Interaction of U(VI) with Äspö diorite: A batch and in situ ATR FT-IR sorption study

Pristine diorite drill cores, obtained from the Äspö Hard Rock Laboratory (HRL, Sweden), were used to study the retention properties of fresh, anoxic crystalline rock material towards the redox-sensitive uranium. Batch sorption experiments and spectroscopic methods were applied for this study. The impact of various parameters, such as solid-to-liquid ratio (2–200 g/L), grain size (0.063–0.2 mm, 0.5–1 mm, 1–2 mm), temperature (room temperature and 10 °C), contact time (5–108 days), initial U(VI) concentration (3 × 10⁻⁹ to 6 × 10⁻⁵ M), and background electrolyte (synthetic Äspö groundwater and 0.1 M NaClO₄) on the U(VI) sorption onto anoxic diorite was studied under anoxic conditions (N₂). Comparatively, U(VI) sorption onto oxidized diorite material was studied under ambient atmosphere (pCO₂ = 10^−3.5 atm). Conventional distribution coefficients, K_d, and surface area normalized distribution coefficients, K_a, were determined. The K_d value for the U(VI) sorption onto anoxic diorite in synthetic Äspö groundwater under anoxic conditions by investigating the sorption isotherm amounts to 3.8 ± 0.6 L/kg which corresponds to K_a = 0.0030 ± 0.0005 cm (grain size 1–2 mm). This indicates a weak U sorption onto diorite which can be attributed to the occurrence of the neutral complex Ca₂UO₂(CO₃)₃(aq) in solution. This complex was verified as predominating U species in synthetic Äspö groundwater by time-resolved laser-induced fluorescence spectroscopy (TRLFS). Compared to U sorption at room temperature under anoxic conditions, U sorption is further reduced at decreased temperature (10 °C) and under ambient atmosphere. The U species in aqueous solution as well as sorbed on diorite were studied by in situ time-resolved attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. A predominant sorbing species containing a UO₂(CO₃)₃⁴⁻ moiety was identified. The extent of U sorption onto diorite was found to depend more on the low sorption affinity of the Ca₂UO₂(CO₃)₃(aq) complex than on reduction processes of uranium.     

Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite

The solubility of synthetic ZnS_(cr) was measured at 25–250 °C and P = 150 bars as a function of pH in aqueous sulfide solutions (~ 0.015–0.15 m of total reduced sulfur). The solubility determinations were performed using a Ti flow-through hydrothermal reactor. The solubility of ZnS_(cr) was found to increase slowly with temperature over the whole pH range from 2 to ~ 10. The values of the Zn–S–HS complex stability constant, β, were determined for Zn(HS)₂⁰_(aq), Zn(HS)₃^?, Zn(HS)₄^2?, and ZnS(HS)^?. Based on the experimental values the Ryzhenko–Bryzgalin electrostatic model parameters for these stability constants were calculated, and the ZnS_(cr) solubility and the speciation of Zn in sulfide-containing hydrothermal solutions were evaluated. The most pronounced solubility increase, about 3 log units at m(S_total) = 0.1 for the temperatures from 25 to 250 °C, was found in acidic solutions (pH ~ 3 to 4) in the Zn(HS)₂⁰_(aq) predominance field. In weakly alkaline solutions, where Zn(HS)₃^? and Zn(HS)₄^2? are the dominant Zn–S–HS complexes, the ZnS_(cr) solubility increases by 1 log unit at the same conditions. It was found that ZnS(HS)^? and especially Zn(HS)₄^2? become less important in high temperature solutions. At 25 °C and m(S_total) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(S_total) = 0.1, the maximum fraction of Zn(HS)₄^2? is only 20% of the total Zn concentration (i.e. at pH_t ~ 7.5), whereas at 350 °C and 3 <pH_t <10, the fraction of Zn(HS)₄^2? and ZnS(HS)^? is less than 0.05% and 2.5% respectively, of the total Zn concentration and Zn(HS)₂⁰ and Zn(HS)₃^? predominate. The measured equilibrium formation constants were combined with the literature data on the stability of Zn–Cl complexes in order to evaluate the concentration and speciation of Zn in chloride solutions. It was found that at acidic pH, and in more saline fluids having total chloride > 0.05 m, Zn–Cl complexes are responsible for hydrothermal Zn transport with no significant contribution of Zn–S–HS complexes. The hydrosulfide/sulfide complexes will play a more important role in lower salinity (< 0.05 m chloride) hydrothermal solutions which are characteristic of many epithermal ore depositing environments. The value of Δ_fG° (β-ZnS_(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.     

