Actinide crystal-liquid partitioning for clinopyroxene and Ca3(PO4)2

Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca₃ (PO₄)₂] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10^?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The D_Pu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.     

Retention behaviour of humic substances onto mineral surfaces and consequences upon thorium (IV) mobility: case of iron oxides

The influence of humic acids (HA) on the retention of Th(IV) onto the surface of Fe oxides has been investigated. Thorium (IV) is here considered as an analogue of tetravalent radionuclides (Zr, Hf, U, Np, Pu). Hematite (α–Fe₂O₃) and gœthite (α–FeOOH) have been chosen as model phases because of their widespread presence in the earth's crust. Retention experiments were performed by batch procedure at constant ionic strength and varying pH in the range 2–10; the HA concentration varied in the range 1–100 mg l⁻¹. Compared with the former data obtained on the retention of Th(IV) with the same hematite sample free of HA, the study of a ternary system (i.e. hematite–HA–Th), clearly shows the influence of HA on the retention mechanisms of Th(IV) even in neutral to slightly alkaline medium. In particular, it is illustrated that the retention of Th(IV) onto Fe oxides closely depends upon the ratio between humic and surface (Fe oxide) sites. This ratio has to be greater than a critical value in order to impede the sorption of Th(IV).     

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.     

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH₃ to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. The objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al³⁺ (2.8 or 5 mM), HCO₃⁻ (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO₂(CO₃)₂⁻² and UO₂(CO₃)₃⁻⁴) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO₂(OH)₃⁻ and UO₂(OH)₄⁻²) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO₂CO₃], cejkaite [Na₄(UO2)(CO₃)₃] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO₂)(SiO₄)·1.5H₂O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.     

Solubility and sorption of redox-sensitive radionuclides (Np,Pu) in J-13 water from the Yucca Mountain site: comparison between experiment and theory

This study presents the characterization of Pu-bearing precipitates and the results from uptake studies of Np and Pu on inorganic colloidal particulates in J-13 water from the Yucca Mountain site. Plutonium solubilities determined experimentally at pH values of 6, 7, and 8.5 are about two orders of magnitude higher than those calculated using the existing thermodynamic database indicating the influence of colloidal Pu(IV) species. Solid phase characterization using X-ray diffraction revealed primarily Pu(IV) in all precipitates formed at pH 6, 7, and 8.5. The solubility controlling Pu-bearing solids precipitated at ambient temperature consisted of amorphous Pu(OH)₄(s) with several Pu–O distances between 2.3 and 2.7 Å that are characteristic for Pu(IV) colloids. High temperature (90 °C) increased solid phase crystallinity and produced Pu(IV) solids that contained Pu oxidation state impurities. X-ray absorption spectroscopic studies revealed diminished Pu–O and Pu–Pu distances that were slightly different from those in crystalline PuO₂(s). A Pu–O bond of 1.86 Å was identified that is consistent with the plutonyl(V) distance of 1.81 Å in PuO₂⁺(aq). Hematite, montmorillonite, and silica colloids were used for uptake experiments with ²³⁹Pu(V) and ²³⁷Np(V). The capacity of hematite to sorb Pu significantly exceeded that of montmorillonite and silica. A low desorption rate was indicative of highly stable Pu-hematite colloids, which may facilitate Pu transport to the accessible environment. Neptunium uptake on all mineral phases was far less than Pu(V) uptake suggesting that a potential Pu(V)–Pu(IV) reductive sorption process was involved. The temperature effect on Pu solubility and pseudocolloid formation is also discussed.     

