structures of the dissolving and precipitating minerals. As otavite is isostructural with respect to calcite, it precipitates by epitaxial growth directly on the calcite, efficiently slowing dissolution. In contrast, otavite’s structure is appreciably different from that of aragonite. Thus, it will precipitate by random three dimensional heterogeneous nucleation, leaving some pore space at the otavite-aragonite interface. This pore space allows aragonite dissolution to continue relatively unaffected by thin layers of precipitated otavite. Due to the inefficiency of otavite coatings to slow aragonite and ground aragonite shell dissolution, aragonite appears to be a far better Cd scavenging material for cleaning polluted waste waters.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Effect of orthophosphate on the dissolution kinetics of biogenic magnesian calcites

The dissolution behavior of two biogenic Mg-calcites, the echinoid, Tripneustes (12 mol% MgCO₃), and the red alga, Neogoniolithon (18 mol% MgCO₃ plus brucite), was studied using free-drift methods in distilled water and phosphate-spiked solutions at 25°C and P_CO2 = 1 atm. Small concentrations of phosphate strongly inhibit dissolution rates. Inhibition increases with increased phosphate levels and with approach toward saturation. Near saturation, dissolution rates are reduced by 10³ by the presence of 0.6 μmol adsorbed-P/m². The magnitude of phosphate inhibition is similar to that observed for low-Mg calcite, and like calcite, the mechanism of inhibition is probably by adsorption of P at surface kink sites. Phosphate appears to inhibit removal of Mg and Ca equally during Mg-calcite dissolution. Rates of brucite dissolution are unaffected by phosphate.Mg-calcites containing >8.5 mol% MgCO₃ should be thermodynamically unstable relative to aragonite in most natural waters. Recent work, however, shows that in contrast to its effect on the behavior of Mg-calcites. phosphate does not inhibit aragonite dissolution. The presence of phosphate might thus reverse the relative stability of these two minerals during diagenesis of shallow marine carbonate sediments.     

Rapid releases of metal salts and nutrients following the deposition of volcanic ash into aqueous environments

Deposition of volcanic ash into aqueous environments leads to dissolution of adsorbed metal salts and aerosols, increasing the bioavailability of key nutrients. Volcanogenic fertilization events could increase marine primary productivity, leading to a drawdown of atmospheric CO₂. Here we conduct flow-through experiments on unhydrated volcanic ash samples from a variety of locations and sources, measuring the concentrations and fluxes of elements into de-ionized water and two contrasting ocean surface waters. Comparisons of element fluxes show that dissolution of adsorbed surface salts and aerosols dominates over glass dissolution, even in sustained low pH conditions. These surface ash-leachates appear unstable, decaying in situ even if kept unhydrated. Volcanic ash from recent eruptions is shown to have a large fertilization potential in both fresh and saline water. Fluorine concentrations are integral to bulk dissolution rates and samples with high F concentrations display elevated fluxes of some nutrients, particularly Fe, Si, and P. Bio-limiting micronutrients are released in large quantities, suggesting that subsequent biological growth will be limited by macronutrient availability. Importantly, acidification of surface waters and high fluxes of toxic elements highlights the potential of volcanic ash-leachates to poison aqueous environments. In particular, large pH changes can cause undersaturation of CaCO₃ polymorphs, damaging populations of calcifying organisms. Deposition of volcanic ash can both fertilize and/or poison aqueous environments, causing significant changes to surface water chemistry and biogeochemical cycles.     

Rare earths in barites: distribution and effects on aqueous partitioning

A large variety of barites collected from marine and continental environments was analyzed by neutron activation for the rare-earth elements (REE) La, Ce, Sm, Eu and Dy. Relative to chondrites, all barites show a decrease of the lighter REE from La toward Eu. The abundance and distribution of rare earths in barites show a distinction of barite types. Deep-sea barites have large REE concentrations as do other authigenic deep-sea minerals and display the chondrite normalized Eu minimum, but not the negative Ce anomaly, of sea water. Other barites, mostly on land, some hydrothermal, and others of shallow marine origin, display lower total Ree concentrations. Chondrite normalized positive Eu anomalies are displayed by those varieties of reducing sedimentary and metamorphic origin.Distribution of REE in barite can be attributed both to crystallographic constraints of substitution, and to solution complexing of REE in the precipitating medium. Plots of rare earth partitioning versus effective ion size suggest that the decreasing enrichment toward Eu for all barite types is caused by crystallographic constraints due to contraction of the substituting REE ion sizes relative to the size of the host Ba ion. Solution effects on REE substitution in barite can be evaluated by writing solid solution distribution equations based on mass action of REE and Ba sulfates and the lanthanide (Ln) solution species Ln (CO₃)^?5₄), LnSO⁺₄, LnCl⁺² and LnF⁺². Under normal sea water conditions, solution complexing plays a minor role. However, increased alkalinities of reducing sediments and increased brine chlorinities could cause significant complexing and deplete REE heavier than Eu. Besides Dy in barites, this could be true for aqueous precipitation of REE in general.     

The mobility of thorium in natural waters at low temperatures

Thermodynamic properties of 32 dissolved thorium species and 9 thorium-bearing solid phases have been collected from the literature, critically evaluated and estimated where necessary for 25°C and 1 atm pressure. Although the data are incomplete, especially for thorium minerals and organic complexes, some tentative conclusions can be drawn. Dissolved thorium is almost invariably complexed in natural waters. For example, based on ligand concentrations typical of ground water (ΣCl = 10 ppm, ΣF = 0.3 ppm, ΣSO₄ = 100 ppm, andΣPO₄ = 0.1 ppm), the predominant thorium species are Th(SO₄)⁰₂, ThF²⁺₂, and Th(HPO₄)₂⁰below pH ≈ 4.5; Th(HPO₄)^2?₃ from about pH 4.5 to 7.5; and Th(OH)⁰₄ above pH 7.5. Based on stability constants for thorium citrate, oxalate and EDTA complexes, it seems likely that organic complexes predominate over inorganic complexes of thorium in organic-rich stream waters, swamp waters, soil horizons, and waterlogged recent sediments. The thorium dissolved in seawater is probably present in organic complexes and as Th(OH)⁰₄. The tendency for thorium to form strong complexes enhances its potential for transport in natural waters by many orders of magnitude below pH 7 in the case of inorganic complexing, and below about pH 8 when organic complexing is important. The existence of complexes in addition to those formed with hydroxyl, is apparent from the fact that measured dissolved thorium in fresh surface waters (pH values generally 5–8) usually ranges from about 0.01 to 1 ppb and in surface seawater (pH = 8.1) is about 0.00064 ppb. This may be contrasted with the computed solubility of thorianite in pure water which is only 0.00001 ppb Th as Th(OH)⁰₄ above pH 5. Although complexing increases the solubility of thorium-bearing heavy minerals below pH 8, maximum thorium concentrations in natural waters are probably limited in general by the paucity and slow solution rate of these minerals and by sorption processes, rather than by mineral-solution equilibria.     

The mechanism of surface chemical kinetics of dissolution of minerals

This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δH^n0 ,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.