Assessing the potential for CO2 adsorption in a subbituminous coal,Huntly Coalfield,New Zealand,using small angle scattering techniques

Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (R_max 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 10⁶ cm^? 1 to 4.26 × 10⁶ cm^? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m³/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m³/t daf for carbon dioxide. The resulting ratio of CO₂:CH₄ ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores.     

Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Significant amounts of sulfuric acid (H₂SO₄) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R_Si, R_Al, R_Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R_Si value was obtained at pH 1 and 45 °C (−9.07 mol g⁻¹ s⁻¹), while the lowest log R_Si value was obtained at pH 4 and 25 °C (−11.20 mol g⁻¹ s⁻¹). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol⁻¹ (pH 1) to 37.7 kJ mol⁻¹ (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H₂SO₄/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.     

Kinetics of selenium release in mine waste from the Meade Peak Phosphatic Shale,Phosphoria Formation,Wooley Valley,Idaho, USA

Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyrite_ss) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe₂ and organo-selenides.Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q, from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ? Q) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q. Se release (mg/L) follows a first order reaction with a rate constant, k, = 1.35 – 6.35e?3 h^? 1 (11.8–55.6 yr^? 1).Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ～ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e?3 h^? 1 (19.2 yr^? 1).Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump.     

The effect of isosaccharinic acid and gluconic acid on the retention of Eu(III), Am(III) and Th(IV) by calcite

Calcite is an important component of many potential host rocks currently under consideration for the disposal of radioactive wastes. Even in the chemically disturbed zone formed around a cementitious repository, this mineral remains largely unaffected by the hyper-alkaline waters migrating out of the near field. Thus, due to its abundance and geochemical stability, calcite could play an important role in the retardation of radionuclides released from a repository for nuclear wastes. Actinides are an important class of elements present in almost all radioactive waste streams, and for this reason, investigations of their retention behaviour under representative chemical conditions are particularly relevant to assessing safe disposal in the long term. Organic ligands originating from the degradation of cellulosic materials in the repository or present as cement additives could possibly reduce the retardation of tri- and tetravalent actinides due to the formation of stable metal–ligand complexes in solution. In this study, isosaccharinic acid (ISA) and gluconic acid (GLU) have been taken as representatives of cellulose degradation products and concrete admixtures, respectively. Batch-type sorption experiments have been conducted to investigate the effect of ISA and GLU on the retardation of ¹⁵²Eu, ²⁴¹Am and ²²⁸Th by calcite. ¹⁵²Eu and ²⁴¹Am are representatives of the trivalent lanthanides and actinides, respectively, and ²²⁸Th is a representative of the tetravalent actinides.High ISA and GLU concentrations in solution were found to significantly affect the sorption of the radionuclides. R_d values for Eu(III) and Am(III) decreased significantly at ISA concentrations above 10⁻⁵ M and at GLU concentrations above 10⁻⁷ M. The critical concentration limits were similar for Th(IV), that is 2 × 10⁻⁵ M in the case of ISA and 10⁻⁶ M in the case of GLU. The effects of ISA and GLU on the immobilisation of Eu(III), Am(III) and Th(IV) were interpreted in terms of complex formation in solution. In the case of Eu(III) and Am(III) in ACW, the metal–ligand complexes were found to have a 1:1 stoichiometry. Complexation constants of these aqueous ISA and GLU complexes with Eu(III) and Am(III) were determined and discussed in connection with the presently unclear situation concerning the stability constant of the $\mathrm{Eu}(\mathrm{OH}{)}_3^0$ species. In the case of Th(IV) in ACW, it was assumed that a Th(IV)–ISA–Ca complex and a Th(IV)–GLU–Ca complex are formed, both having a 1:2:1 stoichiometry. The complexation constants of these complexes were determined and compared with the literature data.Assuming maximum concentrations for ISA and GLU in the pore water of the disturbed zone of a cementitious repository based on representative near-field conditions ([ISA]_aq = 3 × 10⁻⁶ M, [GLU]_aq = 10⁻⁷ M), it is predicted that the formation of aqueous ISA and GLU complexes would not significantly affect Eu(III), Am(III) and Th(IV) sorption on calcite.     