Refinement of the crystal structure of bonshtedtite, Na3Fe(PO4)(CO3)

The crystal structure of bonshtedtite, Na₃Fe(PO₄)(CO₃) (monoclinic, P2₁/m, a = 5.137(4), b = 6.644(4), c = 8.908(6) Å, β = 90.554(14)°, V = 304.0(4) ų, Z = 2) has been refined to R ₁ = 0.041 on the basis of 1314 unique reflections. The structure is similar to that of other minerals of the bradleyite group. It is based on the [Fe(PO₄)(CO₃)]^3? layers oriented parallel to (001). The layers are formed by corner-sharing PO₄ tetrahedra and FeO₄(CO₃) complexes, where FeO₆ tetrahedra and CO₃ triangles are edge-shared. The topology of the octa-tetrahedral layer in bonshtedtite is similar to that of the autunite-group minerals, but it differs from the latter in terms of local topological properties.     

甘肃龙首山成矿带新水井铀(钍)矿床元素迁移规律及成矿作用过程研究

新水井铀(钍)矿床位于甘肃省龙首山成矿带,是碱交代型铀矿床的典型代表,其矿体完全产于钠交代蚀变花岗岩中,成矿过程可划分为钠交代蚀变、铀钍矿化和成矿后3个主要阶段。文章对该矿床花岗岩原岩、蚀变岩及矿石开展了系统主微量元素分析,采用Grant等浓度线法探讨了钠交代蚀变和铀钍矿化阶段的元素迁移规律,结果表明:钠交代蚀变阶段为富含Na、Ca、过渡族元素(Sc、V、Cr、Co、Ni)、U、Th及CO2、H2O等挥发分的复杂流体,钠交代过程中原岩中的大离子亲石元素(Rb、Ba)和部分轻稀土元素(LREE)不同程度带出;而铀钍成矿阶段成矿流体则富集重稀土元素(HREE)、U、Th、PO43-等成分,CO2等挥发分大量逸出。结合前人研究,认为新水井矿床成矿流体可能来自地幔流体和大气降水热液的混合;等挥发分CO2的逸出是新水井矿床最重要的矿质沉淀机制,导致了铀钍矿物和磷酸盐矿物(磷灰石)的共沉淀,而磷灰石的沉淀又促进了以磷酸盐形式搬运的Th元素的沉淀。     

Carbon isotope fractionation of Thermoanaerobacter kivui in different growth media and at different total inorganic carbon concentration

Chemolithotrophic homoacetogenic bacteria apparently express a characteristic stable carbon isotope fractionation and may contribute significantly to acetate production in anoxic environments. However, fractionation factors (ε) in bacterial cultures have rarely been determined and the effect of substrate availability has not been assessed. We therefore studied the kinetic carbon isotope effect in cultures of Thermoanaerobacter kivui grown at 55 °C. The fractionation factor in HCO₃⁻ buffered medium was ca. 15‰ more negative than that in PO₄³⁻ buffered medium. To test whether the difference was caused by the initial substrate ratio of H₂ and total inorganic carbon (TIC; 0.5 in HCO₃⁻ vs. 4.0 in PO₄³⁻ buffered medium), T. kivui was grown in either [3-(N-morpholino) propanesulfonic acid, MOPS] buffered or PO₄³⁻ buffered media with different HCO₃⁻ concentration. Indeed, the fractionation factor became more negative with increasing HCO₃⁻ concentration and decreasing H₂/TIC ratio. While pH had only a small effect, the fractionation was generally more negative in MOPS buffered than in phosphate buffered media, indicating that the buffer system also affected fractionation. Collectively, the results show that substrate availability and other environmental factors affect the magnitude of isotope fractionation during acetate production by chemolithotrophic homoacetogenesis.     

Behavior of Uranium in the Yellow River Plume (Yellow River Estuary)

The Yellow River (Huanghe) is the second largest river in China and is known for its high turbidity. It also has remarkably high levels of dissolved uranium (U) concentrations (up to 38 nmol 1^-1). To examine the mixing behavior of dissolved U between river water and seawater, surface water samples were collected along a salinity gradient from the Yellow River plume during September 2004 and were measured for dissolved U concentration,²³⁴U:²³⁸U activity ratio, phosphate (PO₄ ^3–), and suspended particulate matter. Laboratory experiments were also conducted to simulate the mixing process in the Yellow River plume using unfiltered Yellow River water and filtered seawater. The results showed a nonconservative behavior for dissolved U at salinities < 20 with an addition of U to the plume waters estimated at about 1.4 X 10⁵ mol yr^–1. A similarity between variations in dissolved U and PO₄ ^3– with salinity was also found. There are two major mechanisms, desorption from suspended sediments and diffusion from interstitial waters of bottom sediments, that may cause the elevated concentrations of dissolved U and PO₄ ^3– in mid-salinity waters. Mixing experiments indicate that desorption seems more responsible for the elevated dissolved U concentrations, whereas diffusion influences more the enrichment of PO₄ ^3–.     