Effects of fluorine on the solubilities of Nb,Ta, Zr and Hf minerals in highly fluxed water-saturated haplogranitic melts

The effect of fluorine on the solubilities of Mn-columbite (MnNb₂O₆), Mn-tantalite (MnTa₂O₆), zircon (ZrSiO₄) and hafnon (HfSiO₄) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab₇₂Or₂₈) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P₂O₅, 1.05 wt.% Li₂O and 1.83 wt.% B₂O₃. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF₃ to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb₂O₅] and [MnO] 1 [Ta₂O₅] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10^− 4 (mol²/kg²), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10^− 4 (mol/kg) ZrO₂ and 4.04 ± 0.2 × 10^− 4 (mol/kg) HfO₂ for melts with 0 wt.% F to 3.81 ± 0.3 × 10^− 4 (mol/kg) ZrO₂ and 6.18 ± 0.04 × 10^− 4 (mol/kg) HfO₂ for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.     

Rock alteration in alkaline cement waters over 15 years and its relevance to the geological disposal of nuclear waste

The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO₃)₂ + 2OH⁻ → Mg(OH)₂ + CaCO₃ + CO₃²⁻_(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)₂ dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.     

Triassic volcanism in eastern Heilongjiang and Jilin provinces,NE China: Chronology,geochemistry, and tectonic implications

With the aim of constraining the Early Mesozoic tectonic evolution of the eastern section of the Central Asian Orogenic Belt (CAOB), we undertook zircon U–Pb dating and geochemical analyses (major and trace elements, Sr–Nd isotopes) of volcanic rocks of the Luoquanzhan Formation and Daxinggou Group in eastern Heilongjiang and Jilin provinces, China. The analyzed rocks consist mainly of dacite and rhyolite, with SiO₂ contents of 68.52–76.65 wt%. Three samples from the Luoquanzhan Formation and one from the Daxinggou Group were analyzed using laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U–Pb zircon techniques. Three zircons with well-defined oscillatory zoning yielded weighted mean ²⁰⁶Pb/²³⁸U ages of 217 ± 1, 214 ± 2, and 208 ± 1 Ma, and one zircon with oscillatory zoning yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 201 ± 1 Ma. These ages are interpreted to represent the timing of eruption of the volcanic rocks. The Triassic volcanic rocks are characterized by high SiO₂ and low MgO concentrations, enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), depletion in high field strength elements (HFSEs) and heavy rare earth elements (HREEs), (⁸⁷Sr/⁸⁶Sr)_i = 0.7040–0.7050 (Luoquanzhan Formation) and 0.7163–0.7381 (Daxinggou Group), and ε_Nd (t) = 1.89–3.94 (Luoquanzhan Formation) and 3.42–3.68 (Daxinggou Group). These geochemical features indicate an origin involving the partial melting of juvenile lower crust (Nd model ages (T_DM2) of 651–821 Ma) and that compositional variation among the volcanic rocks arose from mineral fractionation and minor assimilation. These volcanic rocks formed within an extensional environment following collision of the NCC and Jiamusi-Khanka Massif during the Late Paleozoic–Early Triassic.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Global calibration of a novel,branched GDGT-based soil pH proxy

Recently, 6-methyl branched glycerol dialkyl glycerol tetraethers (brGDGTs) were separated from 5-methyl brGDGTs, which are used in brGDGT-based proxies. Here we analyzed brGDGTs in 27 soil samples along the 400 mm isoline of mean annual precipitation in China by using tandem 2D liquid chromatography. The fractional abundance of 6-methyl brGDGTs showed a positive correlation with soil pH, while that of 5-methyl brGDGTs decreased with increasing soil pH. The abundance ratio of 6-/5-methyl brGDGTs, namely the isomerization of branched tetraethers (IBT), was calculated. The correlation of IBT with pH (pH = 6.33 − 1.28 × IBT; R² 0.89; root mean squared error, RMSE, 0.24) was much stronger than that of the traditionally used cyclization index of branched tetraethers (CBT) with pH (R² 0.52; RMSE 0.49) and comparable with that of CBT′ with pH (R² 0.88; RMSE 0.25). Compiling all available data from 319 soil samples resulted in a global calibration: pH = 6.53 − 1.55 × IBT (R² 0.72; RMSE 0.65), which has a better correlation than the CBT_5ME-pH proxy (R² 0.63; RMSE 0.78), but a weaker correlation than the CBT′-pH proxy (R² 0.85; RMSE 0.52). Our result suggests that the IBT is a promising indicator for soil pH, particularly in cases when some compounds in the CBT′ index cannot be determined.     

Weathering of ilmenite from Chavara deposit and its comparison with Manavalakurichi placer ilmenite,southwestern India

The magnetic fractions of ilmenite from the beach placer deposit of Chavara, southwest India have been studied for mineralogical and chemical composition to assess the range of their physical and chemical variations with weathering. Chavara deposit represents a highly weathered and relatively homogenous concentration. Significant variation in composition has been documented with alteration. The most magnetic of the fractions of ilmenite, separated at 0.15 Å, and with a susceptibility of 3.2 × 10^?6 m³ kg^?1, indicates the presence of haematite–ilmenite intergrowth. An iron-poor, titanium-rich component of the ilmenite ore has been identified from among the magnetic fractions of the Chavara ilmenite albeit with an undesirably high Nb₂O₅ (0.28%), Cr₂O₃ (0.23%) and Th (149 ppm) contents. The ilmenite from Chavara is compared with that from the nearby Manavalakurichi deposit of similar geological setting and provenance. The lower ferrous iron oxide (2.32–14.22%) and higher TiO₂ (56.31–66.45%) contents highlight the advanced state of alteration of Chavara. This is also evidenced by the relatively higher Fe³⁺/Fe²⁺ ratio compared to Manavalakurichi ilmenite. In fact, the ilmenite has significantly been converted to pseudorutile/leucoxene.     

Arsenic mobility in mildly alkaline drainage from an orogenic lode gold deposit,Bralorne mine,British Columbia

The historical (1932–1971) Bralorne mine produced over 87 million grams of Au from an archetypal orogenic lode gold deposit in southwest British Columbia. High concentrations of As in mine drainage, however, represent an on-going environmental concern prompting a detailed study of effluent chemistry. The discharge rate at the mine portal was monitored continuously over a fourteen-month period during which effluent samples were collected on a quasi-weekly basis. Water samples were also collected on synoptic surveys of the adit between the portal and the main source of flow in the flooded workings. Total concentrations of As in the mildly alkaline (pH = 8.7) portal drainage average 3034 μg/L whereas at the source they average 5898 μg/L. As emergent waters from the flooded workings flow toward the portal, their dissolved oxygen content and pH increase from 0 to 10 mg/L and from 7.7 to 9, respectively. Near the emergence point, dissolved Fe precipitates rapidly, sorbing both As(III) and As(V). With increasing distance from the emergence point, dissolved As(III) concentrations drop to detection limits through sorption on hydrous ferric oxide and through oxidation to As(V). Concentrations of dissolved As(V), on the other hand, increase and stabilize, reflecting lower sorption at higher pH and the lack of available sorbent. Nonetheless, based on synoptic surveys, approximately 35% of the source As load is sequestered in the adit resulting in As sediment concentrations averaging 8.5 wt%. The remaining average As load of 1.34 kg/d is discharged from the portal. Partitioning of As(V) between dissolved and particulate phases in portal effluent is characterized by a sorption density of 0.37 mol As (mol Fe)⁻¹ and by a distribution coefficient (K_d) of 130 L/g HFO. The relatively high sorption density may reflect co-precipitation of As with Fe oxyhydroxides rather than a purely adsorption-controlled process. Results of this study show that the As self-mitigating capacity of drainage from orogenic lode gold deposits may be poor in high-pH and Fe-limited settings.     

Spatial variability of initial 230Th/232Th in modern Porites from the inshore region of the Great Barrier Reef