The redox chemistry of Pu(V)O2+ interaction with common mineral surfaces in dilute solutions and seawater

It has long been recognized that the Pu⁴⁺ ion can be readily adsorbed on solid surfaces, but it has been assumed that the generally more abundant Pu(V)O₂⁺ ion should have little affinity for surfaces. Our results indicate that Pu(V)O₂⁺ can be adsorbed from dilute solutions and seawater on goethite, aragonite, calcite, and δ-MnO₂. Adsorption on δ-MnO₂ is severely depressed in seawater, probably as a result of site competition with seawater cations.The sorption behavior of PuO₂⁺ is influenced by oxidation-reduction reactions occurring on the mineral surfaces. Adsorption on δ-MnO₂ results in oxidation of adsorbed Pu(IV) and Pu(V) to Pu(VI). However, adsorption on goethite results in a reaction in which Pu(IV) and Pu(VI) are formed on the mineral surface. The Pu(VI) is slowly reduced to Pu(IV), leaving Pu(IV) as the dominant surface Pu species. This reaction can be photochemically catalyzed. PuO₂⁺ adsorbed on carbonate minerals behaves similarly to Np(V)O₂⁺ and undergoes little change in oxidation state after adsorption.     

Laboratory actinide partitioning: Whitlockite/liquid and influence of actinide concentration levels

Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting “haplobasaltic” silicate liquid at 1 bar pressure and 1250°C at oxygen fugacities from 10^?8.5 and 10^?0.7 bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions (fO₂ = 10^?8.5), because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu⁺³, Pu⁺⁴, Th⁺⁴, U⁺⁴, and U⁺⁶ are, for whitlockite 3.6/<?0.6/1.2/0.5/?0.002. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO₂ indicate that Si is involved in the substitution of U in whitlockite with U + 2Si ? Ca + 2P being the most likely mechanism. D_u is lower. 0.3 vs 0.5. at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high U concentrations.     

The geochemical effects of benzene,toluene, and xylene (BTX) biodegradation

The geochemical effects of microbially mediated degradation of aromatic hydrocarbons were observed as changes in solution composition of an artificial groundwater in packed-sand laboratory columns. Benzene, toluene, and xylene, both individually and in a combined fashion, were used as substrates in biodegradation experiments conducted under oxygenated and anoxic conditions in columns filled with quartz, calcite, or Fe³⁺-coated quartz sand. Typically, column effluent had increased concentrations of dissolved inorganic C, decreased pH, and decreased concentrations of NO₃ and dissolved O₂ relative to column influent. Efficiency of CO₂ generation was similar for the three different substrates, ranging from 22.5 to 26.6% organic C converted to CO₂. When all three substrates were combined, the percentage of CO₂ produced fell within the range observed in the single substrate experiments. Nitrate disappearance was more varied as a function of substrate identity, with greatest amounts lost when toluene was the substrate. Calcite dissolved as a result of CO₂ generated during the biodegradation reactions, and empirically calculated dissolution rates varied between 1.9 and 4.0 x 10⁻⁹ mmol cm⁻² s⁻¹. The calcite dissolution rate was slower than the biodegradation rate, as evidenced by excess generation of CO₂ relative to Ca²⁺ production. The decrease in pH was less in experiments with calcite present than in those with quartz sand present due to buffering by calcite dissolution. Dissolution of Fe oxyhydroxides was not observed under any experimental conditions.     