The main limiting factor in obtaining precise and accurate uranium-series (U-series) ages of corals that lived during the last few hundred years is the ability to constrain and correct for initial thorium-230 (²³⁰Th₀), which is proportionally much higher in younger samples. This is becoming particularly important in palaeoecological research where accurate chronologies, based on the ²³⁰Th chronometer, are required to pinpoint changes in coral community structure and the timing of mortality events in recent time (e.g. since European settlement of northern Australia in the 1850s). In this study, thermal ionisation mass spectrometry (TIMS) U-series dating of 43 samples of known ages collected from living Porites spp. from the far northern, central and southern inshore regions of the Great Barrier Reef (GBR) was performed to spatially constrain initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀) variability. In these living Porites corals, the majority of ²³⁰Th/²³²Th₀ values fell within error of the conservative bulk Earth ²³⁰Th/²³²Th atomic value of 4.3 ± 4.3 × 10^?6 (2σ) generally assumed for ²³⁰Th₀ corrections where the primary source is terrestrially derived. However, the results of this study demonstrate that the accuracy of ²³⁰Th ages can be further improved by using locally determined ²³⁰Th/²³²Th₀ values for correction, supporting the conclusion made by Shen et al. (2008) for the Western Pacific. Despite samples being taken from regions adjacent to contrasting levels of land modification, no significant differences were found in ²³⁰Th/²³²Th₀ between regions exposed to varying levels of sediment during river runoff events. Overall, 39 of the total 43 ²³⁰Th/²³²Th₀ atomic values measured in samples from inshore reefs across the entire region show a normal distribution ranging from 3.5 ± 1.1 to 8.1 ± 1.1 × 10^?6, with a weighted mean of 5.76 ± 0.34 × 10^?6 (2σ, MSWD = 8.1). Considering the scatter of the data, the weighted mean value with a more conservative assigned error of 25% (i.e. 5.8 ± 1.4 × 10^?6) that encompasses the full variation of the 39 ²³⁰Th/²³²Th₀ measurements is recommended as a more appropriate value for initial ²³⁰Th corrections for U-series dating of most Porites samples from inshore regions of the GBR. This will result in significant improvement in both the precision and accuracy of the corrected ²³⁰Th ages related to those based on the assumed bulk Earth ²³⁰Th/²³²Th₀ value of 4.3 ± 4.3 × 10^?6. However, several anomalously high ²³⁰Th/²³²Th₀ values reaching up to 28.0 ± 1.6 × 10^?6 occasionally found in some coral annual bands coinciding with El Niño years imply high ²³⁰Th/²³²Th₀ sources and highlight the complexities of understanding ²³⁰Th/²³²Th₀ variability. For U-series dating of young coral samples from such sites where anomalous ²³⁰Th/²³²Th₀ values occur, we suggest replicate dating of multiple growth bands with known age difference to verify age accuracy.     

Emission of phosphine in intertidal marshes of the Yangtze Estuary

Emission of phosphine, a gaseous form of P, is presently considered a potential pathway of the P biogeochemical cycle in aquatic sediments. This study investigated the emission fluxes of phosphine and its potential production mechanisms in the intertidal marshes of the Yangtze Estuary. It is shown that the relatively high emission fluxes of phosphine were measured in warm seasons, with the values of 3.85–24.9 ng m^?2 h^?1 and 4.21–36.5 ng m^?2 h^?1 in August and September, respectively. In contrast, lower fluxes of phosphine appeared in May (1.23–6.32 ng m^?2 h^?1) and January (0.21–0.91 ng m^?2 h^?1). Also, the fluxes of phosphine were generally higher in the freshwater marsh, compared with the brackish marsh. The spatio-temporal pattern of phosphine emissions was observed to be mainly associated with sediment structure, temperature and salinity. Meanwhile, the significant correlations of phosphine emissions with sedimentary P and alkaline phosphatase activities reflect that phosphine probably derives from the microbial transformations of PO₄ and organic P. In addition, it is estimated that approximately 1.08 × 10⁶ g of phosphine is released annually from sediments into the pelagic water of the Yangtze Estuary. Therefore, it is concluded that phosphine emissions may be an important internal source of P, making a significant contribution to the occurrence of algal blooms especially during warm seasons.     

The Ranger uranium deposit,northern Australia: Timing constraints,regional and ore-related alteration,and genetic implications for unconformity-related mineralisation

The Ranger 1 unconformity-related uranium deposit in the Northern Territory of Australia is one of the world's largest uranium deposits and has ranked in the top two Australian producers of uranium in recent years. Mineralisation at the Ranger, Jabiluka and other major unconformity-related deposits in the Alligator Rivers Uranium Field (ARUF) occurs in Paleoproterozoic metamorphic basement rocks immediately beneath the unconformity with the Paleo- to Mesoproterozoic McArthur Basin.The sites of uranium mineralisation and associated alteration at the Ranger 1 deposit (Number 3 orebody) were fundamentally controlled by reactivated shear zones that were initiated during the regional Nimbuwah tectonothermal event. The timing of shearing at medium metamorphic grade was constrained by ion microprobe U–Pb dating of zircons in two pegmatites, one weakly foliated (1867.0 ± 3.5 Ma) and another that is unfoliated and cuts the shear fabric (1862.8 ± 3.4 Ma). The younger age of ~ 1863 Ma represents the minimum age of D1 shearing during the Nimbuwah event at the Ranger 1 deposit (Number 3 orebody). Titanite within veins of amphibole-plagioclase-apatite yielded an ion microprobe U–Pb age of 1845.4 ± 4.2 Ma, which represents a previously unrecognised hydrothermal event in the ARUF. Based on previous data, retrograde hydrothermal alteration during D2 reactivation of D1 shear zones is interpreted to have occurred at ~ 1800 Ma during the regional Shoobridge tectonothermal event.Detailed paragenetic observations supported by whole-rock geochemical data from the Ranger 1 deposit (Number 3 orebody) reveal a sequence of post-D2 hydrothermal events, as follows. (1) Intense magnesium-rich chlorite alteration and brecciation, focussed within schists of the Upper Mine Sequence in the Cahill Formation. (2) Silicification of Lower Mine Sequence carbonate rock units and overlying schist units, comprising quartz ± Mg-foitite (tourmaline) ± muscovite ± pyrite ± marcasite, and rare uraninite (early U1). (3) Formation of main stage uranium ore and heterolithic breccias including clasts of olivine–phyric dolerite, with breccia matrix composed of uraninite (U1), Mg-chlorite ± Mg-foitite and minor pyrite and chalcopyrite. (4) A second generation of uraninite (U2) veinlets with disordered graphitic carbon and quartz of hydrothermal origin. (5) Late-stage veinlets of massive uraninite (U3). As inferred in a previous study and confirmed herein, olivine–phyric dolerite dykes at Ranger are mineralised and chloritised, and are geochemically similar to the regional Oenpelli Dolerite. A maximum age for uranium mineralisation at the Ranger 1 deposit is therefore set by the age of the Oenpelli Dolerite (~ 1723 Ma).In-situ ion microprobe U–Pb analysis of texturally oldest U1 uraninite yielded a discordia array with a ²⁰⁶Pb/²³⁸U-²⁰⁷Pb/²³⁵U upper intercept age of 1688 ± 46 Ma. The oldest individual ion microprobe ²⁰⁷Pb–²⁰⁶Pb age is 1684 ± 7 Ma whereas the oldest age determined by in-situ electron microprobe chemical dating of U1 uraninite is ~ 1646 Ma. Another sample containing both U1 and U2 uraninite yielded discordant data with a ²⁰⁶Pb/²³⁸U–²⁰⁷Pb/²³⁵U upper intercept age of 1421 ± 68 Ma. When the ²⁰⁷Pb/²⁰⁶Pb ages are considered the data are suggestive of U2 uraninite formation and possible resetting of the U1 age between ~ 1420 Ma and ~ 1040 Ma. All ion microprobe analyses of U1 and U2 uraninite indicate variable and possibly repeated lead loss. In contrast ion microprobe U–Pb dating of the third generation of uraninite (U3) yielded several near-concordant analyses and a ²⁰⁶Pb/²³⁸U–²⁰⁷Pb/²³⁵U upper intercept age of 474 ± 6 Ma. This age is supported by electron microprobe chemical ages of U3 uraninite between 515 Ma and 385 Ma.The new results constrain the timing of initial uranium mineralisation at the Ranger 1 deposit (Number 3 orebody) to the period ~ 1720 Ma to ~ 1680 Ma, which just overlaps with a previous U–Pb age of 1737 ± 20 Ma for uraninite-rich whole-rock samples. Our results are consistent with individual laser-ICPMS ²⁰⁷Pb/²⁰⁶Pb and chemical ages of uraninite as old as 1690–1680 Ma reported from other deposits and prospects in the ARUF.Whole-rock geochemical data in this study of the Ranger 1 deposit (Number 3 orebody) and in other studies in the ARUF demonstrate that zones of intense chloritisation associated with uranium mineralisation experienced large metasomatic gains of Mg, U, Co, Ni, Cu and S and losses of Si, Na, Ca, Sr, Ba, K, Rb, Y and the light REE. More broadly in the ARUF, a regionally extensive illite–hematite ± kaolinite-bearing ‘paleoregolith’ zone in basement beneath the McArthur Basin exhibits depletion of about half of its uranium as well as major losses in Na, Sr, Pb, Ba and minor losses of Mg. These features together with new petrographic observations suggest this zone is a regional sub-McArthur Basin alteration zone produced by interaction with diagenetic or hydrothermal fluids of primary basinal origin, rather than representing a low-temperature paleo-weathering zone before the deposition of the McArthur Basin, as previously suggested.Based on these results and a synthesis of previous work, a new multi-stage model is proposed for the Ranger 1 ore-forming mineral system that may apply to other major unconformity-related uranium deposits in the ARUF and which may be used for targeting new deposits in the region. As in most recent models, oxidised diagenetic brines within the McArthur Basin are envisaged as crucial in mobilising uranium. However, a different architecture of fluid flow is proposed involving the sub-unconformity regional basement alteration zone as a preferential source of leached uranium. Possibly driven by convection during regional magmatism at ~ 1725–1705 Ma, oxidised basinal brines were drawn downwards and laterally through fault networks and fractures in the regional sub-unconformity alteration zone, leaching uranium from hematite-altered basement rocks. Simultaneously within deeper and lateral parts of the hydrothermal system, Mg-metasomatism produced chloritic alteration and brines with increased acidity and silica content (from the desilicification of the basement rock), analogous to processes described in sub-seafloor hydrothermal systems. Silicification occurred locally (e.g., Ranger deposit) within upflow zones of convective systems due to decreases in temperature and/or pressure of the brines and/or CO₂ generation during carbonate dissolution. Interruptions to convection during transient regional extensional or strike-slip tectonic events resulted in generalised lateral and downwards flow of fluids from the McArthur Basin through deepened zones of sub-unconformity alteration, transferring leached uranium into reactivated shear zones within the basement. The main stage of uraninite precipitation at the Ranger deposit and elsewhere in the ARUF is proposed to have occurred between ~ 1720 Ma and ~ 1680 Ma as a result of reduction of oxidised and evolved basin-derived ore fluids during reaction with pre-existing Fe^2 +-bearing minerals and/or mixing of the ore fluids with basement-reacted silica-rich brines.A second, volumetrically minor but locally high-grade, stage of uraninite mineralisation was associated with hydrothermal disordered carbon and quartz of presently unknown origin. Available data suggest formation between ~ 1420 Ma and ~ 1040 Ma. Almost a billion years later at ~ 475 Ma, fluids capable of mobilising uranium again resulted in uraninite (U3) deposition as sparse veinlets in the Ranger deposit, representing the first documentation of uranium mineralisation of this age in the region.     