Geochemical behaviour of LREE,Y and Zr in uranium mineralized and non-mineralized granite from Darshanapur area,in the Gogi-Kurlagere fault zone,Bhima basin,Yadgiri district,Karnataka

Granite core samples (n=14) from the Gogi-Kurlagere fault zone in the central part of the Bhima basin were studied in terms of LREE, Y and Zr mobility during uranium mineralization. LREE, Zr and Y along with LILE (Ba, Rb) and P show behavioral differences in the mineralised and the non-mineralised samples. Average ΣLREE in mineralised granite (240 ppm) is higher than in non-mineralised samples (157 ppm). The average Zr and Y in the mineralised granite are 193 ppm and 17 ppm, while the corresponding abundances of these elements in non-mineralised portion are 148 ppm and 11 ppm respectively. Besides enrichment of U, Th, Ba, Pb and Rb and depletion of Sr are observed in mineralized granite in comparison to non-mineralized granite. Hydrothermal alteration has led to the mobility of these elements, which again dependent on the overall geochemical behavior of the migrating fluid. REE and Y in association with uranyl [(UO₂)²⁺] ion were transported as carbonate complexes like [UO₂(CO₃)₃]^4- and [REE (CO₃)₃]^3- and were later incorporated into favourable structural loci by precipitating minerals like pitchblende and coffinite.     

Geology, Geochemistry, and Genesis of the Tongcun Reduced Porphyry Mo (Cu) Deposit, NW Zhejiang Province, China

The Tongcun Mo(Cu) deposit in Kaihua city of Zhejiang Province,eastern China,occurs in and adjacent to the Songjiazhuang granodiorite porphyry and is a medium-sized and important porphyry type ore deposit.Two irregular Mo(Cu) orebodies consist of various types of hydrothermal veinlets.Intensive hydrothermal alteration contains skarnization,chloritization,carbonatization,silicification and sericitization.Based on mineral assemblages and crosscutting relationships,the oreforming processes are divided into five stages,i.e.,the early stage of garnet + epidote ± chlorite associated with skarnization and K-feldspar + quartz ± molybdenite veins associated with potassicsilicic alteration,the quartz-sulfides stage of quartz + molybdenite ± chalcopyrite ± pyrite veins,the carbonatization stage of calcite veinlets or stockworks,the sericite + chalcopyrite ± pyrite stage,and the late calcite + quartz stage.Only the quartz-bearing samples in the early stage and in the quartzsulfides stage are suitable for fluid inclusions(FIs) study.Four types of FIs were observed,including1) CO_2-CH_4 single phase FIs,2) CO_2-bearing two- or three-phase FIs,3) Aqueous two-phase FIs,and4) Aqueous single phase FIs.FIs of the early stages are predominantly CO_2- and CH_4-rich FIs of the CO_2-CH4-H_2O-NaCl system,whereas minerals in the quartz-sulfides stage contain CO_2-rich FIs of the CO_2-H_2O-NaCl system and liquid-rich FIs of the H_2O-NaCl system.For the CO_2-CH_4 single phase FIs of the early mineralization stage,the homogenization temperatures of the CO_2 phase range from 15.4 ℃ to 25.3 ℃(to liquid),and the fluid density varies from 0.7 g/cm~3 to 0.8 g/cm~3;for two- or three-phase FIs of the CO_2-CH_4-H_2O-NaCl system,the homogenization temperatures,salinities and densities range from 312℃ to 412℃,7.7 wt%NaCl eqv.to 10.9 wt%NaCl eqv.,and 0.9 g/cm~3 to 1.0 g/cm~3,respectively.For CO_2-H_2O-NaCI two- or threephase FIs of the quartz-sulfides stage,the homogenization temperatures and salinities range from255℃ to 418℃,4.8 wt%NaCl eqv.to 12.4 wt%NaCl eqv.,respectively;for H_2O-NaCl two-phase FIs,the homogenization temperatures range from 230 ℃ to 368 ℃,salinities from 11.7 wt%NaCl eqv.to16.9 wt%NaCl eqv.,and densities from 0.7 g/cm~3 to 1.0 g/cm~3.Microthermometric measurements and Laser Raman spectroscopy analyses indicate that CO_2 and CH_4 contents and reducibility(indicated by the presence of CH_4) of the fluid inclusions trapped in quartz-sulfides stage minerals are lower than those in the early stage.Twelve molybdenite separates yield a Re-Os isochron age of 163 ± 2.4 Ma,which is consistent with the emplacement age of the Tongcun,Songjiazhuang,Dayutang and Huangbaikeng granodiorite porphyries.The S18OSMow values of fluids calculated from quartz of the quartz-sulfides stage range from 5.6‰ to 8.6‰,and the JDSMOw values of fluid inclusions in quartz of this stage range from-71.8‰ to-88.9‰,indicating a primary magmatic fluid source.534SV-cdt values of sulfides range from+1.6‰ to +3.8‰,which indicate that the sulfur in the ores was sourced from magmatic origins.Phase separation is inferred to have occurred from the early stage to the quartz-sulfides stage and resulted in ore mineral precipitation.The characteristics of alteration and mineralization,fluid inclusion,sulfur and hydrogen-oxygen isotope data,and molybdenite Re-Os ages all suggest that the Tongcun Mo(Cu) deposit is likely to be a reduced porphyry Mo(Cu) deposit associated with the granodiorite porphyry in the Tongcun area.     