Age and composition of Antarctic sub-glacial bedrock reflected by detrital zircons,erratics, and recycled microfossils in the Ellsworth Land–Antarctic Peninsula–Weddell Sea–Dronning Maud Land sector (240°E–0°–015°E)

The age and composition of the 14 × 10⁶ km² of Antarctica's surface obscured by ice is unknown except for some dated detrital minerals and erratics. In remedy, we present four new analyses (U–Pb age, T_DM^C, εHf, and rock type) of detrital zircons from Neogene turbidites as proxies of Antarctic bedrock, and review published proxies: detrital hornblendes analysed for Ar–Ar age and bulk Sm–Nd isotopes; Pb isotope compositions of detrital K-feldspars; erratics and dropstones that reflect age and composition; and recycled microfossils that reflect age and facies. This work deals with the 240°E–0°–015°E sector, and complements Veevers and Saeed's (2011) analysis of the 70°E–240°E sector. Each sample is located in its ice-drainage basin for backtracking to the potential provenance. Gaps in age between sample and upslope exposure are specifically attributable to the provenance. The major provenance of detritus west of the Antarctic Peninsula (AP) is West Antarctica, and of detritus east of the AP East Antarctica. We confirm that the Central Antarctic provenance about a core of the Gamburtsev Subglacial Mountains (GSM) and the Vostok Subglacial Highlands (VSH) contains a basement that includes igneous (mafic granitoids) and metamorphic rocks with peak U–Pb ages of 0.65–0.50, 1.20–0.9, 2.1–1.9, 2.8–2.6, and 3.35–3.30 Ga, T_DM^C of 3.6–1.3 Ga, and mainly negative εHf. The potential provenance of zircons of 650–500 Ma age with T_DM^C ages of 1.55 Ga, and of zircons of 1200–900 Ma age with positive εHf lies beneath the ice in East Antarctica south and southeast of Dronning Maud Land within the Antarctic part of the East African–Antarctic Orogen. Zircons with the additional ages of 1.7–1.4 Ga, 2.1–1.9 Ga, and 3.35–3.00 Ga have a potential provenance in the GSM.     