Accumulation of mantle gases in a permanently stratified volcanic lake (Lac Pavin,France)

Lac Pavin is a volcanic crater lake in the Massif Central (France), characterized by a permanent vertical density stratification resulting from a strong and persistent chemocline between about 60 and 70 m depth. The deep water below the chemocline forms the monimolimnion, in which most dissolved ions as well as helium, carbon dioxide, and methane are strongly enriched. The ³He/⁴He isotope ratio of the excess helium is (9.09 ± 0.01) · 10⁻⁶, or (6.57 ± 0.01) R_a. These findings clearly indicate a flux of mantle-derived magmatic gases into the monimolimnion.In order to derive the fluxes of magmatic volatiles into Lac Pavin, it is essential to understand the hydrologic characteristics of the lake. Previously published two-box models have assumed groundwater input at the lake bottom, a short residence time in the monimolimnion, and biogenic origin of the CO₂. We propose an alternative model with a flux of magmatic gases, but not of water, into the monimolimnion, and a weak diffusive coupling between the monimolimnion and the overlying mixolimnion which leads to a long deep-water residence time (≈ 70 yr). We reassess the carbon budget of the lake and conclude that the major part of the accumulated CO₂ in the monimolimnion is of magmatic origin. From the model-derived water exchange rates, we calculated a mantle ⁴He flux of (6 ± 2) · 10¹¹ atoms m⁻² s⁻¹. This value lies near the lower end of the range found in comparable volcanic lakes. The flux of magmatic CO₂ is estimated as (1.2 ± 0.4) · 10⁻⁷ mol m⁻² s⁻¹, which is also comparatively low. The monimolimnion appears to be in steady state with respect to these fluxes, therefore no further, potentially hazardous, accumulation of CO₂ takes place.     

Preliminary estimate of CO2 output from Pantelleria Island volcano (Sicily,Italy): evidence of active mantle degassing

Total CO₂ output from fumaroles, bubbling and water dissolved gases and soil gases was investigated at Pantelleria Island volcano, Italy. The preliminary results indicate an overall output of 0.39 Mt a⁻¹ of CO₂ from the island. The main contribution to the total output was from diffuse soil degassing (about 0.32 Mt a⁻¹), followed by dissolved CO₂ (0.034 Mt a⁻¹), focussed soil degassing (0.028 Mt a⁻¹) and bubbling CO₂ (0.013 Mt a⁻¹). The contribution of CO₂ from fumarole gases was found to be negligible (1.4×10⁻⁶ Mt a⁻¹). Carbon-13 values for CO₂ coupled with those for associated He in gases from fumaroles and sites of focussed soil degassing clearly rule out any significant organic CO₂ component and suggest a common mantle origin for these gas species. The inferred mantle source beneath Pantelleria would seem to have peculiar geochemical characteristics, quite distinct from those of mantle producing MORB but compatible with those of magmatic sources of central Mediterranean and central European volcanoes. These findings indicate that the Pantelleria volcanic complex is a site of active mantle degassing that is worthy of attention for future geochemical surveillance of the island.     