Metallogenesis at the Carris W–Mo–Sn deposit (Gerês,Portugal): Constraints from fluid inclusions,mineral geochemistry,Re–Os and He–Ar isotopes

The Carris orebody consists of two partially exploited W–Mo–Sn quartz veins formed during successive shear stages and multipulse fluid fillings. They cut the Variscan post-D3 Gerês I-type granite. The most important ore minerals are wolframite, scheelite, molybdenite and cassiterite. There are two generations of wolframite. The earlier generation of wolframite is rare and has the highest WO₄Mn content (91 mol%) and the most common wolframite contains 26–57 mol% WO₄Mn. Re–Os dating of molybdenite from the ore quartz veins and surrounding granite yields ages of 279 ± 1.2 Ma and 280.3 ± 1.2 Ma, respectively which are in very good agreement with the previous ID-TIMS U–Pb zircon age for the Carris granite (280 ± 5 Ma).³He/⁴He ratio of pyrite ranging between 0.73 and 2.71 Ra (1 Ra = 1.39 × 10^− 6) and high ³He/³⁶Ar (0.8–5 × 10^− 3) indicate a mixture of a crustal radiogenic helium fluid with a mantle derived-fluid.The fluid inclusion studies on quartz intergrown with wolframite and scheelite, beryl and fluorite reveal that two distinct fluid types were involved in the genesis of this deposit. The first was a low to medium salinity aqueous carbonic fluid (CO₂ between 4 and 14 mol%) with less than 1.95 mol% N₂, which was only found in quartz associated with wolframite. The other was a low salinity aqueous fluid found in all the four minerals. The homogenization temperatures indicate minimum entrapment temperatures of 226–310 °C (average 280 °C) for the H₂O–CO₂–N₂–NaCl fluid and average temperatures of 266 °C for scheelite and 242 °C, 190 °C and 160 °C for the last generations of beryl, fluorite and quartz, respectively. It was estimated that wolframite was deposited ~ 7 km depth, assuming a lithostatic pressure, probably due to strong pressure fluctuation caused by seismic events triggered by brittle tectonics during the exhumation event. Precipitation of scheelite and sulphides took place later, at the same depth, but under a hydrostatic or suprahydrostatic pressure regime, and probably caused by mixing between the magmatic–hydrothermal fluid and meteoric waters that deeply penetrated the basement during post-Variscan decompression.     

Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO₂ concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO₂ varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO₃ and Fe(CO₃)₃³⁻, with formation constants log^*β°_1,1,1 = 10.76 ± 0.38 and log β°_1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO₂ and at T = (25 ± 1) °C, as log^*K_s,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO₂-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers.     

Metallogenic age and hydrothermal evolution of the Jidetun Mo deposit in central Jilin Province,northeast China: Evidence from fluid inclusions,isotope systematics,and geochronology

The Jidetun deposit is a large porphyry Mo deposit that is located in central Jilin Province, northeast China. The Mo mineralization occurs mainly at the edge of porphyritic granodiorite, as well as the adjacent monzogranite. Field investigations, cross-cutting relationships, and mineral paragenetic associations indicate four stages of hydrothermal activity. To determine the relationships between mineralization and associated magmatism, and better understand the metallogenic processes in ore district, we have undertaken a series of studies incluiding molybdenite Re–Os and zircon U–Pb geochronology, fluid inclusions microthermometry, and C–H–O–S–Pb isotope compositions. The molybdenite Re–Os dating yielded a well-defined isochron age of 168.9 ± 1.9 Ma (MSWD = 0.34) that is similar to the weighted mean ²⁰⁶Pb/²³⁸U age of 173.5 ± 1.5 Ma (MSWD = 1.8) obtained from zircons from the porphyritic granodiorite. The results lead to the conclusion that Mo mineralization, occurred in the Middle Jurassic (168.9 ± 1.9 Ma), was spatially, temporally, and genetically related to the porphyritic granodiorite (173.5 ± 1.5 Ma) rather than the older monzogranite (180.1 ± 0.6 Ma). Fluid inclusion and stable (C–H–O) isotope data indicate that the initial H₂O–NaCl fluids of mineralization stage I were of high-temperature and high-salinity affinity and exsolved from the granodiorite magma as a result of cooling and fractional crystallization. The fluids then evolved during mineralization stage II into immiscible H₂O–CO₂–NaCl fluids that facilitated the transport of metals (Mo, Cu, and Fe) and their separation from the ore-bearing magmas due to the influx of abundant external CO₂ and heated meteoric water. Subsequently, during mineralization stage III and IV, increase of pH in residual ore-forming fluids on account of CO₂ escape, and continuous decrease of ore-forming temperatures caused by the large accession of the meteoric water into the fluid system, reduced solubility and stability of metal clathrates, thus facilitating the deposition of polymetallic sulfides.