Sorption of Np(V) and Np(IV) onto kaolinite: Effects of pH,ionic strength,carbonate and humic acid

The sorption of Np(V) and Np(IV) onto kaolinite has been studied in the absence and presence of humic acid (HA) in a series of batch equilibrium experiments under different experimental conditions: [Np]₀: 1.0 × 10^-6 or 1.0 × 10^-5 M, [HA]₀: 0 or 50 mg/L, I: 0.01 or 0.1 M NaClO₄, solid to liquid ratio: 4 g/L, pH: 6–11, anaerobic or aerobic conditions, without or with carbonate. The results showed that the Np(V) sorption onto kaolinite is affected by solution pH, ionic strength, Np concentration, presence of carbonate and HA. In the absence of carbonate, the Np(V) uptake increased with pH up to ∼96% at pH 11. HA further increased the Np(V) sorption between pH 6 and 9 but decreased the Np(V) sorption between pH 9 and 11. In the presence of carbonate, the Np(V) sorption increased with pH and reached a maximum of 54% between pH 8.5 and 9. At higher pH values, the Np(V) sorption decreased due to the presence of dissolved neptunyl carbonate species with a higher negative charge that were not sorbed onto the kaolinite surface which is negatively charged in this pH range. HA again decreased the Np(V) uptake in the near-neutral to alkaline pH range due to formation of aqueous neptunyl humate complexes. The decrease of the initial Np(V) concentration from 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁶ M led to a shift of the Np(V) adsorption edge to lower pH values. A higher ionic strength increased the Np(V) uptake onto kaolinite in the presence of carbonate but had no effect on Np(V) uptake in the absence of carbonate.     

Francolite geochemistry—compositional controls during formation,diagenesis, metamorphism and weathering

Francolite in unaltered Tertiary phosphorites is highly substituted with about 1.2% Na, 0.25% Sr, 0.36% Mg and 2.7% SO₄ within the structure in substitution for Ca and PO₄. These substitutions reflect the composition of the solution from which francolite forms and are not influenced by the mechanism, rate or redox conditions of formation. The remarkably constant composition for a wide range of samples reflects the relative constant composition of sea water, during Tertiary times. Francolite in sulphate-reducing sediments forms in an uppermost zone where bioturbation maintains the concentrations of Na, Sr, Mg and SO₄ at sea water concentrations. The structura-CO₂ content of unaltered francolites vary from 1.4% to 6.3%, in response to variations in pH. The maximum level of carbonate substitution is limited by the disruption of the francolite structure at levels above 6.3% CO₂. For the samples considered here F/P₂O₅ ratios vary with X-ray CO₂ contents showing that PO₄^3? is replaced by (CO₃^2? + F?) and not by CO₃^2? alone. In Phosphoria Formation francolite the Na/P₂O₅ ratios and X-ray CO₂ contents show areal trends related to burial depth and thermal metamorphism. These two processes together with weathering and fresh water diageneses explain all observed variation in francolite composition.     

An Apatite II permeable reactive barrier to remediate groundwater containing Zn,Pb and Cd

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca_10−xNa_x(PO₄)_6−x(CO₃)_x(OH)₂], where x < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO₄ and NO₃. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO₄ reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb₁₀(PO₄)₆(OH,Cl)₂] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L⁻¹), has reduced Zn to near background in this region (about 100 μg L⁻¹), and has reduced SO₄ by between 100 and 200 mg L⁻¹ and NO₃ to below detection (50 μg L⁻¹). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).